OLEFIN POLYMERIZATION PROCESS AND CATALYST COMPOSITION

专利摘要:
titanium phosphinimide and titanium iminoimidazolide catalyst systems with activator supports. these are catalyst compositions containing activator supports and half metallocene titanium phosphinimide complexes or half metallocene titanium iminoimidazolidide complexes. these catalyst compositions can be used to produce olefin polymers that have relatively broad molecular weight distributions and low levels of long chain branching.
公开号:BR112017007160B1
申请号:R112017007160-6
申请日:2015-09-29
公开日:2021-07-27
发明作者:Carlos A. Cruz；Jared L. Barr；Jeremy M. Praetorius
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
[0001] Polyolefins such as high density polyethylene homopolymer (HDPE) and linear low density polyethylene copolymer (LLDPE) can be produced using various combinations of catalyst systems and polymerization processes. Traditional Ziegler catalyst systems can produce olefin polymers that have, for example, good extrusion processability and polymer melt strength, typically due to their broad molecular weight distribution (MWD). In some end use applications, it may be beneficial for the olefin polymer to also have low levels of long chain branching. Furthermore, it may be beneficial for the catalyst system employed to efficiently incorporate a comonomer, as well as having a greater sensitivity to hydrogen to allow a wider range of melt index and molecular weight of polymer to be produced. Consequently, it is to these purposes that the present invention is directed. SUMMARY OF THE INVENTION
[0002] This summary is provided in order 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 essential or required features of the claimed matter. Nor is this summary intended to be used to limit the scope of the matter claimed.
[0003] Generally, the present invention is directed to half metallocene titanium compounds, catalyst compositions containing such half metallocene titanium compounds, methods for preparing the catalyst compositions, methods for using the catalyst compositions to polymerize olefins , polymer resins produced using such catalyst compositions, and articles produced using such polymer resins.
[0004] According to one aspect of the invention, the half metallocene titanium compound may have the structure of formula (II):

[0005] According to another aspect of the invention, the half metallocene titanium compound may have the structure of formula (III):

[0006] In these formulas, each Cp can independently be any cyclopentadienyl, indenyl or fluorenyl group disclosed herein, and each X can independently be any monoanionic ligand disclosed herein. Independently, R1, R2, R3, RA and RB can be H or any halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxyl group, or a C1 to C36 hydrocarbylsilyl group disclosed in this document.
[0007] Other aspects of the present invention are directed to catalyst compositions containing any half metallocene titanium compound disclosed herein, any activator support disclosed herein, and optionally, any cocatalyst disclosed herein. Such catalyst compositions can be used to produce, for example, ethylene-based homopolymers and copolymers for a variety of end-use applications.
[0008] The present invention also contemplates and encompasses olefin polymerization processes. Such processes may 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 half metallocene titanium compounds and any of the optional activator supports and cocatalysts disclosed herein. For example, organoaluminium compounds can be used in catalyst compositions and/or polymerization processes.
[0009] Polymers produced from the polymerization of olefins, which results in homopolymers, copolymers, terpolymers, etc., can be used to produce various articles of manufacture. A non-limiting and representative example of an olefin polymer (eg, an ethylene homopolymer or copolymer) consistent with aspects of this invention can be characterized by the following properties: a ratio of Mw/Mn in a range of about 4 to about 10 (or about 5 to about 9), an HLMI/MI ratio in a range of about 15 to about 75 (or about 25 to about 55), a density in a range of about 0.89 to about 0.97 g/cm3 (or about 0.92 to about 0.94 g/cm3), less than or equal to about 0.008 long chain branches (LCB) per 1,000 atoms of total carbon (or less than or equal to about 0.003 LCB), and a conventional comonomer distribution (eg, the amount of short chain branches (SCB) per 1,000 total polymer carbon atoms in Mn is greater than in Mz).
[0010] Both the summary above and the detailed description below provide examples and are only explanatory. Consequently, the summary set out above and the detailed description below should not be considered restrictive. In addition, features or variations may be provided in addition to those set out in this document. For example, certain aspects and certain modalities may be directed towards various combinations and subcombinations of features described in the detailed description. BRIEF DESCRIPTION OF THE FIGURES
[0011] Figure 1 presents a plot of the molecular weight distributions of polymers produced using a catalyst system that contains a half metallocene titanium compound (example 4), produced using a catalyst system based in standard metallocene (example C2), and produced using a standard Ziegler catalyst system (example C3).
[0012] Figure 2 presents a plot of the short chain branching distribution of a polymer produced using the same experimental conditions as in example 2.
