# Patent

## Title
Metallocene and half sandwich dual catalyst systems for producing broad molecular weight distribution polymers

## Abstract

Disclosed herein are polymerization processes for the production of olefin polymers. These polymerization processes can use a dual catalyst system containing a zirconium or hafnium based metallocene compound and a titanium based half-metallocene compound containing an indenyl group.

## Background
BACKGROUND OF THE INVENTION
Polyolefins such as high density polyethylene (HDPE) homopolymer and linear low density polyethylene (LLDPE) copolymer can be produced using various combinations of catalyst systems and polymerization processes. A chromium based catalyst system can, for example, produce polymers having broad molecular weight distributions.
It would be beneficial to produce such broad molecular weight distribution polymers using non-chromium based catalyst systems. Accordingly, it is to this end that the present invention is directed.
SUMMARY OF THE INVENTION
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter.
The present invention generally relates to new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, aspects of the present invention are directed to catalyst compositions employing two catalyst components. The first catalyst component can comprise a zirconium or hafnium based metallocene compound, while the second catalyst component can comprise a titanium based half-metallocene compound containing an indenyl group. Such catalyst compositions can be used to produce, for example, ethylene-based homopolymers and copolymers having broad molecular weight distributions.
In one aspect, a catalyst composition is disclosed which can comprise catalyst component I comprising a zirconium or hafnium based metallocene compound, catalyst component II comprising a titanium based half-metallocene compound containing an indenyl group, and an activator. Optionally, this catalyst composition can further comprise a co-catalyst.
The present invention also contemplates and encompasses olefin polymerization processes. Such processes can comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer. Generally, the catalyst composition employed can comprise any of the catalyst component I metallocene compounds, any of the catalyst component II half-metallocene compounds, and any of the activators and optional co-catalysts disclosed herein. For example, organoaluminum compounds can be utilized in the catalyst compositions and/or polymerization processes.
Polymers produced from the polymerization of olefins, resulting in homopolymers, copolymers, terpolymers, etc., can be used to produce various articles of manufacture.
Both the foregoing summary and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. Further, features or variations may be provided in addition to those set forth herein. For example, certain aspects and embodiments may be directed to various feature combinations and sub-combinations described in the detailed description.



BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 presents a plot of the molecular weight distributions of the polymers of Examples 1-4.
FIG. 2 presents a plot of the molecular weight distribution of the polymer of Example 5.
FIG. 3 presents a plot of dynamic melt viscosity versus frequency at 190° C. for the polymer of Example 1.
FIG. 4 presents a plot of the molecular weight distributions of the polymers of Example 6 (using MET-B), Example 7 (using MET-B and CpTiCl3 at a 2:1 weight ratio), and Example 8 (using MET-B and CpTiCl3 at a 1:1 weight ratio).



DEFINITIONS
To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein, or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.
Regarding claim transitional terms or phrases, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is open-ended and does not exclude additional, unrecited elements or method steps. The transitional phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. The transitional phrase “consisting essentially of” limits the scope of a claim to the specified components or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention. A “consisting essentially of” claim occupies a middle ground between closed claims that are written in a “consisting of” format and fully open claims that are drafted in a “comprising” format. For example, a feedstock consisting essentially of component A can include impurities typically present in a commercially produced or commercially available sample of component A. When a claim includes different features and/or feature classes (for example, a method step, feedstock features, and/or product features, among other possibilities), the transitional terms comprising, consisting essentially of, and consisting of, apply only to the feature class to which it is utilized and it is possible to have different transitional terms or phrases utilized with different features within a claim. For example, a method can consist of certain steps, but utilize a catalyst system comprising recited components and other non-recited components. While compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components or steps, unless stated otherwise. For example, a catalyst composition consistent with aspects of the present invention can comprise; alternatively, can consist essentially of; or alternatively, can consist of (i) catalyst component I, (ii) catalyst component II, (iii) an activator, and (iv) optionally, a co-catalyst.
The terms “a,” “an,” “the,” etc., are intended to include plural alternatives, e.g., at least one, unless otherwise specified. For instance, the disclosure of “an activator-support” or “a metallocene compound” is meant to encompass one, or mixtures or combinations of more than one, activator-support or metallocene compound, respectively, unless otherwise specified.
Groups of elements are indicated using the numbering scheme indicated in the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985. In some instances, a group of elements can be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.
For any particular compound disclosed herein, the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that can arise from a particular set of substituents, unless indicated otherwise. Thus, a general reference to a compound includes all structural isomers unless explicitly indicated otherwise; e.g., a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group. Additionally, the reference to a general structure or name encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context permits or requires. For any particular formula or name that is presented, any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that can arise from a particular set of substituents.
A chemical “group” is described according to how that group is formally derived from a reference or “parent” compound, for example, by the number of hydrogen atoms formally removed from the parent compound to generate the group, even if that group is not literally synthesized in this manner. These groups can be utilized as substituents or coordinated or bonded to metal atoms. By way of example, an “alkyl group” formally can be derived by removing one hydrogen atom from an alkane, while an “alkylene group” formally can be derived by removing two hydrogen atoms from an alkane. Moreover, a more general term can be used to encompass a variety of groups that formally are derived by removing any number (“one or more”) of hydrogen atoms from a parent compound, which in this example can be described as an “alkane group,” and which encompasses an “alkyl group,” an “alkylene group,” and materials have three or more hydrogen atoms, as necessary for the situation, removed from the alkane. The disclosure that a substituent, ligand, or other chemical moiety can constitute a particular “group” implies that the well-known rules of chemical structure and bonding are followed when that group is employed as described. When describing a group as being “derived by,” “derived from,” “formed by,” or “formed from,” such terms are used in a formal sense and are not intended to reflect any specific synthetic method or procedure, unless specified otherwise or the context requires otherwise.
The term “substituted” when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting. A group or groups can also be referred to herein as “unsubstituted” or by equivalent terms such as “non-substituted,” which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen within that group. Unless otherwise specified, “substituted” is intended to be non-limiting and include inorganic substituents or organic substituents as understood by one of ordinary skill in the art.
The term “hydrocarbon” whenever used in this specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers can be utilized to indicate the presence of particular groups in the hydrocarbon (e.g., halogenated hydrocarbon indicates that the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon (that is, a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl, and the like. Similarly, a “hydrocarbylene group” refers to a group formed by removing two hydrogen atoms from a hydrocarbon, either two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms. Therefore, in accordance with the terminology used herein, a “hydrocarbon group” refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a hydrocarbon. A “hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” can be aliphatic or aromatic, acyclic or cyclic, and/or linear or branched. A “hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” can include rings, ring systems, aromatic rings, and aromatic ring systems, which contain only carbon and hydrogen. “Hydrocarbyl groups,” “hydrocarbylene groups,” and “hydrocarbon groups” include, by way of example, aryl, arylene, arene groups, alkyl, alkylene, alkane group, cycloalkyl, cycloalkylene, cycloalkane groups, aralkyl, aralkylene, and aralkane groups, respectively, among other groups as members.
An aliphatic compound is a class of acyclic or cyclic, saturated or unsaturated, carbon compounds, excluding aromatic compounds, e.g., an aliphatic compound is a non-aromatic organic compound. An “aliphatic group” is a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a carbon atom of an aliphatic compound. Aliphatic compounds and therefore aliphatic groups can contain organic functional group(s) and/or atom(s) other than carbon and hydrogen.
The term “alkane” whenever used in this specification and claims refers to a saturated hydrocarbon compound. Other identifiers can be utilized to indicate the presence of particular groups in the alkane (e.g., halogenated alkane indicates that the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the alkane). The term “alkyl group” is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from an alkane. Similarly, an “alkylene group” refers to a group formed by removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms). An “alkane group” is a general term that refers to a group formed by removing one or more hydrogen atoms (as necessary for the particular group) from an alkane. An “alkyl group,” “alkylene group,” and “alkane group” can be acyclic or cyclic and/or linear or branched unless otherwise specified. Primary, secondary, and tertiary alkyl groups are derived by removal of a hydrogen atom from a primary, secondary, and tertiary carbon atom, respectively, of an alkane. The n-alkyl group can be derived by removal of a hydrogen atom from a terminal carbon atom of a linear alkane. The groups RCH2 (R≠H), R2CH(R≠H), and R3C(R≠H) are primary, secondary, and tertiary alkyl groups, respectively.
A cycloalkane is a saturated cyclic hydrocarbon, with or without side chains, for example, cyclobutane. Other identifiers can be utilized to indicate the presence of particular groups in the cycloalkane (e.g., halogenated cycloalkane indicates that the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the cycloalkane). Unsaturated cyclic hydrocarbons having one endocyclic double or one triple bond are called cycloalkenes and cycloalkynes, respectively. Those having more than one such multiple bond are cycloalkadienes, cycloalkatrienes, and so forth. Other identifiers can be utilized to indicate the presence of particular groups in the cycloalkenes, cycloalkadienes, cycloalkatrienes, and so forth.
A “cycloalkyl group” is a univalent group derived by removing a hydrogen atom from a ring carbon atom of a cycloalkane. For example, a 1-methylcyclopropyl group and a 2-methylcyclopropyl group are illustrated as follows.




Similarly, a “cycloalkylene group” refers to a group derived by removing two hydrogen atoms from a cycloalkane, at least one of which is a ring carbon. Thus, a “cycloalkylene group” includes a group derived from a cycloalkane in which two hydrogen atoms are formally removed from the same ring carbon, a group derived from a cycloalkane in which two hydrogen atoms are formally removed from two different ring carbons, and a group derived from a cycloalkane in which a first hydrogen atom is formally removed from a ring carbon and a second hydrogen atom is formally removed from a carbon atom that is not a ring carbon. A “cycloalkane group” refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group and at least one of which is a ring carbon) from a cycloalkane.

The term “alkene” whenever used in this specification and claims refers a linear or branched hydrocarbon olefin that has one carbon-carbon double bond and the general formula CnH2n. Alkadienes refer to a linear or branched hydrocarbon olefin having two carbon-carbon double bonds and the general formula CnH2n−2, and alkatrienes refer to linear or branched hydrocarbon olefins having three carbon-carbon and the general formula CnH2n−4. Alkenes, alkadienes, and alkatrienes can be further identified by the position of the carbon-carbon double bond(s). Other identifiers can be utilized to indicate the presence or absence of particular groups within an alkene, alkadiene, or alkatriene. For example, a haloalkene refers to an alkene having one or more hydrogen atoms replace with a halogen atom.
An “alkenyl group” is a univalent group derived from an alkene by removal of a hydrogen atom from any carbon atom of the alkene. Thus, “alkenyl group” includes groups in which the hydrogen atom is formally removed from an sp2 hybridized (olefinic) carbon atom and groups in which the hydrogen atom is formally removed from any other carbon atom. For example and unless otherwise specified, 1-propenyl (—CH═CHCH3), 2-propenyl [(CH3)C═CH2], and 3-propenyl (—CH2CH═CH2) groups are encompassed with the term “alkenyl group.” Similarly, an “alkenylene group” refers to a group formed by formally removing two hydrogen atoms from an alkene, either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms. An “alkene group” refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from an alkene. When the hydrogen atom is removed from a carbon atom participating in a carbon-carbon double bond, the regiochemistry of the carbon from which the hydrogen atom is removed, and regiochemistry of the carbon-carbon double bond can both be specified. Other identifiers can be utilized to indicate the presence or absence of particular groups within an alkene group. Alkene groups can also be further identified by the position of the carbon-carbon double bond.
An arene is an aromatic hydrocarbon, with or without side chains (e.g., benzene, toluene, or xylene, among others). An “aryl group” is a group derived from the formal removal of a hydrogen atom from an aromatic ring carbon of an arene. It should be noted that the arene can contain a single aromatic hydrocarbon ring (e.g., benzene or toluene), contain fused aromatic rings (e.g., naphthalene or anthracene), and contain one or more isolated aromatic rings covalently linked via a bond (e.g., biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane). One example of an “aryl group” is ortho-tolyl (o-tolyl), the structure of which is shown here.




An “aralkyl group” is an aryl-substituted alkyl group having a free valance at a non-aromatic carbon atom, for example, a benzyl group, or a 2-phenyleth-1yl group, among others.
A “halide” has its usual meaning. Examples of halides include fluoride, chloride, bromide, and iodide.
The term “polymer” is used herein generically to include olefin homopolymers, copolymers, terpolymers, and so forth. A copolymer is derived from an olefin monomer and one olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Accordingly, “polymer” encompasses 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 were ethylene and 1-hexene, respectively, the resulting polymer could be categorized an as ethylene/1-hexene copolymer.
In like manner, the scope of the term “polymerization” includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process could involve contacting one olefin monomer (e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce a copolymer.
The term “co-catalyst” is used generally herein to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, that can constitute one component of a catalyst composition, when used, for example, in addition to an activator-support. The term “co-catalyst” is used regardless of the actual function of the compound or any chemical mechanism by which the compound may operate.
The terms “chemically-treated solid oxide,” “treated solid oxide compound,” and the like, are used herein to indicate a solid, inorganic oxide of relatively high porosity, which can exhibit Lewis acidic or Brønsted acidic behavior, and which has been treated with an electron-withdrawing component, typically an anion, and which is calcined. The electron-withdrawing component is typically an electron-withdrawing anion source compound. Thus, the chemically-treated solid oxide can comprise a calcined contact product of at least one solid oxide with at least one electron-withdrawing anion source compound. Typically, the chemically-treated solid oxide comprises at least one acidic solid oxide compound. The “activator-support” of the present invention can be a chemically-treated solid oxide. The terms “support” and “activator-support” are not used to imply these components are inert, and such components should not be construed as an inert component of the catalyst composition. The term “activator,” as used herein, refers generally to a substance that is capable of converting a metallocene component into a catalyst that can polymerize olefins, or converting a contact product of a metallocene component and a component that provides an activatable ligand (e.g., an alkyl, a hydride) to the metallocene, when the metallocene compound does not already comprise such a ligand, into a catalyst that can polymerize olefins. This term is used regardless of the actual activating mechanism. Illustrative activators include activator-supports, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and the like. Aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds generally are referred to as activators if used in a catalyst composition in which an activator-support is not present. If the catalyst composition contains an activator-support, then the aluminoxane, organoboron or organoborate, and ionizing ionic materials are typically referred to as co-catalysts.
The term “fluoroorgano boron compound” is used herein with its ordinary meaning to refer to neutral compounds of the form BY3. The term “fluoroorgano borate compound” also has its usual meaning to refer to the monoanionic salts of a fluoroorgano boron compound of the form [cation]+[BY4]−, where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as “organoboron or organoborate compounds.”
The terms “metallocene,” “half-metallocene,” and “hybrid metallocene,” as used herein, describe compounds comprising at least one η3 to η5-cycloalkadienyl-type moiety, wherein η3 to η5-cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of these. Possible substituents on these ligands may include H, therefore this invention comprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, the metallocene is referred to simply as the “catalyst,” in much the same way the term “co-catalyst” is used herein to refer to, for example, an organoaluminum compound.
The terms “catalyst composition,” “catalyst mixture,” “catalyst system,” and the like, do not depend upon the actual product or composition resulting from the contact or reaction of the initial components of the claimed catalyst composition/mixture/system, the nature of the active catalytic site, or the fate of the co-catalyst, the metallocene compound(s), any olefin monomer used to prepare a precontacted mixture, or the activator (e.g., activator-support), after combining these components. Therefore, the terms “catalyst composition,” “catalyst mixture,” “catalyst system,” and the like, encompass the initial starting components of the composition, as well as whatever products) may result from contacting these initial starting components, and this is inclusive of both heterogeneous and homogenous catalyst systems or compositions. The terms “catalyst composition,” “catalyst mixture,” “catalyst system,” and the like, are used interchangeably throughout this disclosure.
The term “contact product” is used herein to describe compositions wherein the components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. Further, contacting of any component can occur in the presence or absence of any other component of the compositions described herein. Combining additional materials or components can be done by any suitable method. Further, the term “contact product” includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Although “contact product” can include reaction products, it is not required for the respective components to react with one another. Similarly, the term “contacting” is used herein to refer to materials which can be blended, mixed, slurried, dissolved, reacted, treated, or otherwise contacted in some other manner.
The term “precontacted” mixture is used herein to describe a first mixture of catalyst components that are contacted for a first period of time prior to the first mixture being used to form a “postcontacted” or second mixture of catalyst components that are contacted for a second period of time. Typically, the precontacted mixture can describe a mixture of a metallocene-type compound (one or more than one), olefin monomer (or monomers), and organoaluminum compound (or compounds), before this mixture is contacted with an activator-support(s) and optional additional organoaluminum compound. Thus, precontacted describes components that are used to contact each other, but prior to contacting the components in the second, postcontacted mixture. Accordingly, this invention can occasionally distinguish between a component used to prepare the precontacted mixture and that component after the mixture has been prepared. For example, according to this description, it is possible for the precontacted organoaluminum compound, once it is contacted with the metallocene-type compound and the olefin monomer, to have reacted to form at least one chemical compound, formulation, or structure different from the distinct organoaluminum compound used to prepare the precontacted mixture. In this case, the precontacted organoaluminum compound or component is described as comprising an organoaluminum compound that was used to prepare the precontacted mixture.
Additionally, the precontacted mixture can describe a mixture of metallocene-type compound(s) and organoaluminum compound(s), prior to contacting this mixture with an activator-support(s). This precontacted mixture also can describe a mixture of metallocene compound(s), olefin monomer(s), and activator-support(s), before this mixture is contacted with an organoaluminum co-catalyst compound or compounds.
Similarly, the term “postcontacted” mixture is used herein to describe a second mixture of catalyst components that are contacted for a second period of time, and one constituent of which is the “precontacted” or first mixture of catalyst components that were contacted for a first period of time. Typically, the term “postcontacted” mixture is used herein to describe the mixture of metallocene-type compound(s), olefin monomer(s), organoaluminum compound(s), and activator-support(s) formed from contacting the precontacted mixture of a portion of these components with any additional components added to make up the postcontacted mixture. Often, the activator-support can comprise a chemically-treated solid oxide. For instance, the additional component added to make up the postcontacted mixture can be a chemically-treated solid oxide (one or more than one), and optionally, can include an organoaluminum compound which is the same as or different from the organoaluminum compound used to prepare the precontacted mixture, as described herein. Accordingly, this invention can also occasionally distinguish between a component used to prepare the postcontacted mixture and that component after the mixture has been prepared.
Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, the typical methods, devices and materials are herein described.
All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. The publications discussed throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.
Applicants disclose several types of ranges in the present invention. When Applicants disclose or claim a range of any type, Applicants' intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein. For example, when the Applicants disclose or claim a chemical moiety having a certain number of carbon atoms, Applicants' intent is to disclose or claim individually every possible number that such a range could encompass, consistent with the disclosure herein. For example, the disclosure that a moiety is a C1 to C18 hydrocarbyl group, or in alternative language, a hydrocarbyl group having from 1 to 18 carbon atoms, as used herein, refers to a moiety that can be selected independently from a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range between these two numbers (for example, a C1 to C8 hydrocarbyl group), and also including any combination of ranges between these two numbers (for example, a C2 to C4 and a C12 to C16 hydrocarbyl group).
Similarly, another representative example follows for the number-average molecular weight (Mn) of an olefin polymer produced in an aspect of this invention. By a disclosure that the Mn can be in a range from about 8,000 to about 25,000 g/mol, Applicants intend to recite that the Mn can be equal to about 8,000, about 9,000, about 10,000, about 11,000, about 12,000, about 13,000, about 14,000, about 15,000, about 16,000, about 17,000, about 18,000, about 19,000, about 20,000, about 21,000, about 22,000, about 23,000, about 24,000, or about 25,000 g/mol. Additionally, the Mn can be within any range from about 8,000 to about 25,000 (for example, from about 10,000 to about 22,000), and this also includes any combination of ranges between about 8,000 and about 25,000 (for example, the Mn can be in a range from about 8,000 to about 10,000, or from about 15,000 to about 25,000). Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these two examples.
Applicants reserve the right to proviso out or exclude any individual members of any such group, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application. Further, Applicants reserve the right to proviso out or exclude any individual substituents, analogs, compounds, ligands, structures, or groups thereof, or any members of a claimed group, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed generally to new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, the present invention relates to dual component catalyst compositions and polymerization processes utilizing such catalyst compositions.
Catalyst Component I
Catalyst component I can comprise a metallocene compound and, more particularly, a zirconium or hafnium based metallocene compound. In one aspect, for instance, catalyst component I can comprise an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group. In another aspect, catalyst component I can comprise an unbridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group. In yet another aspect of this invention, catalyst component I can comprise an unbridged metallocene compound having formula (IA):