[0013] Figure 3 presents a plot of the radius of gyration against the molecular weight for a linear pattern and polymers produced using the same experimental conditions as in example 6.
[0014] Figure 4 presents a plot of the amount of long-chain branches (LCB) per 1,000,000 total carbon atoms as a function of the molecular weight of polymers produced using the same experimental conditions as in example 6.
[0015] Figure 5 presents a dynamic rheology plot (viscosity versus frequency) at 190 oC for the polymers of examples 4 and 21-22, produced using different amounts of diethylzinc (TEN).
[0016] Figure 6 presents a plot of the molecular weight distributions of the polymers of examples 4 and 21-22, produced using different amounts of diethylzinc (TEN). DEFINITIONS
[0017] In order to more clearly define the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition of the IUPAC Chemical Terminology Compendium, 2nd Ed (1997) may apply, provided that this definition does not conflict with any other disclosure or definition. applied herein, or make undefined or disallowed any claim to which that definition applies. 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 by reference controls.
[0018] Although compositions and methods are described herein in terms of "comprising" several components or several steps, compositions and methods may also "consist essentially" or "consist" of various components or several steps, unless stated otherwise. For example, a catalyst composition consistent with aspects of the present invention may comprise; alternatively, it may consist essentially of; or alternatively, it may consist of; (i) a half metallocene titanium compound, (ii) an activator support, and (iii) optionally, a cocatalyst.
[0019] The terms "a", "an", "the", etc. are intended to include plural alternatives, eg at least one, unless otherwise specified. For example, the disclosure of "an activator support" or "a half metallocene titanium compound" is intended to encompass one, or mixtures or combinations of more than one, activator support or half metallocene titanium compound, respectively , unless otherwise specified.
[0020] Generally, 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 cases, 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 to 12 elements, and halogens or halides for Group 17 elements.
[0021] For any particular compound disclosed herein, the general structure or given name is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that may arise from a particular set of substituents, unless it is otherwise indicated. Thus, a general reference to a compound includes all structural isomers unless explicitly stated otherwise; for example, 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 group. -butyl and a tert-butyl group. Additionally, 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 shown, any formula or general name given also encompasses all conformational isomers, regioisomers and stereoisomers that may arise from a particular set of substituents.
[0022] The term "substituted" when used to describe a group, for example, when referring to a substituted analogue of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and if intended to be non-limiting. A group or groups may also be referred to herein as "unsubstituted" or by equivalent terms such as "unsubstituted", which refers to the original group in which the non-hydrogen moiety does not replace a hydrogen in that group. Unless otherwise specified, "substituted" is intended to be non-limiting and to include inorganic substituents or organic substituents as understood by one of ordinary skill in the art.
[0023] The term "hydrocarbon", whenever used in this specification or in the claims, refers to a compound that contains only carbon and hydrogen. Other identifiers can be used to indicate the presence of particular groups in the hydrocarbon (for example, a halogenated hydrocarbon indicates the presence of one or more halogen atoms that replace an equivalent amount of hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is used herein according to the definition specified by the IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon (ie, a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include alkyl, alkenyl, aryl and aralkyl groups, among other groups.
[0024] The term "polymer" is used generically herein to include olefin homopolymers, copolymers and terpolymers, and so on. A copolymer is derived from one olefin monomer and one olefin comonomer, while a terpolymer is derived from one olefin monomer and two olefin comonomers. Accordingly, "polymer" encompasses copolymers, terpolymers, etc., derived from any olefin monomer and comonomer disclosed herein. Similarly, an ethylene polymer can include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, and the like. As an example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer can be categorized as an ethylene/1-hexene copolymer.
[0025] Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process may involve contacting an olefin monomer (eg ethylene) and an olefin comonomer (eg 1-hexene) in order to produce a copolymer.
[0026] The term "cocatalyst" is used generally herein to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionic ionizing compounds, organoaluminium compounds, organozinc compounds, organomagnesium compounds, compounds of organolithium, and the like, which can constitute a component of a catalyst composition, when used, for example, in addition to an activator support. The term "cocatalyst" is used regardless of the actual function of the compound or any chemical mechanism by which the compound may operate.
[0027] The terms "catalyst composition", "catalyst mixture", "catalyst system", and the like do not depend on the actual product or composition that results from the contact or reaction of the initial components of the composition/mixture/ of the disclosed or claimed catalyst system, the nature of the active catalytic site, or the fate of the cocatalyst, half metallocene titanium compound or activator support, after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system", and the like, which cover the initial initiating components of the composition, as well as any product (or any products) that may result in placing in contact these initial initiating components, and this is inclusive of both heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition", "catalyst mixture", "catalyst system", and the like may be used interchangeably throughout this disclosure.
[0028] The term "contact product" is used herein to describe compositions in which the components are brought into contact together in any order, in any manner, and for any length of time. For example, components can be brought into contact by blending or blending. Furthermore, contacting any component can occur in the presence or absence of any other component. Combining additional materials or components can be done by any suitable method. In addition, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Although “contact product” may include reaction products, the respective components are not required to react with each other. Similarly, the term "contact" is used herein to refer to materials that can be mixed, mixed, slurried, dissolved, reacted, treated, or otherwise brought into contact in some other way. Therefore, the term "contact" encompasses the "reaction" of two or more components, and it also encompasses the "mixture" or "mixture" of two or more components that do not react with each other.
[0029] Although any methods, devices and materials similar or equivalent to the same described herein may be used in the practice or testing of the invention, typical methods, devices and materials are described herein.
[0030] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructions and methodologies that are described in the publications, which may be used in connection with the presently disclosed invention.
[0031] Depositors disclose many types of tracks in the present invention. When depositors disclose or claim a range of any type, the intention of the depositors is to individually disclose or claim any possible number such range may reasonably be expected to cover, including the endpoints of the range as well as any sub-ranges and combinations of sub-ranges covered therein. For example, when depositors disclose or claim a chemical moiety that has a certain amount of carbon atoms, the intent of the depositors is to individually disclose or claim any possible number that such range may cover, 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 1 to 18 carbon atoms, as used herein, refers to a moiety that can have 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 hydrocarbyl group C1 to C8), and also includes any combination of bands between these two numbers (for example, a hydrocarbyl group C2 to C4 and C12 to C16).
[0032] Similarly, another representative example follows the Mw/Mn ratio of an olefin polymer produced in one aspect of this invention. Through a disclosure that the Mw/Mn can be in a range of about 4 to about 10, depositors intend to cite that the Mw/Mn can be any rate in the range and, for example, can be equal to about 4, about 5, about 6, about 7, about 8, about 9 or about 10. Additionally, the Mw/Mn can be in any range from about 4 to about 10 (e.g. about 5 to about 9), and this also includes any combination of ranges between about 4 and about 10 (for example, the Mw/Mn can be in a range of about 4 to about 6, or about from 7 to about 9). Likewise, all other ranges disclosed in this document should be interpreted in a manner similar to these examples.
[0033] Depositors reserve the right to suppress or exclude any individual members of any such group, including any sub-ranges or combinations of sub-ranges in the group, which may be claimed under a band or in any similar manner, if for any reason the applicants choose to claim less than the full extent of disclosure, for example, consider a reference that applicants may be inattentive at the time of filing the patent application. In addition, applicants reserve the right to suppress or exclude any individual substituents, analogues, compounds, linkers and structures, or groups thereof, or any members of a claimed group, if for any reason applicants choose to claim less than the measure total disclosure, for example, consider a reference that applicants may be inattentive at the time of filing the patent application. DETAILED DESCRIPTION OF THE INVENTION
[0034] The present invention is generally directed to new catalyst compositions, new methods for preparing catalyst compositions, new methods for using catalyst compositions to polymerize olefins, polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, the present invention relates to half metallocene titanium phosphinimide complexes and half metallocene titanium iminoimidazolidide complexes, to catalyst compositions employing such half metallocene titanium complexes, to polymerization processes using such half metallocene titanium complexes. catalyst, and the resulting olefin polymers produced from the polymerization processes.TITANIUM PHOSPHINIMIDES AND TITANIUM IMINOIMIDAZOLIDES
[0035] In one aspect of this invention, the half metallocene titanium compounds may have the formula:

[0036] In formula (I), Cp, L, and each X are independent elements of the half metallocene titanium compound. Accordingly, the half metallocene titanium compound having the formula (I) can be described using any combination of Cp, L and X disclosed herein.
[0037] Unless otherwise specified, formula (I) 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 fractions (for example, these formulas are not intended to exhibit cis or trans isomers, or R or S diastereoisomers), although such compounds are contemplated and encompassed by such formulas and/or structures.