Within formula (IA), M, CpA, CpB, X4, and X5 are independent elements of the unbridged metallocene compound. Accordingly, the unbridged metallocene compound having formula (IA) can be described using any combination of M, CpA, CpB, X4, and X5 disclosed herein.
Unless otherwise specified, formula (IA) above, any other structural formulas disclosed herein, and any metallocene complex, compound, or species disclosed herein are not designed to show stereochemistry or isomeric positioning of the different moieties (e.g., these formulas are not intended to display cis or trans isomers, or R or S diastereoisomers), although such compounds are contemplated and encompassed by these formulas and/or structures.
In accordance with aspects of this invention, the metal in formula (IA), M, can be Zr or Hf. In one aspect, for instance, M can be Zr, while in another aspect, M can be Hf.
X4 and X5 in formula (IA) independently can be a monoanionic ligand. In some aspects, suitable monoanionic ligands can include, but are not limited to, H (hydride), BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, —OBR12, or —OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group. It is contemplated that X4 and X5 can be either the same or a different monoanionic ligand.
In one aspect, X4 and X5 independently can be H, BH4, a halide (e.g., F, Cl, Br, etc.), a C1 to C18 hydrocarbyl group, a C1 to C18 hydrocarboxy group, a C1 to C18 hydrocarbylaminyl group, a C1 to C18 hydrocarbylsilyl group, or a C1 to C18 hydrocarbylaminylsilyl group. Alternatively, X4 and X5 independently can be H, BH4, a halide, OBR12, or OSO2R1, wherein R1 is a C1 to C18 hydrocarbyl group. In another aspect, X4 and X5 independently can be H, BH4, a halide, a C1 to C12 hydrocarbyl group, a C1 to C12 hydrocarboxy group, a C1 to C12 hydrocarbylaminyl group, a C1 to C12 hydrocarbylsilyl group, a C1 to C12 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C12 hydrocarbyl group. In another aspect, X4 and X5 independently can be H, BH4, a halide, a C1 to C10 hydrocarbyl group, a C1 to C10 hydrocarboxy group, a C1 to C10 hydrocarbylaminyl group, a C1 to C10 hydrocarbylsilyl group, a C1 to C10 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C10 hydrocarbyl group. In yet another aspect, X4 and X5 independently can be H, BH4, a halide, a C1 to C8 hydrocarbyl group, a C1 to C8 hydrocarboxy group, a C1 to C8 hydrocarbylaminyl group, a C1 to C8 hydrocarbylsilyl group, a C1 to C8 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C8 hydrocarbyl group. In still another aspect, X4 and X5 independently can be a halide or a C1 to C18 hydrocarbyl group. For example, X4 and X5 can be Cl.
The hydrocarbyl group which can be X4 and/or X5 in formula (IA) can be a C1 to C36 hydrocarbyl group, including, but not limited to, a C1 to C36 alkyl group, a C2 to C36 alkenyl group, a C4 to C36 cycloalkyl group, a C6 to C36 aryl group, or a C7 to C36 aralkyl group. For instance, X4 and X5 independently can be a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C4 to C18 cycloalkyl group, a C6 to C18 aryl group, or a C7 to C18 aralkyl group; alternatively, X4 and X5 independently can be a C1 to C12 alkyl group, a C2 to C12 alkenyl group, a C4 to C12 cycloalkyl group, a C6 to C12 aryl group, or a C7 to C12 aralkyl group; alternatively, X4 and X5 independently can be a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C4 to C10 cycloalkyl group, a C6 to C10 aryl group, or a C7 to C10 aralkyl group; or alternatively, X4 and X5 independently can be a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5 to C8 cycloalkyl group, a C6 to C8 aryl group, or a C7 to C8 aralkyl group.
Accordingly, in some aspects, the alkyl group which can be X4 and/or X5 in formula (IA) can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, or an octadecyl group; or alternatively, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group. In some aspects, the alkyl group which can be X4 and/or X5 in formula (IA) can be a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an iso-pentyl group, a sec-pentyl group, or a neopentyl group; alternatively, a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, a n-propyl group; alternatively, an iso-propyl group; alternatively, a tert-butyl group; or alternatively, a neopentyl group.
Suitable alkenyl groups which can be X4 and/or X5 in formula (IA) can include, but are not limited to, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, or an octadecenyl group. Such alkenyl groups can be linear or branched, and the double bond can be located anywhere in the chain. In one aspect, X4 and/or X5 in formula (IA) can be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, or a decenyl group, while in another aspect, X4 and/or X5 in formula (IA) can be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, or a hexenyl group. For example, X4 and/or X5 can be an ethenyl group; alternatively, a propenyl group; alternatively, a butenyl group; alternatively, a pentenyl group; or alternatively, a hexenyl group. In yet another aspect, X4 and/or X5 can be a terminal alkenyl group, such as a C3 to C18 terminal alkenyl group, a C3 to C12 terminal alkenyl group, or a C3 to C8 terminal alkenyl group. Illustrative terminal alkenyl groups can include, but are not limited to, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-yl group, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-yl group, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.
X4 and/or X5 in formula (IA) can be a cycloalkyl group, including, but not limited to, a cyclobutyl group, a substituted cyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, a substituted cycloheptyl group, a cyclooctyl group, or a substituted cyclooctyl group. For example, X4 and/or X5 in formula (IA) can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group. Moreover, X4 and/or X5 in formula (IA) can be a cyclobutyl group or a substituted cyclobutyl group; alternatively, a cyclopentyl group or a substituted cyclopentyl group; alternatively, a cyclohexyl group or a substituted cyclohexyl group; alternatively, a cycloheptyl group or a substituted cycloheptyl group; alternatively, a cyclooctyl group or a substituted cyclooctyl group; alternatively, a cyclopentyl group; alternatively, a substituted cyclopentyl group; alternatively, a cyclohexyl group; or alternatively, a substituted cyclohexyl group. Substituents which can be utilized for the substituted cycloalkyl group are independently disclosed herein and can be utilized without limitation to further describe the substituted cycloalkyl group which can be X4 and/or X5 in formula (IA).
In some aspects, the aryl group which can be X4 and/or X5 in formula (IA) can be a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. In an aspect, the aryl group can be a phenyl group or a substituted phenyl group; alternatively, a naphthyl group or a substituted naphthyl group; alternatively, a phenyl group or a naphthyl group; alternatively, a substituted phenyl group or a substituted naphthyl group; alternatively, a phenyl group; or alternatively, a naphthyl group. Substituents which can be utilized for the substituted phenyl groups or substituted naphthyl groups are independently disclosed herein and can be utilized without limitation to further describe the substituted phenyl groups or substituted naphthyl groups which can be X4 and/or X5 in formula (IA).
In an aspect, the substituted phenyl group which can be X4 and/or X5 in formula (IA) can be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group. In other aspects, the substituted phenyl group can be a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group; alternatively, a 3-substituted phenyl group or a 3,5-disubstituted phenyl group; alternatively, a 2-substituted phenyl group or a 4-substituted phenyl group; alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group; alternatively, a 2-substituted phenyl group; alternatively, a 3-substituted phenyl group; alternatively, a 4-substituted phenyl group; alternatively, a 2,4-disubstituted phenyl group; alternatively, a 2,6-disubstituted phenyl group; alternatively, a 3,5-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Substituents which can be utilized for these specific substituted phenyl groups are independently disclosed herein and can be utilized without limitation to further describe these substituted phenyl groups which can be the X4 and/or X5 group(s) in formula (IA).
In some aspects, the aralkyl group which can be X4 and/or X5 group in formula (IA) can be a benzyl group or a substituted benzyl group. In an aspect, the aralkyl group can be a benzyl group or, alternatively, a substituted benzyl group. Substituents which can be utilized for the substituted aralkyl group are independently disclosed herein and can be utilized without limitation to further describe the substituted aralkyl group which can be the X4 and/or X5 group(s) in formula (IA).
In an aspect, each non-hydrogen substituent(s) for the substituted cycloalkyl group, substituted aryl group, or substituted aralkyl group which can be X4 and/or X5 in formula (IA) independently can be a C1 to C18 hydrocarbyl group; alternatively, a C1 to C8 hydrocarbyl group; or alternatively, a C1 to C5 hydrocarbyl group. Specific hydrocarbyl groups are independently disclosed herein and can be utilized without limitation to further describe the substituents of the substituted cycloalkyl groups, substituted aryl groups, or substituted aralkyl groups which can be X4 and/or X5 in formula (IA). For instance, the hydrocarbyl substituent can be an alkyl group, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group, and the like. Furthermore, the hydrocarbyl substituent can be a benzyl group, a phenyl group, a tolyl group, or a xylyl group, and the like.
A hydrocarboxy group is used generically herein to include, for instance, alkoxy, aryloxy, aralkoxy, and -(alkyl, aryl, or aralkyl)-O-(alkyl, aryl, or aralkyl) groups, and these groups can comprise up to about 36 carbon atoms (e.g., C1 to C36, C1 to C18, C1 to C10, or C1 to C8 hydrocarboxy groups). Illustrative and non-limiting examples of hydrocarboxy groups which can be X4 and/or X5 in formula (IA) can include, but are not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group, a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, a benzoxy group, an acetylacetonate group (acac), and the like. In an aspect, the hydrocarboxy group which can be X4 and/or X5 in formula (IA) can be a methoxy group; alternatively, an ethoxy group; alternatively, an n-propoxy group; alternatively, an isopropoxy group; alternatively, an n-butoxy group; alternatively, a sec-butoxy group; alternatively, an isobutoxy group; alternatively, a tert-butoxy group; alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group; alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxy group; alternatively, a tert-pentoxy group; alternatively, a 3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group; alternatively, a neo-pentoxy group; alternatively, a phenoxy group; alternatively, a toloxy group; alternatively, a xyloxy group; alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxy group; or alternatively, an acetylacetonate group.
The term hydrocarbylaminyl group is used generically herein to refer collectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl, dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, or aralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwise specified, the hydrocarbylaminyl groups which can be X4 and/or X5 in formula (IA) can comprise up to about 36 carbon atoms (e.g., C1 to C36, C1 to C18, C1 to C10, or C1 to C8 hydrocarbylaminyl groups). Accordingly, hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl and dihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl group which can be X4 and/or X5 in formula (IA) can be, for instance, a methylaminyl group (—NHCH3), an ethylaminyl group (—NHCH2CH3), an n-propylaminyl group (—NHCH2CH2CH3), an iso-propylaminyl group (—NHCH(CH3)2), an n-butylaminyl group (—NHCH2CH2CH2CH3), a t-butylaminyl group (—NHC(CH3)3), an n-pentylaminyl group (—NHCH2CH2CH2CH2CH3), a neo-pentylaminyl group (—NHCH2C(CH3)3), a phenylaminyl group (—NHC6H5), a tolylaminyl group (—NHC6H4CH3), or a xylylaminyl group (—NHC6H3(CH3)2); alternatively, a methylaminyl group; alternatively, an ethylaminyl group; alternatively, a propylaminyl group; or alternatively, a phenylaminyl group. In other aspects, the hydrocarbylaminyl group which can be X4 and/or X5 in formula (IA) can be, for instance, a dimethylaminyl group (—N(CH3)2), a diethylaminyl group (—N(CH2CH3)2), a di-n-propylaminyl group (—N(CH2CH2CH3)2), a di-iso-propylaminyl group (—N(CH(CH3)2)2), a di-n-butylaminyl group (—N(CH2CH2CH2CH3)2), a di-t-butylaminyl group (—N(C(CH3)3)2), a di-n-pentylaminyl group (—N(CH2CH2CH2CH2CH3)2), a di-neo-pentylaminyl group (—N(CH2C(CH3)3)2), a di-phenylaminyl group (—N(C6H5)2), a di-tolylaminyl group (—N(C6H4CH3)2), or a di-xylylaminyl group (—N(C6H3(CH3)2)2); alternatively, a dimethylaminyl group; alternatively, a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; or alternatively, a di-phenylaminyl group.
In accordance with some aspects disclosed herein, one or both of X4 and X5 independently can be a C1 to C36 hydrocarbylsilyl group; alternatively, a C1 to C24 hydrocarbylsilyl group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C8 hydrocarbylsilyl group. In an aspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group can be any hydrocarbyl group disclosed herein (e.g., a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5 to C8 cycloalkyl group, a C6 to C8 aryl group, a C7 to C8 aralkyl group, etc.). As used herein, hydrocarbylsilyl is intended to cover (mono)hydrocarbylsilyl (—SiH2R), dihydrocarbylsilyl (—SiHR2), and trihydrocarbylsilyl (—SiR3) groups, with R being a hydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C3 to C36 or a C3 to C18 trihydrocarbylsilyl group, such as, for example, a trialkylsilyl group or a triphenylsilyl group. Illustrative and non-limiting examples of hydrocarbylsilyl groups which can be the X4 and/or X5 group(s) in formula (IA) can include, but are not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, and the like.
A hydrocarbylaminylsilyl group is used herein to refer to groups containing at least one hydrocarbon moiety, at least one N atom, and at least one Si atom. Illustrative and non-limiting examples of hydrocarbylaminylsilyl groups which can be X4 and/or X5 can include, but are not limited to —N(SiMe3)2, —N(SiEt3)2, and the like. Unless otherwise specified, the hydrocarbylaminylsilyl groups which can be X4 and/or X5 can comprise up to about 36 carbon atoms (e.g., C1 to C36, C1 to C18, C1 to C12, or C1 to C8 hydrocarbylaminylsilyl groups). In an aspect, each hydrocarbyl (one or more) of the hydrocarbylaminylsilyl group can be any hydrocarbyl group disclosed herein (e.g., a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5 to C8 cycloalkyl group, a C6 to C8 aryl group, a C7 to C8 aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl is intended to cover —NH(SiH2R), —NH(SiHR2), —NH(SiR3), —N(SiH2R)2, —N(SiHR2)2, and —N(SiR3)2 groups, among others, with R being a hydrocarbyl group.
In an aspect, X4 and X5 independently can be —OBR12 or —OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group, or alternatively, a C1 to C18 hydrocarbyl group. The hydrocarbyl group in OBR12 and/or OSO2R1 independently can be any hydrocarbyl group disclosed herein, such as, for instance, a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C4 to C18 cycloalkyl group, a C6 to C18 aryl group, or a C7 to C18 aralkyl group; alternatively, a C1 to C12 alkyl group, a C2 to C12 alkenyl group, a C4 to C12 cycloalkyl group, a C6 to C12 aryl group, or a C7 to C12 aralkyl group; or alternatively, a C1 to C8 alkyl group, a C2 to C8 alkenyl group, a C5 to C8 cycloalkyl group, a C6 to C8 aryl group, or a C7 to C8 aralkyl group.
In one aspect, X4 and X5 independently can be H, BH4, a halide, or a C1 to C36 hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while in another aspect, X4 and X5 independently can be H, BH4, or a C1 to C18 hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, or hydrocarbylaminylsilyl group. In yet another aspect, X4 and X5 independently can be a halide; alternatively, a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively, a C1 to C18 hydrocarbylaminyl group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C18 hydrocarbylaminylsilyl group. In still another aspect, both X4 and X5 can be H; alternatively, F; alternatively, Cl; alternatively, Br; alternatively, I; alternatively, BH4; alternatively, a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively, a C1 to C18 hydrocarbylaminyl group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C18 hydrocarbylaminylsilyl group.
X4 and X5 independently can be, in some aspects, H, a halide, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylaminyl, a dialkylaminyl, a trihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, a halide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy, or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl; alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl; alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl; alternatively, H; alternatively, a halide; alternatively, methyl; alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy; alternatively, an aryloxy; alternatively, acetylacetonate; alternatively, an alkylaminyl; alternatively, a dialkylaminyl; alternatively, a trihydrocarbylsilyl; or alternatively, a hydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, and hydrocarbylaminylsilyl can be a C1 to C36, a C1 to C18, a C1 to C12, or a C1 to C8 alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, and hydrocarbylaminylsilyl.
Moreover, X4 and X5 independently can be, in certain aspects, a halide or a C1 to C18 hydrocarbyl group; alternatively, a halide or a C1 to C8 hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, or phenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, a C1 to C18 alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, a C1 to C8 alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl, triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.
In formula (IA), CpA and CpB independently can be a substituted or unsubstituted cyclopentadienyl or indenyl group. In one aspect, CpA and CpB independently can be an unsubstituted cyclopentadienyl or indenyl group. Alternatively, CpA and CpB independently can be a substituted indenyl or cyclopentadienyl group, for example, having up to 5 substituents.
If present, each substituent on CpA and CpB independently can be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group. Importantly, each substituent on CpA and/or CpB can be either the same or a different substituent group. Moreover, each substituent can be at any position on the respective cyclopentadienyl or indenyl ring structure that conforms with the rules of chemical valence. In an aspect, the number of substituents on CpA and/or on CpB and/or the positions of each substituent on CpA and/or on CpB are independent of each other. For instance, two or more substituents on CpA can be different, or alternatively, each substituent on CpA can be the same. Additionally or alternatively, two or more substituents on CpB can be different, or alternatively, all substituents on CpB can be the same. In another aspect, one or more of the substituents on CpA can be different from the one or more of the substituents on CpB, or alternatively, all substituents on both CpA and/or on CpB can be the same. In these and other aspects, each substituent can be at any position on the respective cyclopentadienyl or indenyl ring structure. If substituted, CpA and/or CpB independently can have one substituent, two substituents, three substituents, four substituents, and so forth.
In formula (IA), each substituent on CpA and/or on CpB independently can be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group. In some aspects, each substituent independently can be H; alternatively, a halide; alternatively, a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 halogenated hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C12 hydrocarbyl group or a C1 to C12 hydrocarbylsilyl group. The halide, C1 to C36 hydrocarbyl group, C1 to C36 hydrocarboxy group, and C1 to C36 hydrocarbylsilyl group which can be a substituent on CpA and/or on CpB in formula (IA) can be any halide, C1 to C36 hydrocarbyl group, C1 to C36 hydrocarboxy group, and C1 to C36 hydrocarbylsilyl group described herein (e.g., as pertaining to X4 and X5 in formula (IA)). A substituent on CpA and/or on CpB in formula (IA) can be, in certain aspects, a C1 to C36 halogenated hydrocarbyl group, where the halogenated hydrocarbyl group indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbyl group. The halogenated hydrocarbyl group often can be a halogenated alkyl group, a halogenated alkenyl group, a halogenated cycloalkyl group, a halogenated aryl group, or a halogenated aralkyl group. Representative and non-limiting halogenated hydrocarbyl groups include pentafluorophenyl, trifluoromethyl (CF3), and the like.
As a non-limiting example, if present, each substituent on CpA and/or CpB independently can be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group (or other substituted aryl group), a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group; alternatively, H; alternatively, Cl; alternatively, CF3; alternatively, a methyl group; alternatively, an ethyl group; alternatively, a propyl group; alternatively, a butyl group; alternatively, a pentyl group; alternatively, a hexyl group; alternatively, a heptyl group; alternatively, an octyl group, a nonyl group; alternatively, a decyl group; alternatively, an ethenyl group; alternatively, a propenyl group; alternatively, a butenyl group; alternatively, a pentenyl group; alternatively, a hexenyl group; alternatively, a heptenyl group; alternatively, an octenyl group; alternatively, a nonenyl group; alternatively, a decenyl group; alternatively, a phenyl group; alternatively, a tolyl group; alternatively, a benzyl group; alternatively, a naphthyl group; alternatively, a trimethylsilyl group; alternatively, a triisopropylsilyl group; alternatively, a triphenylsilyl group; or alternatively, an allyldimethylsilyl group.
Illustrative and non-limiting examples of unbridged metallocene compounds having formula (IA) and suitable for use as catalyst component I can include, but are not limited to, the following compounds:










and the like, as well as combinations thereof.

Further non-limiting examples of unbridged metallocene compounds having formula (IA) and suitable for use as catalyst component I can include, but are not limited to, the following compounds:







and the like, as well as combinations thereof.

Catalyst component I is not limited solely to unbridged metallocene compounds. For example, catalyst component I can comprise a bridged metallocene compound, such as a bridged zirconium or hafnium based metallocene compound containing a fluorenyl group. In some aspects of this invention, catalyst component I can comprise a bridged metallocene compound having formula (IB):




Within formula (IB), M, CpC, X4, X5, E, RX, and RY are independent elements of the bridged metallocene compound. Accordingly, the bridged metallocene compound having formula (IB) can be described using any combination of M, CpC, X4, X5, E, RX, and RY disclosed herein.
The selections for M, X4, and X5 in formula (IB) are the same as those described herein above for formula (IA). In formula (IB), CpC can be a substituted cyclopentadienyl, indenyl, or fluorenyl group. In one aspect, CpC can be a substituted cyclopentadienyl group, while in another aspect, CpC can be a substituted indenyl group.
In some aspects, CpC can contain no additional substituents, e.g., other than bridging group E, discussed further herein below. In other aspects, CpC can be further substituted with one substituent, two substituents, three substituents, four substituents, and so forth. If present, each substituent on CpC independently can be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group. Importantly, each substituent on CpC can be either the same or a different substituent group. Moreover, each substituent can be at any position on the respective cyclopentadienyl, indenyl, or fluorenyl ring structure that conforms with the rules of chemical valence. In general, any substituent on CpC, independently, can be H or any halide, C1 to C36 hydrocarbyl group, C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 to C36 hydrocarbylsilyl group described herein (e.g., as pertaining to substituents on CpA and CpB in formula (IA)).
In one aspect, for example, each substituent on CpC independently can be a C1 to C12 hydrocarbyl group or a C1 to C12 hydrocarbylsilyl group. In another aspect, each substituent on CpC independently can be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group.
Similarly, RX and RY in formula (IB) independently can be H or any halide, C1 to C36 hydrocarbyl group, C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 to C36 hydrocarbylsilyl group disclosed herein (e.g., as pertaining to substituents on CpA and CpB in formula (IA)). In one aspect, for example, RX and RY independently can be H or a C1 to C12 hydrocarbyl group. In another aspect, RX and RY independently can be a C1 to C10 hydrocarbyl group. In yet another aspect, RX and RY independently can be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group, and the like. In still another aspect, RX and RY independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, or a benzyl group.
Bridging group E in formula (IB) can be (i) a bridging group having the formula >EARARB, wherein EA can be C or Si, and RA and RB independently can be H or a C1 to C18 hydrocarbyl group; (ii) a bridging group having the formula —CRCRD—CRERF—, wherein RC, RD, RE, and RF independently can H or a C1 to C18 hydrocarbyl group; or (iii) a bridging group having the formula —SiRGRH—SiRIRJ—, wherein RG, RH, RI, and RJ independently can be H or a C1 to C18 hydrocarbyl group.
In the first option, the bridging group E can have the formula >EARARB, wherein EA can C or Si, and RA and RB independently can be H or any C1 to C18 hydrocarbyl group disclosed herein. In some aspects of this invention, RA and RB independently can be a C1 to C12 hydrocarbyl group; alternatively, RA and RB independently can be a C1 to C8 hydrocarbyl group; alternatively, RA and RB independently can be an alkyl, alkenyl, or aryl group having up to 8 carbon atoms; alternatively, RA and RB independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, or a benzyl group; or alternatively, RA and RB independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a phenyl group, or a benzyl group. In these and other aspects, RA and RB can be either the same or different.
In the second option, the bridging group E can have the formula —CRCRD—CRERF—, wherein RC, RD, RE, and RF independently can be H or any C1 to C18 hydrocarbyl group disclosed herein. For instance, RC, RD, RE, and RF independently can be H or a methyl group.
In the third option, the bridging group E can have the formula —SiRGRH—SiRIRJ—, wherein RG, RH, RI, and RJ independently can be H or any C1 to C18 hydrocarbyl group disclosed herein. For instance, RG, RH, RI, and RJ independently can be H or a methyl group.
Illustrative and non-limiting examples of bridged metallocene compounds having formula (IB) and/or suitable for use as catalyst component I can include, but are not limited to, the following compounds (Me=methyl, t-Bu=tert-butyl):













and the like, as well as combinations thereof.

Further non-limiting examples of bridged metallocene compounds having formula (IB) and/or suitable for use as catalyst component I can include, but are not limited to, the following compounds (Ph=phenyl):













and the like, as well as combinations thereof.

Catalyst Component II

Catalyst component II can comprise a titanium based half-metallocene compound containing an indenyl group. In an aspect of this invention, catalyst component II can comprise a half-metallocene compound having formula (IIA):




Within formula (IIA), InA, X1, X2, and X3 are independent elements of the half-metallocene compound. Accordingly, the half-metallocene compound having formula (IIA) can be described using any combination of InA, X1, X2, and X3 disclosed herein.
As noted with formula (IA) and unless otherwise specified, formula (IIA) above, any other structural formulas disclosed herein, and any half-metallocene complex, compound, or species disclosed herein are not designed to show stereochemistry or isomeric positioning of the different moieties (e.g., these formulas are not intended to display cis or trans isomers, or R or S diastereoisomers), although such compounds are contemplated and encompassed by these formulas and/or structures.
In formula (IIA), X1, X2, and X3 independently can be monoanionic ligands, and X1, X2, and X3 can be either the same or different monoanionic ligands. The selections for X1, X2, and X3 in formula (IIA) are the same as those described herein above for X4 and X5 in formula (IA). Thus, X1, X2, and X3 independently can be H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, —OBR12, or —OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group. In some aspects, X1, X2, and X3 independently can be any halide or any C1 to C18 hydrocarbyl group disclosed herein. For example, X1, X2, and X3 can be Cl.
In formula (IIA), InA can be a substituted or unsubstituted indenyl group. In one aspect, InA can be an unsubstituted indenyl group. Alternatively, InA can be a substituted indenyl group, having one substituent, two substituents, three substituents, four substituents, five substituents, six substituents, or seven substituents. If present, each substituent on InA independently can be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group. Importantly, each substituent on InA can be either the same or a different substituent group. Moreover, each substituent can be at any position on the indenyl ring structure that conforms with the rules of chemical valence. In general, any substituent on InA, independently, can be H or any halide, C1 to C36 hydrocarbyl group, C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 to C36 hydrocarbylsilyl group described herein (e.g., as pertaining to substituents on CpA and CpB in formula (IA)).
In one aspect, for example, each substituent on InA independently can be a C1 to C12 hydrocarbyl group or a C1 to C12 hydrocarbylsilyl group. In another aspect, each substituent on InA independently can be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group.
Illustrative and non-limiting examples of half-metallocene compounds having formula (IIA) and suitable for use as catalyst component II can include, but are not limited to, the following compounds:




and the like, as well as combinations thereof.