[0038] Each X in formula (I) can independently be a monoanionic ligand. In some aspects, suitable monoanionic linkers may include, but are not limited to, H (hydride), BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxyl group, a C1 to C36 hydrocarbylaminyl group, a group C1 to C36 hydrocarbylsilyl, a C1 to C36 hydrocarbylaminylsilyl group, —OBRX2, or —OSO2RX, where RX is a C1 to C36 hydrocarbyl group. It is contemplated that each X can be the same monoanionic ligand or a different monoanionic ligand.
[0039] In one aspect, each X may independently be H, BH4, a halide (e.g. F, Cl, Br, etc.), a C1 to C18 hydrocarbyl group, a C1 to C18 hydrocarboxyl group, a C1 hydrocarbylaminyl group to C18, a C1 to C18 hydrocarbylsilyl group, or a C1 to C18 hydrocarbylaminylsilyl group. Alternatively, each X can independently be H, BH4, a halide, OBRX2, or OSO2RX, where RX is a C1 to C18 hydrocarbyl group. In another aspect, each X may independently be H, BH4, a halide, a C1 to C12 hydrocarbyl group, a C1 to C12 hydrocarboxyl group, a C1 to C12 hydrocarbylaminyl group, a C1 to C12 hydrocarbylsilyl group, a C1 to C12 hydrocarbylaminylsilyl group , OBRX2, or OSO2RX, where RX is a C1 to C12 hydrocarbyl group. In another aspect, each X may independently be H, BH4, a halide, a C1 to C10 hydrocarbyl group, a C1 to C10 hydrocarboxyl group, a C1 to C10 hydrocarbylaminyl group, a C1 to C10 hydrocarbylsilyl group, a C1 to C10 hydrocarbylaminylsilyl group , OBRX2, or OSO2RX, where RX is a C1 to C10 hydrocarbyl group. In yet another aspect, each X may independently be H, BH4, a halide, a C1 to C8 hydrocarbyl group, a C1 to C8 hydrocarboxyl group, a C1 to C8 hydrocarbylaminyl group, a C1 to C8 hydrocarbylsilyl group, a C1 to C1 to hydrocarbylaminylsilyl group C8, OBRX2, or OSO2RX, where RX is a C1 to C8 hydrocarbyl group. In yet another aspect, each X can independently be a halide or a C1 to C18 hydrocarbyl group. For example, both Xs can be Cl.
The hydrocarbyl group which may be an X (one or both) in formula (I) may be a C1 to C36 hydrocarbyl group, including, but not limited to, a C1 to C36 alkyl group, a C2 to alkenyl group. C36, a C4 to C36 cycloalkyl group, a C6 to C36 aryl group, or a C7 to C36 aralkyl group. For example, each X can independently 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, each X may independently 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, each X may independently 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, each X can independently 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.
[0041] Consequently, in some aspects, the alkyl group that may be an X in the formula (I) may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a group heptyl, an octyl group, a nonyl group, a decyl group, an 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 may be an X in formula (I) and may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-group butyl, a sec-butyl group, a tert-butyl group, an 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 an n-propyl group; alternatively an iso-propyl group; alternatively a tert-butyl group; or alternatively, a neopentyl group.
Suitable alkenyl groups which may be an X in the formula (I) may 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, an 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 straight or branched, and the double bond can be located anywhere in the chain. In one aspect, each X in formula (I) can independently 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, each X in formula (I) may independently be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, or a hexenyl group. For example, an X 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, an X may be a terminal alkenyl group, such as a terminal C3 to C18 alkenyl group, a terminal C3 to C12 alkenyl group, or a terminal C3 to C8 alkenyl group. Illustrative end alkenyl groups may include, but are not limited to, a prop-2-en-1-yl group, a bute-and-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 group dece-9-en-1-il, and so on.
[0043] Each X in formula (I) may independently 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 cyclohexyl group substituted, a cycloheptyl group, a substituted cycloheptyl group, a cyclooctyl group, or a substituted cyclooctyl group. For example, an X in formula (I) may be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group. Furthermore, each X in formula (I) can independently 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. The substituents which may be used for the substituted cycloalkyl group are independently disclosed herein and may be used without limitation in order to further describe the substituted cycloalkyl group which may be an X in formula (I).
[0044] In some aspects, the aryl group which may be an X in formula (I) may be a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. In one 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 that can be used for substituted phenyl groups or substituted naphthyl groups are independently disclosed herein and can be used without limitation in order to further describe substituted phenyl groups or substituted naphthyl groups that can be an X in the formula (I).
[0045] In one aspect, the substituted phenyl group which may be an X in the formula (I) may be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4 phenyl group -disubstituted, 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 may 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. The substituents that can be used for those specific substituted phenyl groups are independently disclosed herein and can be used without limitation in order to further describe those substituted phenyl groups that can be an X in formula (I).