Half-metallocene compounds having formula (IIA) can be synthesized using any suitable procedure, such as disclosed in Weiss et al., Organometallics 2005, 24, 2577-2581, the disclosure of which is incorporated herein by reference in its entirety.
Activator-Supports
The present invention encompasses various catalyst compositions containing an activator, such as activator-support. In one aspect, the activator-support can comprise a chemically-treated solid oxide. Alternatively, in another aspect, the activator-support can comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non-layered aluminosilicate mineral, or combinations thereof.
Generally, chemically-treated solid oxides exhibit enhanced acidity as compared to the corresponding untreated solid oxide compound. The chemically-treated solid oxide also can function as a catalyst activator as compared to the corresponding untreated solid oxide. While the chemically-treated solid oxide can activate a metallocene or half-metallocene complex in the absence of co-catalysts, it is not necessary to eliminate co-catalysts from the catalyst composition. The activation function of the activator-support can enhance the activity of catalyst composition as a whole, as compared to a 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 organoaluminum compounds, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and the like.
The chemically-treated solid oxide can comprise a solid oxide treated with an electron-withdrawing anion. While not intending to be bound by the following statement, it is believed that treatment of the solid oxide with an electron-withdrawing component augments or enhances the acidity of the oxide. Thus, either the activator-support exhibits Lewis or Brønsted acidity that is typically greater than the Lewis or Brønsted acid strength of the untreated solid oxide, or the activator-support has a greater number of acid sites than the untreated solid oxide, or both. One method to quantify the acidity of the chemically-treated and untreated solid oxide materials can be by comparing the polymerization activities of the treated and untreated oxides under acid catalyzed reactions.
Chemically-treated solid oxides of this invention generally can be formed from an inorganic solid oxide that exhibits Lewis acidic or Brønsted acidic behavior and has a relatively high porosity. The solid oxide can be chemically-treated with an electron-withdrawing component, typically an electron-withdrawing anion, to form an activator-support.
According to one aspect of the present invention, the solid oxide used to prepare the chemically-treated solid oxide can have a pore volume greater than about 0.1 cc/g. According to another aspect of the present invention, the solid oxide can have a pore volume greater than about 0.5 cc/g. According to yet another aspect of the present invention, the solid oxide can have a pore volume greater than about 1.0 cc/g.
In another aspect, the solid oxide can have a surface area of from about 100 to about 1000 m2/g. In yet another aspect, the solid oxide can have a surface area of from about 200 to about 800 m2/g. In still another aspect of the present invention, the solid oxide can have a surface area of from about 250 to about 600 m2/g.
The chemically-treated solid oxide can comprise a solid inorganic oxide comprising oxygen and one or more elements 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 one or more elements selected from the lanthanide or actinide elements (See: Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G., Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, the inorganic oxide can comprise oxygen and an element, or elements, 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 the chemically-treated solid oxide can include, but are not limited to, Al2O3, B2O3, BeO, Bi2O3, 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, coatings of one oxide with another, and combinations thereof. For example, the solid oxide can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof.
The solid oxide of this invention encompasses oxide materials such as alumina, “mixed oxide” compounds thereof such as silica-alumina, and combinations and mixtures thereof. The mixed oxide compounds such as silica-alumina can be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activator-support of the present invention, either singly or in combination, can include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide of this invention also encompasses oxide materials such as silica-coated alumina, as described in U.S. Pat. No. 7,884,163, the disclosure of which is incorporated herein by reference in its entirety.
The electron-withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Brønsted acidity of the solid oxide upon treatment (as compared to the solid oxide that is not treated with at least one electron-withdrawing anion). According to one aspect of the present invention, the electron-withdrawing component can be an electron-withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion. Examples of electron-withdrawing anions can include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, 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 also can be employed in the present invention. It is contemplated that the electron-withdrawing anion can be, or can comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and the like, or any combination thereof, in some aspects of this invention. In other aspects, the electron-withdrawing anion can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and the like, or combinations thereof.
Thus, for example, the activator-support (e.g., chemically-treated solid oxide) used in the catalyst compositions of the present invention can be, or can comprise, fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, or combinations thereof. In one aspect, the activator-support can be, or can comprise, fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, or any combination thereof. In another aspect, the activator-support can comprise fluorided alumina; alternatively, chlorided alumina; alternatively, sulfated alumina; alternatively, fluorided silica-alumina; alternatively, sulfated silica-alumina; alternatively, fluorided silica-zirconia; alternatively, chlorided silica-zirconia; or alternatively, fluorided silica-coated alumina.
When the electron-withdrawing component comprises a salt of 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 the acid during calcining. Factors that dictate the suitability of the particular salt to serve as a source for the electron-withdrawing anion can include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse reactivity of the cation, ion-pairing effects between the cation and anion, hygroscopic properties imparted to the salt by the cation, and the like, and thermal stability of the anion. Examples of suitable cations in the salt of the electron-withdrawing anion can include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H+, [H(OEt2)2]+, and the like.
Further, combinations of one or more different electron-withdrawing anions, in varying proportions, can be used to tailor the specific acidity of the activator-support to the desired level. Combinations of electron-withdrawing components can be contacted with the oxide material simultaneously or individually, and in any order that affords the desired chemically-treated solid oxide acidity. For example, one aspect of this invention can employ two or more electron-withdrawing anion source compounds in two or more separate contacting steps.
Thus, a process by which a chemically-treated solid oxide can be prepared is as follows: a selected solid oxide, or combination of solid oxides, can be contacted with a first electron-withdrawing anion source compound to form a first mixture; this first mixture can be calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture then can be calcined to form a treated solid oxide. In such a process, the first and second electron-withdrawing anion source compounds can be either the same or different compounds.
According to another aspect of the present invention, the chemically-treated solid oxide can comprise a solid inorganic oxide material, a mixed oxide material, or a combination of inorganic oxide materials, that is chemically-treated with an electron-withdrawing component, and optionally treated with a metal source, including metal salts, metal ions, or other metal-containing compounds. Non-limiting examples of the metal or metal ion can include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, or combinations thereof. Examples of chemically-treated solid oxides that contain a metal or metal ion can include, but are not limited to, chlorided zinc-impregnated alumina, fluorided titanium-impregnated alumina, fluorided zinc-impregnated alumina, chlorided zinc-impregnated silica-alumina, fluorided zinc-impregnated silica-alumina, sulfated zinc-impregnated alumina, chlorided zinc aluminate, fluorided zinc aluminate, sulfated zinc aluminate, silica-coated alumina treated with hexafluorotitanic acid, silica-coated alumina treated with zinc and then fluorided, and the like, or any combination thereof.
Any method of impregnating the solid oxide material with a metal can be used. The method by which the oxide is contacted with a metal source, typically a salt or metal-containing compound, can include, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like. If desired, the metal-containing compound can be added to or impregnated into the solid oxide in solution form, and subsequently converted into the supported metal upon calcining. Accordingly, the solid inorganic oxide can further comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals. For example, zinc often can be used to impregnate the solid oxide because it can provide improved catalyst activity at a low cost.
The solid oxide can be treated with metal salts or metal-containing compounds before, after, or at the same time that the solid oxide is treated with the electron-withdrawing anion. Following any contacting method, the contacted mixture of solid compound, electron-withdrawing anion, and the metal ion can be calcined. Alternatively, a solid oxide material, an electron-withdrawing anion source, and the metal salt or metal-containing compound can be contacted and calcined simultaneously.
Various processes can be used to form the chemically-treated solid oxide useful in the present invention. The chemically-treated solid oxide can comprise the contact product of one or more solid oxides with one or more electron-withdrawing anion sources. It is not required that the solid oxide be calcined prior to contacting the electron-withdrawing anion source. Typically, the contact product can be calcined either during or after the solid oxide is contacted with the electron-withdrawing anion source. The solid oxide can be calcined or uncalcined. Various processes to prepare solid oxide activator-supports that can be employed in this invention have been reported. For example, such methods are described in U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, and 6,750,302, the disclosures of which are incorporated herein by reference in their entirety.
According to one aspect of the present invention, the solid oxide material can be chemically-treated by contacting it with an electron-withdrawing component, typically an electron-withdrawing anion source. Further, the solid oxide material optionally can be chemically treated with a metal ion, and then calcined to form a metal-containing or metal-impregnated chemically-treated solid oxide. According to another aspect of the present invention, the solid oxide material and electron-withdrawing anion source can be contacted and calcined simultaneously.
The method by which the oxide is contacted with the electron-withdrawing component, typically a salt or an acid of an electron-withdrawing anion, can include, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like. Thus, following any contacting method, the contacted mixture of the solid oxide, electron-withdrawing anion, and optional metal ion, can be calcined.
The solid oxide activator-support (i.e., chemically-treated solid oxide) thus can be produced by a process comprising:
1) contacting a solid oxide (or solid oxides) with an electron-withdrawing anion source compound (or compounds) to form a first mixture; and
2) calcining the first mixture to form the solid oxide activator-support.
According to another aspect of the present invention, the solid oxide activator-support (chemically-treated solid oxide) can be produced by a process comprising:
1) contacting a solid oxide (or solid oxides) with a first electron-withdrawing anion source compound to form a first mixture;
2) calcining the first mixture to produce a calcined first mixture;
3) contacting the calcined first 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 activator-support.
According to yet another aspect of the present invention, the chemically-treated solid oxide can be produced or formed by contacting the solid oxide with the electron-withdrawing anion source compound, where the solid oxide compound is calcined before, during, or after contacting the electron-withdrawing anion source, and where there is a substantial absence of aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds.
Calcining of the treated solid oxide generally can be conducted in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature from about 200° C. to about 900° C., and for a time of about 1 minute to about 100 hours. Calcining can be conducted at a temperature of from about 300° C. to about 800° C., or alternatively, at a temperature of from about 400° C. to about 700° C. Calcining can be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcining can be carried out for about 1 to about 10 hours at a temperature of from about 350° C. to about 550° C. Any suitable ambient atmosphere can be employed during calcining. Generally, calcining can be conducted in an oxidizing atmosphere, such as air. 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 solid oxide material 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 in the form of a particulate solid. For example, the solid oxide material can be treated with a source of sulfate (termed a “sulfating agent”), a source of bromide ion (termed a “bromiding agent”), a source of chloride ion (termed a “chloriding agent”), a source of fluoride ion (termed a “fluoriding agent”), or a combination thereof, and calcined to provide the solid oxide activator. Useful acidic activator-supports can include, but are not limited to, bromided alumina, chlorided alumina, fluorided alumina, sulfated alumina, bromided silica-alumina, chlorided silica-alumina, fluorided silica-alumina, sulfated silica-alumina, bromided silica-zirconia, chlorided silica-zirconia, fluorided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, alumina treated with hexafluorotitanic acid, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, fluorided boria-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pillared montmorillonite, optionally treated with fluoride, chloride, or sulfate; phosphated alumina or other aluminophosphates optionally treated with sulfate, fluoride, or chloride; or any combination of the above. Further, any of these activator-supports optionally can be treated or impregnated with a metal ion.
In an aspect, the chemically-treated solid oxide can comprise a fluorided solid oxide in the form of a particulate solid. The fluorided solid oxide can be formed by contacting a solid oxide with a fluoriding 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, the one to three carbon alcohols because of their volatility and low surface tension. Examples of suitable fluoriding agents can include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) ((NH4)2SiF6), ammonium hexafluorophosphate (NH4 PF6), hexafluorotitanic acid (H2TiF6), ammonium hexafluorotitanic acid ((NH4)2TiF6), hexafluorozirconic acid (H2ZrF6), AlF3, NH4AlF4, analogs thereof, and combinations thereof. Triflic acid and ammonium triflate also can be employed. For example, ammonium bifluoride (NH4HF2) can be used as the fluoriding agent, due to its ease of use and availability.
If desired, the solid oxide can be treated with a fluoriding agent during the calcining step. Any fluoriding agent capable of thoroughly contacting the solid oxide during the calcining step can be used. For example, in addition to those fluoriding agents described previously, volatile organic fluoriding agents can be used. Examples of volatile organic fluoriding agents useful in this aspect of the invention can include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. Calcining temperatures generally must be high enough to decompose the compound and release fluoride. Gaseous hydrogen fluoride (HF) or fluorine (F2) itself also can be used with the solid oxide if fluorided while calcining. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4−) also can be employed. One convenient method of contacting the solid oxide with the fluoriding agent can be to vaporize a fluoriding agent into a gas stream used to fluidize the solid oxide during calcination.
Similarly, in another aspect of this invention, the chemically-treated solid oxide can comprise a chlorided solid oxide in the form of a particulate solid. The chlorided solid oxide can be formed by contacting a solid oxide with a chloriding agent. The chloride ion can be added to the oxide by forming a slurry of the oxide in a suitable solvent. The solid oxide can be treated with a chloriding agent during the calcining step. Any chloriding agent capable of serving as a source of chloride and thoroughly contacting the oxide during the calcining step can be used, such as SiCl4, SiMe2Cl2, TiCl4, BCl3, and the like, including mixtures thereof. Volatile organic chloriding agents can be used. Examples of suitable volatile organic chloriding agents can 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 also can be used with the solid oxide during calcining. One convenient method of contacting the oxide with the chloriding agent can be to vaporize a chloriding agent into a gas stream used to fluidize the solid oxide during calcination.
The amount of fluoride or chloride ion present before calcining the solid oxide generally can be from about 1 to about 50% by weight, where the weight percent is based on the weight of the solid oxide, for example, silica-alumina, before calcining According to another aspect of this invention, the amount of fluoride or chloride ion present before calcining the solid oxide can be from about 1 to about 25% by weight, and according to another aspect of this invention, from about 2 to about 20% by weight. According to yet another aspect of this invention, the amount of fluoride or chloride ion present before calcining the solid oxide can be from about 4 to about 10% by weight. Once impregnated with halide, the halided oxide can be dried by any suitable method including, but not limited to, suction filtration followed by evaporation, drying under vacuum, spray drying, and the like, although it is also possible to initiate the calcining step immediately without drying the impregnated solid oxide.
The silica-alumina used to prepare the treated silica-alumina typically can have a pore volume greater than about 0.5 cc/g. According to one aspect of the present invention, the pore volume can be greater than about 0.8 cc/g, and according to another aspect of the present invention, greater than about 1.0 cc/g. Further, the silica-alumina generally can have a surface area greater than about 100 m2/g. According to another aspect of this invention, the surface area can be greater than about 250 m2/g. Yet, in another aspect, the surface area can be greater than about 350 m2/g.
The silica-alumina utilized in the present invention typically can have an alumina content from about 5 to about 95% by weight. According to one aspect of this invention, the alumina content of the silica-alumina can be from about 5 to about 50%, or from about 8% to about 30%, alumina by weight. In another aspect, high alumina content silica-alumina compounds can be employed, in which the alumina content of these silica-alumina compounds typically ranges from about 60% to about 90%, or from about 65% to about 80%, alumina by weight. According to yet another aspect of this invention, the solid oxide component can comprise alumina without silica, and according to another aspect of this invention, the solid oxide component can comprise silica without alumina.
The sulfated solid oxide can comprise sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide can be treated further with a metal ion such that the calcined sulfated oxide comprises a metal. According to one aspect of the present invention, the sulfated solid oxide can comprise sulfate and alumina. In some instances, the sulfated alumina can be formed by a process wherein the alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt such as ammonium sulfate. This process generally can be performed by forming a slurry of the alumina in a suitable solvent, such as alcohol or water, in which the desired concentration of the sulfating agent has been added. Suitable organic solvents can include, but are not limited to, the one to three carbon alcohols because of their volatility and low surface tension.
According to one aspect of this invention, the amount of sulfate ion present before calcining can be from about 0.5 to about 100 parts by weight sulfate ion to about 100 parts by weight solid oxide. According to another aspect of this invention, the amount of sulfate ion present before calcining can be from about 1 to about 50 parts by weight sulfate ion to about 100 parts by weight solid oxide, and according to still another aspect of this invention, from about 5 to about 30 parts by weight sulfate ion to about 100 parts by weight solid oxide. These weight ratios are based on the weight of the solid oxide before calcining. Once impregnated with sulfate, the sulfated oxide can be dried by any suitable method including, but not limited to, suction filtration followed by evaporation, drying under vacuum, spray drying, and the like, although it is also possible to initiate the calcining step immediately.
According to another aspect of the present invention, the activator-support used in preparing the catalyst compositions of this invention can comprise an ion-exchangeable activator-support including, but not limited to, silicate and aluminosilicate compounds or minerals, either with layered or non-layered structures, and combinations thereof. In another aspect of this invention, ion-exchangeable, layered aluminosilicates such as pillared clays can be used as activator-supports. When the acidic activator-support comprises an ion-exchangeable activator-support, it can optionally be treated with at least one electron-withdrawing anion such as those disclosed herein, though typically the ion-exchangeable activator-support is not treated with an electron-withdrawing anion.
According to another aspect of the present invention, the activator-support of this invention can comprise clay minerals having exchangeable cations and layers capable of expanding. Typical clay mineral activator-supports can include, but are not limited to, ion-exchangeable, layered aluminosilicates such as pillared clays. Although the term “support” is used, it is not meant to be construed as an inert component of the catalyst composition, but rather can be considered an active part of the catalyst composition, because of its intimate association with the metallocene and/or half-metallocene component.
According to another aspect of the present invention, the clay materials of this invention can encompass materials either in their natural state or that have been treated with various ions by wetting, ion exchange, or pillaring. Typically, the clay material activator-support of this invention can comprise clays that have been ion exchanged with large cations, including polynuclear, highly charged metal complex cations. However, the clay material activator-supports of this invention also can encompass clays that have been ion exchanged with simple salts, including, but not limited to, salts of Al(III), Fe(II), Fe(III), and Zn(II) with ligands such as halide, acetate, sulfate, nitrate, or nitrite.
According to another aspect of the present invention, the activator-support can comprise a pillared clay. The term “pillared clay” is used to refer to clay materials that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations. Examples of such ions can include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometallates, and other large ions. Thus, the term pillaring can refer to a simple exchange reaction in which the exchangeable cations of a clay material are replaced with large, highly charged ions, such as Keggin ions. These polymeric cations then can be immobilized within the interlayers of the clay and when calcined are converted to metal oxide “pillars,” effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the supporting pillars between clay layers, the expanded lattice structure can be maintained and the porosity can be enhanced. The resulting pores can vary in shape and size as a function of the pillaring material and the parent clay material used. Examples of pillaring and pillared 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. Pat. Nos. 4,452,910; 5,376,611; and 4,060,480; the disclosures of which are incorporated herein by reference in their entirety.
The pillaring process can utilize clay minerals having exchangeable cations and layers capable of expanding. Any pillared clay that can enhance the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, suitable clay minerals for pillaring can include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layer clays; the fibrous clays including but not limited to sepiolites, attapulgites, and palygorskites; a serpentine clay; illite; laponite; saponite; and any combination thereof. In one aspect, the pillared clay activator-support can comprise bentonite or montmorillonite. The principal component of bentonite is montmorillonite.
The pillared clay can be pretreated if desired. For example, a pillared bentonite can be pretreated by drying at about 300° C. under an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although an exemplary pretreatment is described herein, it should be understood that the preheating can be carried out at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by this invention.
The activator-support 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, phosphated inorganic oxides, and the like. In one aspect, typical support materials that can be used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminum phosphate, silica-titania, coprecipitated silica/titania, mixtures thereof, or any combination thereof.
According to another aspect of the present invention, one or more of the metallocene and/or half-metallocene compounds can be precontacted with an olefin monomer and an organoaluminum compound for a first period of time prior to contacting this mixture with the activator-support. Once the precontacted mixture of metallocene complex(es), olefin monomer, and organoaluminum compound is contacted with the activator-support, the composition further comprising the activator-support can be termed a “postcontacted” mixture. The postcontacted mixture can be allowed to remain in further contact for a second period of time prior to being charged into the reactor in which the polymerization process will be carried out.
According to yet another aspect of the present invention, one or more of the metallocene and/or half-metallocene compounds can be precontacted with an olefin monomer and an activator-support for a first period of time prior to contacting this mixture with the organoaluminum compound. Once the precontacted mixture of the metallocene complex(es), olefin monomer, and activator-support is contacted with the organoaluminum compound, the composition further comprising the organoaluminum can be termed a “postcontacted” mixture. The postcontacted mixture can be allowed to remain in further contact for a second period of time prior to being introduced into the polymerization reactor.
Co-Catalysts
In certain aspects directed to catalyst compositions containing a co-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound, examples of which include non-halide metal hydrocarbyl compounds, metal hydrocarbyl halide compounds, non-halide metal alkyl compounds, metal alkyl halide compounds, and so forth. The hydrocarbyl group (or alkyl group) can be any hydrocarbyl (or alkyl) group disclosed herein. Moreover, in some aspects, the metal of the metal hydrocarbyl can be a group 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14 metal; or alternatively, a group 13 metal. Hence, in some aspects, the metal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metal hydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron, aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium, or potassium; alternatively, magnesium or calcium; alternatively, lithium; alternatively, sodium; alternatively, potassium; alternatively, magnesium; alternatively, calcium; alternatively, zinc; alternatively, boron; alternatively, aluminum; or alternatively, tin. In some aspects, the metal hydrocarbyl or metal alkyl, with or without a halide, can comprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl or alkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or an aluminum hydrocarbyl or alkyl.
In particular aspects directed to catalyst compositions containing a co-catalyst (e.g., the activator can comprise a solid oxide treated with an electron-withdrawing anion), the co-catalyst can comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, or an organolithium compound, and this includes any combinations of these materials. In one aspect, the co-catalyst can comprise an organoaluminum compound. In another aspect, the co-catalyst can comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof. In yet another aspect, the co-catalyst can comprise an aluminoxane compound; alternatively, an organoboron or organoborate compound; alternatively, an ionizing ionic compound; alternatively, an organozinc compound; alternatively, an organomagnesium compound; or alternatively, an organolithium compound.
Organoaluminum Compounds
In some aspects, catalyst compositions of the present invention can comprise one or more organoaluminum compounds. Such compounds can include, but are not limited to, compounds having the formula:

(RZ)3Al;

where each RZ independently can be an aliphatic group having from 1 to 10 carbon atoms. For example, each RZ independently can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which can be used in catalyst compositions disclosed herein can include, but are not limited to, compounds having the formula:

Al(X7)m(X8)3−m,

where each X7 independently can be a hydrocarbyl; each X8 independently can be an alkoxide or an aryloxide, a halide, or a hydride; and m can be from 1 to 3, inclusive. Hydrocarbyl is used herein to specify a hydrocarbon radical group and includes, for instance, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups.

In one aspect, each X7 independently can be any hydrocarbyl having from 1 to about 18 carbon atoms disclosed herein. In another aspect of the present invention, each X7 independently can be any alkyl having from 1 to 10 carbon atoms disclosed herein. For example, each X7 independently 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, each X8 independently can be an alkoxide or an aryloxide, any one of which has from 1 to 18 carbon atoms, a halide, or a hydride. In another aspect of the present invention, each X8 can be selected independently from fluorine and chlorine. Yet, in another aspect, X8 can be chlorine.
In the formula, Al(X7)m(X8)3−m, m can be a number from 1 to 3, inclusive, and typically, m can be 3. The value of m is not restricted to be an integer; therefore, this formula can include sesquihalide compounds or other organoaluminum cluster compounds.
Examples of organoaluminum compounds suitable for use in accordance with the present invention can include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. Specific non-limiting examples of suitable organoaluminum compounds can include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof.
The present invention contemplates a method of precontacting a metallocene or half-metallocene compound with an organoaluminum compound and an olefin monomer to form a precontacted mixture, prior to contacting this precontacted mixture with an activator-support to form a catalyst composition. When the catalyst composition is prepared in this manner, typically, though not necessarily, a portion of the organoaluminum compound can be added to the precontacted mixture and another portion of the organoaluminum compound can be added to the postcontacted mixture prepared when the precontacted mixture is contacted with the solid oxide activator-support. However, the entire organoaluminum compound can be used to prepare the catalyst composition in either the precontacting or postcontacting step. Alternatively, all the catalyst components can be contacted in a single step.
Further, more than one organoaluminum compound can be used in either the precontacting or the postcontacting step. When an organoaluminum compound is added in multiple steps, the amounts of organoaluminum compound disclosed herein include the total amount of organoaluminum compound used in both the precontacted and postcontacted mixtures, and any additional organoaluminum compound added to the polymerization reactor. Therefore, total amounts of organoaluminum compounds are disclosed regardless of whether a single organoaluminum compound or more than one organoaluminum compound is used.
Aluminoxane Compounds
Certain aspects of the present invention provide a catalyst composition which can comprise an aluminoxane compound. As used herein, the terms “aluminoxane” and “aluminoxane compound” refer to aluminoxane compounds, compositions, mixtures, or discrete species, 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 aluminoxane is provided as the poly(hydrocarbyl aluminum oxide), or in which aluminoxane is provided as the combination of an aluminum alkyl compound and a source of active protons such as water. Aluminoxanes also can be referred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes.
The other catalyst components typically can be contacted with the aluminoxane in a saturated hydrocarbon compound solvent, though 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 manner can be collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition can be introduced into the polymerization reactor without being isolated.
The aluminoxane compound of this invention can be an oligomeric aluminum compound comprising linear structures, cyclic structures, or cage structures, or mixtures of all three. Cyclic aluminoxane compounds having the formula:




wherein each R in this formula independently can be a linear or branched alkyl having from 1 to 10 carbon atoms, and p in this formula can be an integer from 3 to 20, are encompassed by this invention. The AlRO moiety shown here also can constitute the repeating unit in a linear aluminoxane. Thus, linear aluminoxanes having the formula:





wherein each R in this formula independently can be a linear or branched alkyl having from 1 to 10 carbon atoms, and q in this formula can be an integer from 1 to 50, are also encompassed by this invention.

Further, aluminoxanes can have cage structures of the formula R5r+αtRr−αbAl4rO3r, wherein each Rt independently can be a terminal linear or branched alkyl group having from 1 to 10 carbon atoms; each Rb independently can be a bridging linear or branched alkyl group having from 1 to 10 carbon atoms; r can be 3 or 4; and α can be equal to nAl(3)−nO(2)+nO(4), wherein nAl(3) is the number of three coordinate aluminum atoms, nO(2) is the number of two coordinate oxygen atoms, and nO(4) is the number of 4 coordinate oxygen atoms.
Thus, aluminoxanes which can be employed in the catalyst compositions of the present invention can be represented generally by formulas such as (R—Al—O)p, R(R—Al—O)qAlR2, and the like. In these formulas, each R group independently can be a linear 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 can include, but are not limited to, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane, and iso-butylaluminoxane can be prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively, and sometimes are referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminum, such as that disclosed in U.S. Pat. No. 4,794,096, incorporated herein by reference in its entirety.
The present invention contemplates many values of p and q in the aluminoxane formulas (R—Al—O)p and R(R—Al—O)qAlR2, respectively. In some aspects, p and q can be at least 3. However, depending upon how the 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 herein.
In preparing a catalyst composition containing an aluminoxane, the molar ratio of the total moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of metallocene complex(es) in the composition generally can be between about 1:10 and about 100,000:1. In another aspect, the molar ratio can be in a range from about 5:1 to about 15,000:1. Optionally, aluminoxane can be added to a polymerization zone in ranges 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. Pat. 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 (RZ)3Al, to form the desired organoaluminoxane compound. While not intending to be bound by this statement, it is believed that this synthetic method can afford a mixture of both linear and cyclic R—Al—O aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes can be prepared by reacting an aluminum alkyl compound, such as (RZ)3Al, with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.
Organoboron & Organoborate Compounds
According to another aspect of the present invention, the catalyst composition can comprise an organoboron or organoborate compound. Such compounds can include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, fluoroorgano boron compounds and fluoroorgano borate compounds are contemplated.
Any fluoroorgano boron or fluoroorgano borate compound can be utilized with the present invention. Examples of fluoroorgano borate compounds that can be used in the present invention can include, but are not limited to, fluorinated aryl borates such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, or mixtures thereof. Examples of fluoroorgano boron compounds that can be used as co-catalysts in the present invention can include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixtures thereof. Although not intending to be bound by the following theory, these examples of fluoroorgano borate and fluoroorgano boron compounds, and related compounds, can form “weakly-coordinating”anions when combined with a transition metal complex (see e.g., U.S. Pat. No. 5,919,983, the disclosure of which is incorporated herein by reference in its entirety). Applicants also contemplate the use of diboron, or bis-boron, compounds or other bifunctional compounds containing two or more boron atoms in the chemical structure, such 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 organoboron compound can be used. According to one aspect of this invention, the molar ratio of the total moles of organoboron or organoborate compound (or compounds) to the total moles of metallocene and half-metallocene compounds in the catalyst composition can be in a range from about 0.1:1 to about 15:1. Typically, the amount of the fluoroorgano boron or fluoroorgano borate compound used can be from about 0.5 moles to about 10 moles of boron/borate compound per mole of metallocene-type complex(es). According to another aspect of this invention, the amount of fluoroorgano boron or fluoroorgano borate compound can be from about 0.8 moles to about 5 moles of boron/borate compound per mole of metallocene-type complex(es).
Ionizing Ionic Compounds
In another aspect, catalyst compositions disclosed herein can comprise an ionizing ionic compound. An ionizing ionic compound is an ionic compound that can function as a co-catalyst to enhance the activity of the catalyst composition. While not intending to be bound by theory, it is believed that the ionizing ionic compound can be capable of reacting with a metallocene-type complex and converting the metallocene complex into one or more cationic metallocene complexes, or incipient cationic metallocene complexes. Again, while not intending to be bound by theory, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or partially extracting an anionic ligand, such as monoanionic ligand X, from the metallocene-type complex. However, the ionizing ionic compound can be a co-catalyst regardless of whether it is ionizes the metallocene and/or half-metallocene compound, abstracts a X ligand in a fashion as to form an ion pair, weakens the metal-X bond in the metallocene or half-metallocene, simply coordinates to a X ligand, or activates the metallocene and/or half-metallocene by some other mechanism.
Further, it is not necessary that the ionizing ionic compound activate the metallocene and/or half-metallocene compound only. The activation function of the ionizing ionic compound can be evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition that does not contain an ionizing ionic compound.
Examples of ionizing ionic compounds can 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)ammonium tetrakis(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(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-b is (trifluoromethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl) borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetraphenylborate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethylphenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and the like, or combinations thereof. Ionizing ionic compounds useful in this invention are not limited to these; other examples of ionizing ionic compounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938, the disclosures of which are incorporated herein by reference in their entirety.
Organozinc, Organomagnesium, & Organolithium Compounds
Other aspects are directed to catalyst compositions which can include an organozinc compound, an organomagnesium compound, an organolithium compound, or a combination thereof. In some aspects, these compounds have the following general formulas:

Zn(X10)(X11);

Mg(X12)(X13);and

Li(X14).

In these formulas, X10, X12, and X14 independently can be a C1 to C18 hydrocarbyl group, and X11 and X13 independently can be H, a halide, or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarboxy group. It is contemplated X10 and X11 (or X12 and X13) can be the same, or that X10 and X11 (or X12 and X13) can be different.
In one aspect, X10, X11, X12, X13, and X14 independently can be any C1 to C18 hydrocarbyl group, C1 to C12 hydrocarbyl group, C1 to C8 hydrocarbyl group, or C1 to C5 hydrocarbyl group disclosed herein. In another aspect, X10, X11, X12, X13, and X14 independently can be any C1 to C18 alkyl group, C2 to C18 alkenyl group, C6 to C18 aryl group, or C7 to C18 aralkyl group disclosed herein; alternatively, any C1 to C12 alkyl group, C2 to C12 alkenyl group, C6 to C12 aryl group, or C7 to C12 aralkyl group disclosed herein; or alternatively, any C1 to C5 alkyl group, C2 to C5 alkenyl group, C6 to C8 aryl group, or C7 to C8 aralkyl group disclosed herein. Thus, X10, X11, X12, X13, and X14 independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a phenyl group, a naphthyl group, a benzyl group, or a tolyl group, and the like. In yet another aspect, X10, X11, X12, X13, and X14 independently can be methyl, ethyl, propyl, butyl, or pentyl (e.g., neopentyl), or both X10 and X11 (or both X12 and X13) can be methyl, or ethyl, or propyl, or butyl, or pentyl (e.g., neopentyl).
X11 and X13 independently can be H, a halide, or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarboxy group (e.g., any C1 to C18, C1 to C12, C1 to C10, or C1 to C8 hydrocarboxy group disclosed herein). In some aspects, X11 and X13 independently can be H, a halide (e.g., Cl), or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarboxy group; alternatively, H, a halide, or a C1 to C8 hydrocarbyl or C1 to C8 hydrocarboxy group; or alternatively, H, Br, Cl, F, I, methyl, ethyl, propyl, butyl, pentyl (e.g., neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, phenoxy, toloxy, xyloxy, or benzoxy.
In other aspects, the organozinc and/or the organomagnesium compound can have one or two hydrocarbylsilyl moieties. Each hydrocarbyl of the hydrocarbylsilyl group can be any hydrocarbyl group disclosed herein (e.g., a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C6 to C18 aryl group, a C7 to C18 aralkyl group, etc.). Illustrative and non-limiting examples of hydrocarbylsilyl groups can include, but are not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, trimethylsilylmethyl, and the like.
Exemplary organozinc compounds which can be used as co-catalysts can include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di(triisoproplysilyl)zinc, di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.
Similarly, exemplary organomagnesium compounds can include, but are not limited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dineopentylmagnesium, di(trimethylsilylmethyl)magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesium bromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide, neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide, methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesium ethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide, trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide, ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesium propoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesium propoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide, propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesium phenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or any combinations thereof.
Likewise, exemplary organolithium compounds can include, but are not limited to, methyllithium, ethyllithium, propyllithium, butyllithium (e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium, phenyllithium, tolyllithium, xylyllithium, benzyllithium, (dimethylphenyl)methyllithium, allyllithium, and the like, or combinations thereof.
Olefin Monomers
Unsaturated reactants that can be employed with catalyst compositions and polymerization processes of this invention typically can include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. This invention encompasses homopolymerization 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 resultant ethylene copolymers, terpolymers, etc., generally can contain a major amount of ethylene (>50 mole percent) and a minor amount of comonomer (<50 mole percent), though this is not a requirement. Comonomers that can be copolymerized with ethylene often can have from 3 to 20 carbon atoms in their molecular chain.
Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins can be employed in this invention. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention can include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes (e.g., 1-octene), the four normal nonenes, the five normal decenes, and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, also can be polymerized as described above. Styrene can also be employed as a monomer in the present invention. In an aspect, the olefin monomer can comprise a C2-C10 olefin; alternatively, the olefin monomer can comprise ethylene; or alternatively, the olefin monomer can comprise propylene.
When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer can 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 can comprise ethylene. In this aspect, examples of suitable olefin comonomers an include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, or combinations thereof. According to one aspect of the present invention, the comonomer can comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; or alternatively, 1-butene, 1-hexene, 1-octene, or any combination thereof.
Generally, the amount of comonomer introduced into a reactor zone to produce a copolymer can be from 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 can be from about 0.01 to about 40 weight percent comonomer based on the total weight of the monomer and comonomer. In still another aspect, the amount of comonomer introduced into a reactor zone can be from about 0.1 to about 35 weight percent comonomer based on the total weight of the monomer and comonomer. Yet, in another aspect, the amount of comonomer introduced into a reactor zone can be from about 0.5 to about 20 weight percent comonomer based on the total weight of the monomer and comonomer.
While not intending to be bound by this theory, where branched, substituted, or functionalized olefins are used as reactants, it is believed that a steric hindrance can impede and/or slow the polymerization process. Thus, branched and/or cyclic portion(s) of the olefin removed somewhat from the carbon-carbon double bond would not be expected to hinder the reaction in the way that the same olefin substituents situated more proximate to the carbon-carbon double bond might. According to one aspect of the present invention, at least one monomer/reactant can be ethylene, so the polymerizations are either a homopolymerization involving only ethylene, or copolymerizations with a different acyclic, cyclic, terminal, internal, linear, branched, substituted, or unsubstituted olefin. 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.
Catalyst Compositions
In some aspects, the present invention employs catalyst compositions containing catalyst component I, catalyst component II, and an activator (one or more than one). These catalyst compositions can be utilized to produce polyolefins—homopolymers, copolymers, and the like—for a variety of end-use applications. Catalyst component I and catalyst component II are discussed hereinabove. In aspects of the present invention, it is contemplated that the catalyst composition can contain more than one catalyst component I metallocene compound and/or more than one catalyst component II half-metallocene compound. Further, additional catalytic compounds—other than those specified as catalyst component I or catalyst component II—can be employed in the catalyst compositions and/or the polymerization processes, provided that the additional catalytic compound(s) does not detract from the advantages disclosed herein. Additionally, more than one activator also may be utilized.
The metallocene compounds of catalyst component I are discussed above. For instance, in some aspects, catalyst component I can comprise (or consist essentially of, or consist of) an unbridged metallocene compound having formula (IA), a bridged metallocene compound having formula (IB), or combinations thereof. The half-metallocene compounds of catalyst component II also are discussed above. For instance, in some aspects, catalyst component II can comprise (or consist essentially of, or consist of) a half-metallocene compound having formula (IIA).
Generally, catalyst compositions of the present invention comprise catalyst component I, catalyst component II, and an activator. In aspects of the invention, the activator can comprise an activator-support (e.g., an activator-support comprising a solid oxide treated with an electron-withdrawing anion). Activator-supports useful in the present invention are disclosed above. Optionally, such catalyst compositions can further comprise one or more than one co-catalyst compound or compounds (suitable co-catalysts, such as organoaluminum compounds, also are discussed above). Thus, a catalyst composition of this invention can comprise catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound. For instance, the activator-support can comprise (or consist essentially of, or consist of) fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, or combinations thereof. Additionally, the organoaluminum compound can comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof. Accordingly, a catalyst composition consistent with aspects of the invention can comprise (or consist essentially of, or consist of) a zirconium or hafnium based metallocene compound, a titanium based half-metallocene compound containing an indenyl group, sulfated alumina (or fluorided silica-alumina, or fluorided silica-coated alumina), and triethylaluminum (or triisobutylaluminum).
In another aspect of the present invention, a catalyst composition is provided which comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and/or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, substantially free or organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has catalyst activity, to be discussed below, in the absence of these additional materials. For example, a catalyst composition of the present invention can consist essentially of catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound, wherein no other materials are present in the catalyst composition which would increase/decrease the activity of the catalyst composition by more than about 10% from the catalyst activity of the catalyst composition in the absence of said materials.
However, in other aspects of this invention, these activators/co-catalysts can be employed. For example, a catalyst composition comprising catalyst component I, catalyst component II, and an activator-support can further comprise an optional co-catalyst. Suitable co-catalysts in this aspect can include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, or any combination thereof; or alternatively, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, or any combination thereof. More than one co-catalyst can be present in the catalyst composition.
In a different aspect, a catalyst composition is provided which does not require an activator-support. Such a catalyst composition can comprise catalyst component I, catalyst component II, and an activator, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.
In a particular aspect contemplated herein, the catalyst composition is a dual catalyst composition comprising an activator (one or more than one), only one catalyst component I metallocene compound, and only one catalyst component II half-metallocene compound. In these and other aspects, the catalyst composition can comprise an activator (e.g., an activator-support comprising a solid oxide treated with an electron-withdrawing anion); only one zirconium or hafnium based metallocene compound (e.g., having formula (IA) or formula (IB)); and only titanium based half-metallocene compound containing an indenyl group (e.g., having formula (IIA)).
This invention further encompasses methods of making these catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
Catalyst component I, catalyst component II, or both, can be precontacted with an olefinic monomer if desired, not necessarily the olefin monomer to be polymerized, and an organoaluminum compound for a first period of time prior to contacting this precontacted mixture with an activator-support. The first period of time for contact, the precontact time, between the metallocene and/or half-metallocene compound(s), the olefinic monomer, and the organoaluminum compound typically ranges from a time period of about 1 minute to about 24 hours, for example, from about 3 minutes to about 1 hour. Precontact times from about 10 minutes to about 30 minutes also can be employed. Alternatively, the precontacting process can be carried out in multiple steps, rather than a single step, in which multiple mixtures can be prepared, each comprising a different set of catalyst components. For example, at least two catalyst components can be contacted forming a first mixture, followed by contacting the first mixture with at least one other catalyst component forming a second mixture, and so forth.
Multiple precontacting steps can be carried out in a single vessel or in multiple vessels. Further, multiple precontacting steps can be carried out in series (sequentially), in parallel, or a combination thereof. For example, a first mixture of two catalyst components can be formed in a first vessel, a second mixture comprising the first mixture plus one additional catalyst component can be formed in the first vessel or in a second vessel, which is typically placed downstream of the first vessel.
In another aspect, one or more of the catalyst components can be split and used in different precontacting treatments. For example, part of a catalyst component can be fed into a first precontacting vessel for precontacting with at least one other catalyst component, while the remainder of that same catalyst component can be fed into a second precontacting vessel for precontacting with at least one other catalyst component, or can be fed directly into the reactor, or a combination thereof. The precontacting can be carried out in any suitable equipment, such as tanks, stirred mix tanks, various static mixing devices, a flask, a vessel of any type, or combinations of these apparatus.
In another aspect of this invention, the various catalyst components (for example, a zirconium or hafnium based metallocene compound, a titanium based half-metallocene containing an indenyl group, an activator-support, an organoaluminum co-catalyst, and optionally an unsaturated hydrocarbon) can be contacted in the polymerization reactor simultaneously while the polymerization reaction is proceeding. Alternatively, any two or more of these catalyst components can be precontacted in a vessel prior to entering the reaction zone. This precontacting step can be continuous, in which the precontacted product can be fed continuously to the reactor, or it can be a stepwise or batchwise process in which a batch of precontacted product can be added to make a catalyst composition. This precontacting step can be carried out over a time period that can range from a few seconds to as much as several days, or longer. In this aspect, the continuous precontacting step generally can last from about 1 second to about 1 hour. In another aspect, the continuous precontacting step can last from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.
Once the precontacted mixture of catalyst component I and/or catalyst component II, the olefin monomer, and the organoaluminum co-catalyst is contacted with the activator-support, this composition (with the addition of the activator-support) can be termed the “postcontacted mixture.” The postcontacted mixture optionally can remain in contact for a second period of time, the postcontact time, prior to initiating the polymerization process. Postcontact times between the precontacted mixture and the activator-support generally range from about 1 minute to about 24 hours. In a further aspect, the postcontact time can be in a range from about 3 minutes to about 1 hour. The precontacting step, the postcontacting step, or both, can increase the productivity of the polymer as compared to the same catalyst composition that is prepared without precontacting or postcontacting. However, neither a precontacting step nor a postcontacting step is required.
The postcontacted mixture can be heated at a temperature and for a time period sufficient to allow adsorption, impregnation, or interaction of precontacted mixture and the activator-support, such that a portion of the components of the precontacted mixture can be immobilized, adsorbed, or deposited thereon. Where heating is employed, the postcontacted mixture generally can be heated to a temperature of from between about 0° F. to about 150° F., or from about 40° F. to about 95° F.
According to one aspect of this invention, the weight ratio of catalyst component I to catalyst component II generally can be in a range from about 20:1 to about 1:20. In another aspect, the weight ratio can be in a range from about 10:1 to about 1:10, from about 10:1 to about 1:8, or from about 10:1 to about 1:5. Yet, in another aspect, the weight ratio can be in a range from about 8:1 to about 1:8, from about 8:1 to about 1:5, from about 8:1 to about 1:4, from about 5:1 to about 1:5; from about 4:1 to about 1:4, from about 3:1 to about 1:3, from about 2:1 to about 1:2, from about 1.5:1 to about 1:1.5, from about 1.25:1 to about 1:1.25, or from about 1.1:1 to about 1:1.1.
When a precontacting step is used, the molar ratio of the total moles of olefin monomer to total moles of metallocene(s) in the precontacted mixture typically can be in a range from about 1:10 to about 100,000:1. Total moles of each component are used in this ratio to account for aspects of this invention where more than one olefin monomer and/or more than one metallocene and/or half-metallocene compound is employed in a precontacting step. Further, 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 organoaluminum compound to activator-support can be in a range from about 10:1 to about 1:1000. If more than one organoaluminum compound and/or more than one activator-support is employed, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminum compound to the activator-support can be 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 metallocene-type compounds (total of catalyst component I and catalyst component II) to activator-support can be in a range from about 1:1 to about 1:1,000,000. If more than one activator-support is employed, this ratio is based on the total weight of the activator-support. In another aspect, this weight ratio can be in a range from about 1:5 to about 1:100,000, or from about 1:10 to about 1:10,000. Yet, in another aspect, the weight ratio of the metallocene-type compounds to the activator-support can be in a range from about 1:20 to about 1:1000.
Catalyst compositions 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 activator-support per hour (abbreviated g/g/hr). In another aspect, the catalyst activity can greater than about 150, greater than about 250, or greater than about 500 g/g/hr. In still another aspect, catalyst compositions of this invention can be characterized by having a catalyst activity greater than about 550, greater than about 650, or greater than about 750 g/g/hr. Yet, in another aspect, the catalyst activity can be greater than about 1000 g/g/hr. These activities are measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90° C. and a reactor pressure of about 390 psig. Generally, the reactor pressure is largely controlled by the pressure of the monomer, but other contributors to the reactor pressure can include hydrogen (if hydrogen is used), isobutane vapor, and comonomer gas or vapor (if comonomer is used). Moreover, such catalyst activities can be achieved when the catalyst composition contains a co-catalyst, such as an organoaluminum compound (e.g., triethylaluminum, triisobutylaluminum, etc.). Additionally, in some aspects, the activator-support can comprise sulfated alumina, fluorided silica-alumina, or fluorided silica-coated alumina, although not limited thereto.
As discussed above, any combination of catalyst component I, catalyst component II, the activator-support, the organoaluminum compound, and the olefin monomer, can be precontacted in some aspects of this invention. When any precontacting occurs with an olefinic monomer, it is not necessary that the olefin monomer used in the precontacting step be the same as the olefin to be polymerized. Further, when a precontacting step among any combination of the catalyst components is employed for a first period of time, this precontacted mixture can be used in a subsequent postcontacting step between any other combination of catalyst components for a second period of time. For example, one or more metallocene compounds, the organoaluminum compound, and 1-hexene can be used in a precontacting step for a first period of time, and this precontacted mixture then can be contacted with the activator-support to form a postcontacted mixture that can be contacted for a second period of time prior to initiating the polymerization reaction. For example, the first period of time for contact, the precontact time, between any combination of the metallocene-type compound(s), the olefinic monomer, the activator-support, and the organoaluminum compound can be from about 1 minute to about 24 hours, from about 3 minutes to about 1 hour, or from about 10 minutes to about 30 minutes. The postcontacted mixture optionally can be allowed to remain in contact for a second period of time, the postcontact time, prior to initiating the polymerization process. According to one aspect of this invention, postcontact times between the precontacted mixture and any remaining catalyst components can be from about 1 minute to about 24 hours, or from about 5 minutes to about 1 hour.
Polymerization Processes
Catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like. One such process for polymerizing olefins in the presence of a catalyst composition of the present invention can comprise contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer (one or more) under polymerization conditions to produce an olefin polymer, wherein the catalyst composition can comprise catalyst component I, catalyst component II, an activator, and an optional co-catalyst. Catalyst components I and II are discussed above. For instance, catalyst component I can comprise an unbridged metallocene compound having formula (IA), a bridged metallocene compound having formula (IB), or combinations thereof. Catalyst component II can comprise, for instance, a half-metallocene compound having formula (IIA).
In accordance with one aspect of the invention, the polymerization process can employ a catalyst composition comprising catalyst component I, catalyst component II, and an activator, wherein the activator comprises an activator-support. Activator-supports useful in the polymerization processes of the present invention are disclosed above. The catalyst composition, optionally, can further comprise one or more than one organoaluminum compound or compounds (or other suitable co-catalyst). Thus, a process for polymerizing olefins in the presence of a catalyst composition can employ a catalyst composition comprising catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound. In some aspects, the activator-support can comprise (or consist essentially of, or consist of) fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, or combinations thereof. In some aspects, the organoaluminum compound can comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof.
In accordance with another aspect of the invention, the polymerization process can employ a catalyst composition comprising catalyst component I, catalyst component II, an activator-support, and an optional co-catalyst, wherein the co-catalyst can comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, or an organolithium compound, or any combination thereof. Hence, aspects of this invention are directed to a process for polymerizing olefins in the presence of a catalyst composition, the processes comprising contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer (one or more) under polymerization conditions to produce an olefin polymer, and the catalyst composition can comprise catalyst component I, catalyst component II, an activator-support, and an aluminoxane compound; alternatively, catalyst component I, catalyst component II, an activator-support, and an organoboron or organoborate compound; alternatively, catalyst component I, catalyst component II, an activator-support, and an ionizing ionic compound; alternatively, catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound; alternatively, catalyst component I, catalyst component II, an activator-support, and an organozinc compound; alternatively, catalyst component I, catalyst component II, an activator-support, and an organomagnesium compound; or alternatively, catalyst component I, catalyst component II, an activator-support, and an organolithium compound. Furthermore, more than one co-catalyst can be employed, e.g., an organoaluminum compound and an aluminoxane compound, an organoaluminum compound and an ionizing ionic compound, etc.
In accordance with another aspect of the invention, the polymerization process can employ a catalyst composition comprising only one catalyst component I metallocene compound, only one catalyst component II half-metallocene compound, an activator-support, and an organoaluminum compound.
In accordance with another aspect of the invention, the polymerization process can employ a catalyst composition comprising catalyst component I, catalyst component II, and an activator, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.
The catalyst compositions of the present invention are intended for any olefin polymerization method using various types of polymerization reactors. As used herein, “polymerization reactor” includes any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of reactors include those that can be referred to as a batch reactor, slurry reactor, gas-phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations thereof. The polymerization conditions for the various reactor types are well known to those of skill in the art. Gas phase reactors can comprise fluidized bed reactors or staged horizontal reactors. Slurry reactors can comprise vertical or horizontal loops. High pressure reactors can comprise autoclave or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes could use intermittent or continuous product discharge. Processes can also include partial or full direct recycle of unreacted monomer, unreacted comonomer, and/or diluent.
Polymerization reactor systems of the present invention can comprise one type of reactor in a system or multiple reactors of the same or different type. 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 into the second reactor. The desired polymerization conditions in one of the reactors can be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors can include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization. Multiple reactor systems can include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure with loop and/or gas phase reactors. The multiple reactors can be operated in series, in parallel, or both.
According to one aspect of the invention, the polymerization reactor system can comprise at least one loop slurry reactor comprising vertical or horizontal loops. Monomer, diluent, catalyst, and comonomer can be continuously fed to a loop reactor where polymerization occurs. Generally, continuous processes can comprise the continuous introduction of monomer/comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent. Reactor effluent can be flashed 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, flashing that can include any combination of heat addition and pressure reduction, separation by cyclonic action in either 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 U.S. Pat. Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415, each of which is incorporated herein by reference in its entirety.
Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquids 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 loop polymerization reactions can occur under bulk conditions where no diluent is used. An example is polymerization of propylene monomer as disclosed in U.S. Pat. No. 5,455,314, which is incorporated by reference herein in its entirety.
According to yet another aspect of this invention, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream can be withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product can be withdrawn from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for multi-step gas-phase polymerization of olefins, in which olefins are polymerized in the gaseous phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and 5,436,304, each of which is incorporated by reference in its entirety herein.
According to still 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 where fresh monomer, initiators, or catalysts are added. Monomer can be entrained in an inert gaseous stream and introduced at one zone of the reactor. Initiators, catalysts, and/or catalyst components can be entrained in a gaseous stream and introduced at another zone of the reactor. The gas streams can be intermixed for polymerization. Heat and pressure can be employed appropriately to obtain optimal polymerization reaction conditions.
According to yet another aspect of the invention, the polymerization reactor can comprise a solution polymerization reactor wherein the monomer/comonomer are contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer/comonomer can be brought in the vapor phase into 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 solution of the polymer in a reaction medium. Agitation can be employed to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Adequate means are utilized for dissipating the exothermic heat of polymerization.
Polymerization reactors suitable for the present invention can 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. Suitable reactor systems for the present invention can further comprise systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycle, storage, loadout, laboratory analysis, and process control.
Polymerization conditions that are controlled for efficiency and to provide desired polymer properties can include temperature, pressure, and the concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. A suitable polymerization temperature can be any temperature below the de-polymerization temperature according to the Gibbs Free energy equation. Typically, this includes from about 60° C. to about 280° C., for example, or from about 60° C. to about 120° C., depending upon the type of polymerization reactor. In some reactor systems, the polymerization temperature generally can fall within a range from about 70° C. to about 100° C., or from about 75° C. to about 95° C.
Suitable pressures will also vary according to the reactor and polymerization type. The pressure for liquid phase polymerizations in a loop reactor is typically less than 1000 psig (6.9 MPa). Pressure for gas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to 3.4 MPa). High pressure polymerization in tubular or autoclave reactors is generally run at about 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also be operated in a supercritical region occurring at generally higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) may offer advantages.
Aspects of this invention are directed to olefin polymerization processes comprising contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer. The olefin polymer (e.g., ethylene polymer) produced by the process can have, for example, a ratio of Mw/Mn in a range from about 4 to about 35, and/or a ratio of Mz/Mw in a range from about 3 to about 15, and/or a Mw in a range from about 100,000 to about 400,000 g/mol, and/or a Mn in a range from about 8,000 to about 30,000 g/mol, and/or a Mz greater than about 1,000,000 g/mol, and/or a density greater than about 0.92 g/cm3, and/or a melt index less than about 5 g/10 min, and/or a ratio of HLMI to MI in a range from about 30 to about 300, and/or less than about 0.008 long chain branches per 1000 total carbon atoms, and/or a zero-shear viscosity at 190° C. in a range from about 1×105 to about 1×107 Pa-sec.
Aspects of this invention also are directed to olefin polymerization processes conducted in the absence of added hydrogen. An olefin polymerization process of this invention can comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition can comprise catalyst component I, catalyst component II, an activator, and an optional co-catalyst, wherein the polymerization process is conducted in the absence of added hydrogen. As one of ordinary skill in the art would recognize, hydrogen can be generated in-situ by metallocene catalyst compositions in various olefin polymerization processes, and the amount generated can vary depending upon the specific catalyst composition and metallocene compound(s) employed, the type of polymerization process used, the polymerization reaction conditions utilized, and so forth.
In other aspects, it may be desirable to conduct the polymerization process in the presence of a certain amount of added hydrogen. Accordingly, an olefin polymerization process of this invention can comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator, and an optional co-catalyst, wherein the polymerization process is conducted in the presence of added hydrogen. For example, the ratio of hydrogen to the olefin monomer in the polymerization process can be controlled, often by the feed ratio of hydrogen to the olefin monomer entering the reactor. The added hydrogen to olefin monomer ratio in the process can be controlled at a weight ratio which falls within a range from about 25 ppm to about 1500 ppm, from about 50 to about 1000 ppm, or from about 100 ppm to about 750 ppm.
In some aspects of this invention, the feed or reactant ratio of hydrogen to olefin monomer can be maintained substantially constant during the polymerization run for a particular polymer grade. That is, the hydrogen:olefin monomer ratio can be selected at a particular ratio within a range from about 5 ppm up to about 1000 ppm or so, and maintained at the ratio to within about +/−25% during the polymerization run. For instance, if the target ratio is 100 ppm, then maintaining the hydrogen:olefin monomer ratio substantially constant would entail maintaining the feed ratio between about 75 ppm and about 125 ppm. Further, the addition of comonomer (or comonomers) can be, and generally is, substantially constant throughout the polymerization run for a particular polymer grade.
However, in other aspects, it is contemplated that monomer, comonomer (or comonomers), and/or hydrogen can be periodically pulsed to the reactor, for instance, in a manner similar to that employed in U.S. Pat. No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, the disclosures of which are incorporated herein by reference in their entirety.
The concentration of the reactants 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 ultimately can determine the desired polymer properties and attributes. Mechanical properties include tensile, flexural, impact, creep, stress relaxation, and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, temperature melt of crystallization, density, stereoregularity, crack growth, long chain branching, and rheological measurements.
This invention is also directed to, and encompasses, the polymers produced by any of the polymerization processes disclosed herein. Articles of manufacture can be formed from, and/or can comprise, the polymers produced in accordance with this invention.
Polymers and Articles
If the resultant polymer produced in accordance with the present invention is, for example, a polymer or copolymer of ethylene, its properties can be characterized by various analytical techniques known and used in the polyolefin industry. Articles of manufacture can be formed from, and/or can comprise, the ethylene polymers of this invention, whose typical properties are provided below.
Polymers of ethylene (homopolymers, copolymers, terpolymers, etc.) produced in accordance with some aspects of this invention generally can have a melt index (MI) from 0 to about 100 g/10 min. Melt indices in the range from 0 to about 50 g/10 min, from 0 to about 10 g/10 min, or from 0 to about 5 g/10 min, are contemplated in other aspects of this invention. For example, a polymer of the present invention can have a melt index in a range from 0 to about 4, from about 0.01 to about 5, from about 0.1 to about 5, from about 0.01 to about 4, from about 0.1 to about 4, from about 0.01 to about 3, or from about 0.1 to about 3 g/10 min.
Ethylene polymers produced in accordance with this invention can have a ratio of HLMI/MI of greater than about 30, such as, for example, in a range from about 30 to about 350, from about 30 to about 300, or from about 30 to about 350. Other suitable ranges for HLMI/MI can include, but are not limited to, from about 35 to about 300, from about 35 to about 250, from about 40 to about 300, from about 40 to about 275, from about 40 to about 250, or from about 40 to about 200, and the like.
The densities of ethylene-based polymers produced using the catalyst systems and processes disclosed herein often are greater than about 0.90 g/cm3. In one aspect of this invention, the density of an ethylene polymer can be greater than about 0.91, greater than about 0.92, or greater than about 0.93 g/cm3. Yet, in another aspect, the density can be in a range from about 0.90 to about 0.97 g/cm3, such as, for example, from about 0.91 to about 0.96 g/cm3, from about 0.92 to about 0.96 g/cm3, or from about 0.93 to about 0.95 g/cm3.
Ethylene polymers, such as homopolymers, copolymers, and terpolymers, consistent with various aspects of the present invention generally can have a broad molecular weight distribution, and often with a high molecular weight tail. Typical weight-average molecular weights (Mw's) of these polymers can be, for instance, in a range from 100,000 to about 500,000 g/mol, from about 100,000 to about 400,000 g/mol, from about 100,000 to about 300,000 g/mol, from about 125,000 to about 400,000 g/mol, or from about 150,000 to about 300,000 g/mol. Likewise, suitable non-limiting ranges of the number-average molecular weight (Mn) can include from about 7,000 to about 35,000 g/mol, from about 8,000 to about 30,000 g/mol, from about 8,000 to about 28,000 g/mol, from about 8,000 to about 25,000 g/mol, or from about 9,000 to about 25,000 g/mol. Moreover, the z-average molecular weight (Mz) of these polymers often can be greater than about 1,000,000 g/mol, and more often, greater than about 1,500,000 g/mol. Contemplated Mz ranges encompassed by the present invention can include, but are not limited to, from about 1,000,000 to about 5,000,000 g/mol, from about 1,000,000 to about 4,000,000 g/mol, from about 1,000,000 to about 3,000,000 g/mol, from about 1,500,000 to about 3,500,000 g/mol, or from about 1,500,000 to about 3,000,000 g/mol.
The ratio of Mw/Mn, or the polydispersity index, for the polymers of this invention often can be in a range from about 4 to about 40. In some aspects disclosed herein, the ratio of Mw/Mn can be in a range from about 4 to about 35, from about 5 to about 30, or from about 8 to about 25. In other aspects, the ratio of Mw/Mn can be in a range from about 6 to about 35, from about 7 to about 35, or from about 7 to about 30. The ratio of Mz/Mw for the polymers of this invention often can in a range from about 3 to about 15. For example, the Mz/Mw ratio can be in a range from about 5 to about 14, from about 6 to about 15, from about 7 to about 14, or from about 8 to about 13.
Olefin polymers disclosed herein, in certain aspects, can have a zero-shear viscosity at 190° C. which falls within a range from about 1×105 to about 1×107 Pa-sec. For example, the zero-shear viscosity of the polymer can be in a range from about 5×105 to about 5×106 Pa-sec, or from about 7×105 to 3×106 Pa-sec.
Generally, polymers produced in aspects of the present invention have low levels of long chain branching, with typically less than about 0.01 long chain branches (LCB) per 1000 total carbon atoms, but greater than zero. In some aspects, the number of LCB per 1000 total carbon atoms can be less than about 0.008, less than about 0.007, less than about 0.006, or less than about 0.005 LCB per 1000 total carbon atoms.
Certain ethylene polymers (e.g., certain copolymers) produced using the polymerization processes and catalyst systems described above can have a conventional comonomer distribution, i.e., a short chain branch content that decreases as molecular weight increases, for example, the higher molecular weight components of the polymer generally have lower comonomer incorporation than the lower molecular weight components. Typically, there is decreasing comonomer incorporation with increasing molecular weight. Often, the amount of comonomer incorporation at higher molecular weights can be about 20% lower, or about 30% lower, or about 50% lower, or about 70% lower, or about 90% lower, than at lower molecular weights. For instance, the number of short chain branches (SCB's) per 1000 total carbon atoms can be greater at Mn than at Mw. Ethylene polymers of this invention can have a SCBD (short chain branching distribution) that is similar to the SCBD found in ethylene polymers produced using traditional Ziegler-Natta catalyst systems (i.e., a conventional comonomer distribution).
An illustrative and non-limiting example of an ethylene polymer of the present invention can be characterized by a ratio of Mw/Mn in a range from about 4 to about 35, and/or a ratio of Mz/Mw in a range from about 3 to about 15, and/or a Mw in a range from about 100,000 to about 400,000 g/mol, and/or a Mn in a range from about 8,000 to about 30,000 g/mol, and/or a Mz greater than about 1,000,000 g/mol, and/or a density greater than about 0.92 g/cm3, and/or a melt index less than about 5 g/10 min, and/or a ratio of HLMI to MI in a range from about 30 to about 300, and/or less than about 0.008 long chain branches per 1000 total carbon atoms, and/or a zero-shear viscosity at 190° C. in a range from about 1×105 to about 1×107 Pa-sec.
Polymers of ethylene, whether homopolymers, copolymers, terpolymers, and so forth, can be formed into various articles of manufacture. Articles which can comprise polymers of this invention include, but are not limited to, an agricultural film, an automobile part, a bottle, a drum, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, a liner, a molded product, a medical device or material, a pipe, a sheet or tape, a toy, and the like. Various processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. Additionally, additives and modifiers are often added to these polymers in order to provide beneficial polymer processing or end-use product attributes. Such processes and materials are described in Modern Plastics Encyclopedia, Mid-November 1995 Issue, Vol. 72, No. 12; and Film Extrusion Manual—Process, Materials, Properties, TAPPI Press, 1992; the disclosures of which are incorporated herein by reference in their entirety.
Applicants also contemplate a method for forming or preparing an article of manufacture comprising a polymer produced by any of the polymerization processes disclosed herein. For instance, a method can comprise (i) contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer (one or more) under polymerization conditions to produce an olefin polymer, wherein the catalyst composition can comprise catalyst component I (e.g., a zirconium or hafnium based unbridged metallocene compound), catalyst component II (e.g., a titanium based half metallocene compound containing an indenyl group), an activator (e.g., an activator-support comprising a solid oxide treated with an electron-withdrawing anion), and an optional co-catalyst (e.g., an organoaluminum compound); and (ii) forming an article of manufacture comprising the olefin polymer. The forming step can comprise blending, melt processing, extruding, molding, or thermoforming, and the like, including combinations thereof.
EXAMPLES
The invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations to the scope of this invention. Various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims.
Melt index (MI, g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a 2,160 gram weight. High load melt index (HLMI, g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a 21,600 gram weight.
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 1.0 mL/minute at a temperature of 145° C. BHT (2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g/L was used as a stabilizer in the TCB. An injection volume of 400 μL was used with a nominal polymer concentration of 1.5 mg/mL. 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 were three Waters Styragel HMW-6E columns (7.8×300 mm) and were calibrated with a broad linear polyethylene standard (Phillips Marlex® BHB 5003) for which the molecular weight had been determined
Samples for melt viscosity measurement were compression molded at 182° C. for a total of 3 min: the samples were allowed to melt at a relatively low pressure for 1 min and then subjected to a high molding pressure for additional 2 min. The molded samples were then quenched in a cold (room temperature) press. Approximate 2 mm×25.4 mm diameter disks were stamped out of the molded slabs for rheological characterization. The fluff samples were stabilized with 0.1 wt. % BHT dispersed in acetone and vacuum dried before molding.
Small-strain oscillatory shear measurements were performed on an ARES rheometer (Rheometrics Inc., now TA Instruments) using parallel-plate geometry. The test chamber of the rheometer was blanketed in nitrogen in order to minimize polymer degradation. Upon sample loading and after oven thermal equilibration, the specimens were squeezed between the plates to a 1.6 mm thickness, and the excess was trimmed. The dynamic shear viscosities were measured over an angular frequency range of 0.03-100 rad/s. The data were fit to the Carreau-Yasuda (C-Y) equation to determine zero-shear viscosity (η0) and other rheological parameters. The C-Y equation is::

|η*(ω)|=η0[1+(τηω)a](n−1)/a  (1)

where |η*(ω)| is the magnitude of complex shear viscosity; η0 is the zero-shear viscosity; τη is the viscous relaxation time; a is a breadth parameter; n is a parameter that fixes the final power law slope, which is fixed at 2/11 in these experiments; and ω is an angular frequency of oscillatory shear deformation.

Sulfated alumina activator-supports were prepared as follows. Bohemite was obtained from W.R. Grace & Company under the designation “Alumina A” and having a surface area of about 300 m2/g and a pore volume of about 1.3 mL/g. This material was obtained as a powder having an average particle size of about 100 microns. This material was impregnated to incipient wetness with an aqueous solution of ammonium sulfate to equal about 15% sulfate. This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 110° C. for about 16 hours. To calcine the resultant powdered mixture, the material was fluidized in a stream of dry air at about 550° C. for about 6 hours. Afterward, the sulfated alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
Examples 1-5
Dual Catalyst Polymerization Experiments
Polymerization experiments were conducted in a one-gallon (3.875-liter) stirred autoclave reactor. Hydrogen, when used, was added from a 325-cc auxiliary vessel, and the amount added was determined via the pressure drop (ΔP) in that vessel from 700 psig starting pressure. The reactor was maintained at the desired temperature throughout the experiment by an automated heating-cooling system. Solutions of the following metallocene and half-metallocene compounds were prepared by dissolving 20 mg of the respective compound in 20 mL of toluene:




Catalyst system components were added to the reactor under a purge of isobutane while the reactor temperature was below 40° C. In Example 1, 0.5 mL of a 25 wt. % solution of triisobutylaluminum in heptanes, 0.2 g of sulfated alumina, 0.5 mL of MET-A solution, and 1 mL of MET-2 solution were added to the reactor. The reactor was then sealed, 2 L of isobutane were added, and stirring was started at 700 rpm. Reactor heating was initiated, and as the reactor temperature approached 75° C., hydrogen (ΔP=26 psig) and ethylene (364 psig) were added. The target temperature of 90° C. was then rapidly attained. The reactor was held at 90° C. for 60 min, and ethylene was fed on demand to maintain 390 psig reactor pressure. At the end of the run, volatiles were removed, the reactor was cooled and opened, and the polymer product was collected and dried. Approximately 156 g of polyethylene were produced in Example 1.
Example 2 was performed using substantially the same procedure as in Example 1, except that hydrogen (ΔP=19 psig) and ethylene (405 psig) were added initially, and reactor pressure was controlled at 424 psig. Approximately 237 g of polyethylene were produced in Example 2.
Example 3 was performed using substantially the same procedure as in Example 2, except that 0.25 mL of MET-A solution (instead of 0.5 mL) were used. Approximately 148 g of polyethylene were produced in Example 3.
Example 4 was performed using substantially the same procedure as in Example 1, except that 1 mL of MET-A solution (instead of 0.5 mL), hydrogen (ΔP=17 psig), and ethylene (463 psig) were added initially, and the reactor temperature and reactor pressure were controlled at 100° C. and 480 psig, respectively. Approximately 219 g of polyethylene were produced in Example 4.
Example 5 was performed using substantially the same procedure as in Example 1, except that 1 mL of MET-B solution (instead of MET-A), 0.1 mL of MET-1 solution (instead of MET-2), hydrogen (ΔP=72 psig), and ethylene (414 psig) were added initially, and the reactor pressure was controlled at 486 psig. Approximately 220 g of polyethylene were produced in Example 5.
Table I summarizes certain properties of the polymers of Examples 1-5. In Table I, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, My is the viscosity-average molecular weight, Mp is the peak molecular weight, and 110 is the zero-shear viscosity at 190° C. in units of Pa-sec. FIG. 1 illustrates the molecular weight distributions (amount of polymer versus logarithm of molecular weight) for the polymers of Examples 1-4, FIG. 2 illustrates the molecular weight distribution for the polymer of Example 5, and FIG. 3 illustrates the viscosity at 190° C. in Pa-sec versus the frequency (rad/sec) for the polymer of Example 1.
As shown in Table I and FIG. 1, the polymers of Examples 1-4 had a broad molecular weight distribution (Mw/Mn's from 7 to 24) with a high molecular weight tail (Mz's from 1,700,000 to 2,500,000 g/mol), and large melt flow ratios (HLMI/MI from 40 to 205). While the Mn for these polymers was in a relatively narrow range of 9,000 to 21,000 g/mol, the ratio of Mz/Mw was relatively broad (from 8 to 12). Compared to the polymers of Examples 1-4, the polymer of Example 5 had a relatively narrow molecular weight distribution and a lower zero-shear viscosity.
Examples 6-8
Dual Catalyst Polymerization Experiments with MET-B and Cyclopentadienyl Titanium Trichloride
In Example 6, 0.5 mL of a 25 wt. % solution of triisobutylaluminum in heptanes, 0.2 g of sulfated alumina, 0.5 mL of MET-B solution, and 26 grams of 1-hexene were added to the reactor. The reactor was then sealed, 2 L of isobutane were added, and stirring was started at 700 rpm. Reactor heating was initiated, and as the reactor temperature approached 70° C., hydrogen (ΔP=16 psig) and ethylene (291 psig) were added. The target temperature of 80° C. was then rapidly attained. The reactor was held at 80° C. for 60 min, and ethylene was fed on demand to maintain 291 psig reactor pressure. At the end of the run, volatiles were removed, the reactor was cooled and opened, and the polymer product was collected and dried. Approximately 198 g of polymer were produced.
Examples 7-8 utilized a dual catalyst system with MET-B and CpTiCl3 (cyclopentadienyl titanium trichloride), and these were performed using substantially the same procedure as in Example 6. The weight ratio of MET-B to CpTiCl3 was 2:1 for Example 7, and the weight ratio of MET-B to CpTiCl3 was 1:1 in Example 8.
Table II summarizes certain properties of the polymers of Examples 6-8, and FIG. 4 illustrates the molecular weight distributions of the polymers of Examples 6-8. As shown in Table II and FIG. 4, the addition of CpTiCl3 to the catalyst system increased both Mw and Mn, but there was no appreciable impact on the breadth of the molecular weight distribution, as demonstrated by the ratio of Mw/Mn.







TABLE I





Polymer Properties of Examples 1-5.





















Mn/1000
Mw/1000
Mz/1000
Mv/1000
Mp/1000


Example
(g/mol)
(g/mol)
(g/mol)
(g/mol)
(g/mol)





1
9.1
219
1956
146
53.5


2
21.2
211
1992
150
63.3


3
15.3
305
2500
207
105.3


4
19.7
146
1788
104
54.3


5
26.0
126
381
105
80.1

















Mw/
Mz/
MI
HLMI

η0


Example
Mn
Mw
(g/10 min)
(g/10 min)
HLMI/MI
(Pa-sec)





1
24.0
8.9
0.21
36.7
174
1.08E+06


2
10.0
9.4
0.26
17.4
67
—


3
20.0
8.2
0.10
20.5
205
—


4
7.4
12.3
2.01
83.6
42
—


5
4.8
3.0
1.12
49.6
44
1.46E+04
















TABLE II





Polymer Properties of Examples 6-8.





















Mn/1000
Mw/1000
Mz/1000
Mv/1000
Mp/1000


Example
(g/mol)
(g/mol)
(g/mol)
(g/mol)
(g/mol)





6
37.1
91
172
82
72.8


7
49.3
135
336
120
100.9


8
62.7
150
278
137
121.7








MI
HLMI


Example
Mw/Mn
Mz/Mw
(g/10 min)
(g/10 min)
HLMI/MI





6
2.45
1.9
1.81
37.9
20.9


7
2.74
2.7
1.03
25.9
25.2


8
2.40
1.9
0.23
6.7
29.1









The invention has been described above with reference to numerous aspects and embodiments, and specific examples. Many variations will suggest themselves to those skilled in the art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. Other embodiments of the invention can include, but are not limited to, the following:
Embodiment 1. A catalyst composition comprising catalyst component I, catalyst component II, an activator, and an optional co-catalyst, wherein catalyst component I comprises a zirconium or hafnium based metallocene compound, and catalyst component II comprises a titanium based half-metallocene compound containing an indenyl group.
Embodiment 2. The composition defined in embodiment 1, wherein the activator comprises any activator disclosed herein.
Embodiment 3. The composition defined in any one of embodiments 1-2, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
Embodiment 4. The composition defined in any one of embodiments 1-2, wherein the activator comprises an activator-support, the activator-support comprising any solid oxide treated with an electron-withdrawing anion disclosed herein.
Embodiment 5. The composition defined in embodiment 4, wherein the solid oxide comprises any solid oxide disclosed herein, e.g., silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; and the electron-withdrawing anion comprises any electron-withdrawing anion disclosed herein, e.g., sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or any combination thereof.
Embodiment 6. The composition defined in embodiment 4, wherein the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.
Embodiment 7. The composition defined in embodiment 4, wherein the activator-support comprises fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof.
Embodiment 8. The composition defined in embodiment 4, wherein the activator-support further comprises any metal or metal ion disclosed herein, e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, or any combination thereof.
Embodiment 9. The composition defined in any one of embodiments 1-2, wherein the activator comprises an activator-support, the activator-support comprising a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non-layered aluminosilicate mineral, or any combination thereof.
Embodiment 10. The composition defined in any one of embodiments 1-9, wherein the co-catalyst comprises any co-catalyst disclosed herein.
Embodiment 11. The composition defined in any one of embodiments 1-10, wherein the co-catalyst comprises an organoaluminum compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.
Embodiment 12. The composition defined in any one of embodiments 1-2, wherein the catalyst composition comprises catalyst component I, catalyst component II, a solid oxide treated with an electron-withdrawing anion, and an organoaluminum compound.
Embodiment 13. The composition defined in embodiment 12, wherein the organoaluminum compound comprises any organoaluminum compound disclosed herein, e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum, etc., or combinations thereof; and the solid oxide treated with an electron-withdrawing anion comprises any solid oxide treated with an electron-withdrawing anion disclosed herein, e.g., fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, etc., or combinations thereof.
Embodiment 14. The composition defined in any one of embodiments 4-13, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.
Embodiment 15. The composition defined in any one of embodiments 1-14, wherein the catalyst composition comprises only one zirconium or hafnium based metallocene compound, and only one titanium based half-metallocene compound containing an indenyl group.
Embodiment 16. The composition defined in any one of embodiments 1-15, wherein catalyst component II comprises any titanium based half-metallocene compound containing an indenyl group disclosed herein, e.g., having formula (IIA):




wherein InA is a substituted or unsubstituted indenyl group, and X1, X2, and X3 independently are a monoanionic ligand.

Embodiment 17. The composition defined in embodiment 16, wherein InA is a substituted indenyl group with any number of substituents disclosed herein, e.g., one substituent, two substituents, etc.
Embodiment 18. The composition defined in any one of embodiments 16-17, wherein each substituent on InA independently is any substituent disclosed herein, e.g., H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group.
Embodiment 19. The composition defined in any one of embodiments 16-18, wherein each substituent on InA independently is any C1 to C12 hydrocarbyl group or C1 to C12 hydrocarbylsilyl group disclosed herein.
Embodiment 20. The composition defined in any one of embodiments 16-19, wherein each substituent on InA independently is H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group.
Embodiment 21. The composition defined in embodiment 16, wherein InA is an unsubstituted indenyl group.
Embodiment 22. The composition defined in any one of embodiments 16-21, wherein X1, X2, and X3 independently are any monoanionic ligand disclosed herein.
Embodiment 23. The composition defined in any one of embodiments 16-22, wherein X1, X2, and X3 independently are H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group.
Embodiment 24. The composition defined in any one of embodiments 16-23, wherein X1, X2, and X3 independently are any halide or C1 to C18 hydrocarbyl group disclosed herein.
Embodiment 25. The composition defined in any one of embodiments 16-24, wherein X1, X2, and X3 are Cl.
Embodiment 26. The composition defined in any one of embodiments 1-25, wherein catalyst component I comprises any zirconium or hafnium based metallocene compound disclosed herein.
Embodiment 27. The composition defined in any one of embodiments 1-26, wherein catalyst component I comprises an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group.
Embodiment 28. The composition defined in any one of embodiments 1-27, wherein catalyst component I comprises an unbridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group.
Embodiment 29. The composition defined in any one of embodiments 1-28, wherein catalyst component I comprises an unbridged metallocene compound having formula (IA):




wherein M is Zr or Hf, CpA and CpB independently are a substituted or unsubstituted cyclopentadienyl or indenyl group, and X4 and X5 independently are a monoanionic ligand.

Embodiment 30. The composition defined in embodiment 29, wherein M is Zr.
Embodiment 31. The composition defined in embodiment 29, wherein M is Hf.
Embodiment 32. The composition defined in any one of embodiments 29-31, wherein CpA and CpB independently are a substituted indenyl or cyclopentadienyl group with any number of substituents disclosed herein, e.g., one substituent, two substituents, etc.
Embodiment 33. The composition defined in any one of embodiments 29-32, wherein each substituent on CpA and CpB independently is any substituent disclosed herein, e.g., H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group.
Embodiment 34. The composition defined in any one of embodiments 29-33, wherein each substituent on CpA and CpB independently is any C1 to C12 hydrocarbyl group or C1 to C12 hydrocarbylsilyl group disclosed herein.
Embodiment 35. The composition defined in any one of embodiments 29-34, wherein each substituent on CpA and CpB independently is H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group.
Embodiment 36. The composition defined in embodiment 29, wherein CpA and CpB independently are an unsubstituted cyclopentadienyl or indenyl group.
Embodiment 37. The composition defined in any one of embodiments 29-36, wherein X4 and X5 independently are any monoanionic ligand disclosed herein.
Embodiment 38. The composition defined in any one of embodiments 29-37, wherein X4 and X5 independently are H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group.
Embodiment 39. The composition defined in any one of embodiments 29-38, wherein X4 and X5 independently are any halide or C1 to C18 hydrocarbyl group disclosed herein.
Embodiment 40. The composition defined in any one of embodiments 29-39, wherein X4 and X5 are Cl.
Embodiment 41. The composition defined in any one of embodiments 1-26, wherein catalyst component I comprises any bridged zirconium or hafnium based metallocene compound containing a fluorenyl group disclosed herein.
Embodiment 42. The composition defined in any one of embodiments 1-26, wherein catalyst component I comprises a bridged metallocene compound having formula (IB):




wherein M is Zr or Hf, CpC is a substituted cyclopentadienyl, indenyl, or fluorenyl group, X4 and X5 independently are a monoanionic ligand, RX and RY independently are H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group, and E is a bridging group selected from a bridging group having the formula >EARARB, wherein EA is C or Si, and RA and RB independently are H or a C1 to C18 hydrocarbyl group, a bridging group having the formula —CRCRD—CRERF—, wherein RC, RD, RE, and RF independently are H or a C1 to C18 hydrocarbyl group, or a bridging group having the formula —SiRGRH—SiRIRJ—, wherein RG, RH, RI, and RJ independently are H or a C1 to C18 hydrocarbyl group.

Embodiment 43. The composition defined in embodiment 42, wherein M is Zr.
Embodiment 44. The composition defined in embodiment 42, wherein M is Hf.
Embodiment 45. The composition defined in any one of embodiments 42-44, wherein CpC is a substituted cyclopentadienyl group with any number of substituents disclosed herein, e.g., one substituent, two substituents, etc., in addition to the bridging group.
Embodiment 46. The composition defined in any one of embodiments 42-45, wherein each substituent on CpC independently is any substituent disclosed herein, e.g., H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group.
Embodiment 47. The composition defined in any one of embodiments 42-46, wherein each substituent on CpC independently is any C1 to C12 hydrocarbyl group or C1 to C12 hydrocarbylsilyl group disclosed herein.
Embodiment 48. The composition defined in any one of embodiments 42-47, wherein each substituent on CpC independently is H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group.
Embodiment 49. The composition defined in embodiment 42, wherein CpC contains no additional substituents, e.g., other than the bridging group.
Embodiment 50. The composition defined in any one of embodiments 42-49, wherein X4 and X5 independently are any monoanionic ligand disclosed herein.
Embodiment 51. The composition defined in any one of embodiments 42-50, wherein X4 and X5 independently are H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group.
Embodiment 52. The composition defined in any one of embodiments 42-51, wherein X4 and X5 independently are any halide or C1 to C18 hydrocarbyl group disclosed herein.
Embodiment 53. The composition defined in any one of embodiments 42-52, wherein X4 and X5 are Cl.
Embodiment 54. The composition defined in any one of embodiments 42-53, wherein RX and RY independently are any substituent disclosed herein, e.g., H or a C1 to C12 hydrocarbyl group.
Embodiment 55. The composition defined in any one of embodiments 42-54, wherein RX and RY independently are H, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, or a benzyl group.
Embodiment 56. The composition defined in any one of embodiments 42-55, wherein E is any bridging group disclosed herein.
Embodiment 57. The composition defined in any one of embodiments 42-56, wherein E is a bridging group having the formula >EARARB, wherein EA is C or Si, and RA and RB independently are any C1 to C12 hydrocarbyl group disclosed herein.
Embodiment 58. The composition defined in any one of embodiments 42-57, wherein E is a bridging group having the formula >EARARB, wherein EA is C or Si, and RA and RB independently are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, or a benzyl group.
Embodiment 59. The composition defined in any one of embodiments 42-56, wherein E is a bridging group having the formula —CRCRD—CRERF—, wherein RC, RD, RE, and RF independently are H or any C1 to C18 hydrocarbyl group disclosed herein, e.g., H or a methyl group.
Embodiment 60. The composition defined in any one of embodiments 42-56, wherein E is a bridging group having the formula —SiRGRH—SiRIRJ—, wherein RG, RH, RI, and RJ independently are H or any C1 to C18 hydrocarbyl group disclosed herein, e.g., H or a methyl group.
Embodiment 61. The composition defined in any one of embodiments 1-60, wherein a weight ratio of catalyst component I to catalyst component II is in any range of weight ratios disclosed herein, e.g., from about 10:1 to about 1:10, from about 10:1 to about 1:5, etc.
Embodiment 62. The composition defined in any one of embodiments 1-61, wherein a weight ratio of catalyst component I to catalyst component II is in a range of from about 4:1 to about 1:4.
Embodiment 63. An olefin polymerization process, the process comprising contacting the catalyst composition defined in any one of embodiments 1-62 with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer.
Embodiment 64. The process defined in embodiment 63, wherein the process is conducted in a batch reactor, a slurry reactor, a gas-phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, or a combination thereof.
Embodiment 65. The process defined in any one of embodiments 63-64, wherein the process is conducted in a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof.
Embodiment 66. The process defined in any one of embodiments 63-65, wherein the process is conducted in a single reactor, e.g., a slurry reactor.
Embodiment 67. The process defined in any one of embodiments 63-65, wherein the process is conducted in two or more reactors.
Embodiment 68. The process defined in any one of embodiments 63-67, wherein the olefin monomer comprises any olefin monomer disclosed herein, e.g., a C2-C20 olefin.
Embodiment 69. The process defined in any one of embodiments 63-68, wherein the olefin monomer comprises ethylene or propylene.
Embodiment 70. The process defined in any one of embodiments 63-69, wherein the olefin monomer comprises ethylene and the olefin comonomer comprises a C3-C10 alpha-olefin.
Embodiment 71
The process defined in any one of embodiments 63-69, wherein the olefin monomer comprises 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 mixture thereof.
Embodiment 72. The process defined in any one of embodiments 63-69, wherein the olefin monomer comprises ethylene, and the olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.
Embodiment 73. The process defined in any one of embodiments 63-72, wherein the olefin polymer comprises any olefin polymer disclosed herein.
Embodiment 74. The process defined in any one of embodiments 63-73, wherein the olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.
Embodiment 75. The process defined in any one of embodiments 63-74, wherein the olefin polymer has a ratio of Mw/Mn in any range disclosed herein, e.g., from about 4 to about 35, from about 8 to about 25, etc.
Embodiment 76. The process defined in any one of embodiments 63-75, wherein the olefin polymer has a ratio of Mz/Mw in any range disclosed herein, e.g., from about 3 to about 15, from about 7 to about 13, etc.
Embodiment 77. The process defined in any one of embodiments 63-76, wherein the olefin polymer has a Mw in any range disclosed herein, e.g., from about 100,000 to about 400,000 g/mol, from about 150,000 to about 300,000 g/mol, etc.
Embodiment 78. The process defined in any one of embodiments 63-77, wherein the olefin polymer has a Mn in any range disclosed herein, e.g., from about 8,000 to about 30,000 g/mol, from about 9,000 to about 25,000 g/mol, etc.
Embodiment 79. The process defined in any one of embodiments 63-78, wherein the olefin polymer has a Mz greater than about 1,000,000 g/mol or in any range disclosed herein, e.g., from about 1,000,000 to about 3,000,000 g/mol.
Embodiment 80. The process defined in any one of embodiments 63-79, wherein the olefin polymer has a density greater than about 0.92 g/cm3 or in any range disclosed herein, e.g., from about 0.93 to about 0.95 g/cm3.
Embodiment 81. The process defined in any one of embodiments 63-80, wherein the olefin polymer has a melt index less than about 5 g/10 min or in any range disclosed herein, e.g., from about 0.1 to about 5 g/10 min.
Embodiment 82. The process defined in any one of embodiments 63-81, wherein the olefin polymer has a ratio of HLMI to MI in any range disclosed herein, e.g., from about 30 to about 300, from about 40 to about 250, etc.
Embodiment 83. The process defined in any one of embodiments 63-82, wherein the olefin polymer has less than about 0.008 long chain branches (LCB) per 1000 total carbon atoms, e.g., less than about 0.005 LCB per 1000 total carbon atoms.
Embodiment 84. The process defined in any one of embodiments 63-83, wherein the olefin polymer has zero-shear viscosity at 190° C. in any range disclosed herein, e.g., from about 1×105 to about 1×107 Pa-sec, from about 5×105 to about 5×106 Pa-sec, etc.
Embodiment 85. An olefin polymer produced by the olefin polymerization process defined in any one of embodiments 63-84.
Embodiment 86. An article comprising the olefin polymer defined in embodiment 85.
Embodiment 87. A method or forming or preparing an article of manufacture comprising an olefin polymer, the method comprising (i) performing the olefin polymerization process defined in any one of embodiments 63-84 to produce the olefin polymer, and (ii) forming the article of manufacture comprising the olefin polymer, e.g., via any technique disclosed herein.
Embodiment 88. The article defined in any one of embodiments 86-87, wherein the article is an agricultural film, an automobile part, a bottle, a drum, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, a liner, a molded product, a medical device or material, a pipe, a sheet or tape, or a toy.

## Claims

1. An olefin polymerization process, the process comprising:
contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer having a Mw in a range from about 100,000 to about 500,000 g/mol, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator, and an optional co-catalyst, wherein:
catalyst component I comprises a zirconium or hafnium based metallocene compound; and
catalyst component II comprises a titanium based half-metallocene compound containing an indenyl group.

2. The process of claim 1, wherein catalyst component II comprises a half metallocene compound having formula (IIA):




wherein:
InA is a substituted or unsubstituted indenyl group; and
X1, X2, and X3 independently are a monoanionic ligand.

3. The process of claim 2, wherein InA is an unsubstituted indenyl group.

4. The process of claim 2, wherein:
each substituent on InA independently is H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group; and
X1, X2, and X3 independently are H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group.

5. The process of claim 2, wherein:
each substituent on InA independently is H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group; and
X1, X2, and X3 independently are a halide or a C1 to C18 hydrocarbyl group.

6. The process of claim 1, wherein catalyst component II comprises:




or any combination thereof.

7. The process of claim 1, wherein catalyst component I comprises an unbridged metallocene compound having formula (IA):




wherein:
M is Zr or Hf;
CpA and CpB independently are a substituted or unsubstituted cyclopentadienyl or indenyl group; and
X4 and X5 independently are a monoanionic ligand.

8. The process of claim 7, wherein CpA and CpB independently are an unsubstituted cyclopentadienyl or indenyl group.

9. The process of claim 1, wherein catalyst component I comprises a bridged metallocene compound having formula (IB):




wherein:
M is Zr or Hf;
CpC is a substituted cyclopentadienyl, indenyl, or fluorenyl group;
X4 and X5 independently are a monoanionic ligand;
RX and RY independently are H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group; and
E is a bridging group selected from:
a bridging group having the formula >EARARB, wherein EA is C or Si, and RA and RB independently are H or a C1 to C18 hydrocarbyl group,
a bridging group having the formula —CRCRD—CRERF—, wherein RC, RD, RE, and RF independently are H or a C1 to C18 hydrocarbyl group, or
a bridging group having the formula —SiRGRH—SiRIRJ—, wherein RG, RH, RI, and RJ independently are H or a C1 to C18 hydrocarbyl group.

10. The process of claim 9, wherein:
RX and RY independently are H or a C1 to C12 hydrocarbyl group; and
E is a bridging group having the formula >EARARB, wherein EA is C or Si, and RA and RB independently are a C1 to C12 hydrocarbyl group.

11. The process of claim 1, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

12. The process of claim 1, wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion.

13. The process of claim 12, wherein the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

14. The process of claim 1, wherein the olefin polymer has:
a ratio of Mw/Mn in a range from about 4 to about 35;
a ratio of Mz/Mw in a range from about 3 to about 15;
a Mw in a range from about 100,000 to about 400,000 g/mol;
a Mn in a range from about 8,000 to about 30,000 g/mol;
a Mz greater than about 1,000,000 g/mol;
a density greater than about 0.92 g/cm3;
a melt index less than about 5 g/10 min;
a ratio of HLMI to MI in a range from about 30 to about 300;
less than about 0.008 long chain branches per 1000 total carbon atoms; or
a zero-shear viscosity at 190° C. in a range from about 1×105 to 1×107 Pa-sec; or any combination thereof.

15. The process of claim 1, wherein the process is conducted in a batch reactor, slurry reactor, gas-phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, or a combination thereof.

16. The process of claim 1, wherein the olefin monomer comprises ethylene or propylene.

17. An olefin polymerization process, the process comprising:
contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer having a Mw in a range from about 100,000 to about 500,000 g/mol, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator-support, and a co-catalyst, wherein:
catalyst component I comprises an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group;
catalyst component II comprises a titanium based half-metallocene compound containing an indenyl group;
the activator-support comprises a solid oxide treated with an electron-withdrawing anion; and
the olefin monomer comprises ethylene.

18. The process of claim 17, wherein:
the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof;
the co-catalyst comprises an organoaluminum compound, the organoaluminum compound comprising trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof; 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 mixture thereof.

19. The process of claim 17, wherein:
a weight ratio of catalyst component I to catalyst component II is in a range of from about 4:1 to about 1:4;
the activator-support comprises fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof; and
the olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.

20. The new process of claim 1, wherein catalyst component II comprises a half metallocene compound having formula (IIA):




wherein:
InA is a substituted or unsubstituted indenyl group; and
X1, X2, and X3 independently are a halide or a C1 to C18 hydrocarbyl group; and the olefin polymer has:
a ratio of Mw/Mn in a range from about 4 to about 40;
a ratio of Mz/Mw in a range from about 3 to about 15;
a Mn in a range from about 7,000 to about 35,000 g/mol; and
a density in a range from about 0.91 to about 0.96 g/cm3.

21. The process of claim 20, wherein:
the process is conducted in a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof;
the olefin monomer comprises ethylene; and the olefin polymer has:
a ratio of HLMI to MI in a range from about 30 to about 350;
a ratio of Mw/Mn in a range from about 5 to about 30; and
a Mz in a range from about 1,000,000 to about 4,000,000 g/mol.

22. The process of claim 17, wherein:
a weight ratio of catalyst component I to catalyst component II is in a range of from about 4:1 to about 1:4;
the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;
the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; and the olefin polymer has:
a ratio of Mw/Mn in a range from about 4 to about 40;
a ratio of Mz/Mw in a range from about 3 to about 15;
a Mn in a range from about 7,000 to about 35,000 g/mol; and
a density in a range from about 0.91 to about 0.96 g/cm3.

23. The process of claim 22, wherein:
the process is conducted in a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; and
the olefin polymer has:
a ratio of HLMI to MI in a range from about 30 to about 350;
a ratio of Mw/Mn in a range from about 5 to about 30; and
a Mz in a range from about 1,000,000 to about 4,000,000 g/mol.