[0046] In some aspects, the aralkyl group which may be an X in formula (I) may be a benzyl group or a substituted benzyl group. In one aspect, the aralkyl group can be a benzyl group or, alternatively, a substituted benzyl group. The substituents which may be used for the substituted aralkyl group are independently disclosed herein and may be used without limitation in order to further describe the substituted aralkyl group which may be an X in formula (I).
[0047] In one aspect, each non-hydrogen substituent (or substituents) for the substituted cycloalkyl group, the substituted aryl group, or the substituted aralkyl group which may be an X in formula (I) may independently be a C1 to hydrocarbyl group C18; alternatively a C1 to C8 hydrocarbyl group; or alternatively a C1 to C5 hydrocarbyl group. Specific hydrocarbyl groups are independently disclosed herein and may be used without limitation in order to further describe the substituents of substituted cycloalkyl groups, substituted aryl groups, or substituted aralkyl groups which may be an X in formula (I) . For example, the hydrocarbyl substituent can be an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, an e-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 neopentyl 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.
[0048] A hydrocarboxyl group is used generically herein to include, for example, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl or aralkyl)-O-(alkyl, aryl or aralkyl) groups, and -O(CO) groups )-(hydrogen or hydrocarbyl), and such groups can comprise up to about 36 carbon atoms (for example, the C1 to C36, C1 to C18, C1 to C10, or C1 to C8) hydrocarboxy groups. Illustrative and non-limiting examples of hydrocarboxyl groups which may be an X in formula (I) may include, but not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n- butoxy, 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, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, a neopentoxy group, a phenoxy group, a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, a group benzoxy, an acetylacetonate (acac) group, a formate group, an acetate group, a stearate group, an oleate group, a benzoate group, and the like. In one aspect, the hydrocarboxyl group which may be an X in formula (I) may 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 neopentoxy group; alternatively, a phenoxy group; alternatively, a toloxy group; alternatively, a xyloxy group; alternatively a 2,4,6-trimethylphenoxy group; alternatively, a benzoxy group; alternatively, an acetylacetonate group; alternatively, a format group; alternatively an acetate group; alternatively, a stearate group; alternatively, an oleate group; or alternatively, a benzoate group.
The term hydrocarbylaminyl group is used generically herein to refer collectively to, for example, alkylaminyl, arylaminyl, aralkylaminyl, dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl or aralkyl)-N- groups (alkyl, aryl or aralkyl), and unless otherwise specified, the hydrocarbylaminyl group which may be an X in formula (I) may comprise up to about 36 carbon atoms (e.g., C1 to C36 hydrocarbylaminyl groups , C1 to C18, C1 to C10 or C1 to C8). Consequently, hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl and dihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl group which may be an X in the formula (I) may be, for example, a methylaminyl group (-NHCH3), an ethylaminyl group (-NHCH2CH3), an n-propylaminyl group (-NHCH2CH2CH3), a iso-propylaminyl group (-NHCH(CH3)2), an n-butylaminyl group (-NHCH2CH2CH2CH3), a t-butylaminyl group (-NHC(CH3)3), an n-pentylaminyl group (-NHCH2CH2CH2CH2CH3), a neopentylaminyl 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 may be an X in formula (I) may be, for example, a dimethylaminyl group (-N(CH3)2), a diethylaminyl group (-N(CH2CH3)2), a di group. -n-propylaminyl (-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 diethylaminyl group; alternatively a di-n-propylaminyl group; or alternatively a diphenylaminyl group.
According to some aspects disclosed herein, each X may independently 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 hydrocarbylysilyl group. In one 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 group C6 to C8 aryl, a C7 to C8 aralkyl group, etc.). As used herein, hydrocarbylsilyl is intended to cover (mono)hydrocarbylsilyl (-SiH2R), dihydrocarbylsilyl (-SiHR2), and trihydrocarbylsilyl (-SiR3) groups, where R is a hydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C3 to C36 or C3 to C18 trihydrocarbylsilyl group, such as, for example, a trialkylsilyl group or a triphenylsilyl group. Illustrative and non-limiting examples of hydrocarbylsilyl groups that can be an X in formula (I) may include, but are not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (for example, triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, and the like.
[0051] A hydrocarbylaminylsilyl group is used herein to refer to groups that contain at least one hydrocarbon moiety, at least one N atom, and at least one Si atom. can be an X include, but not limited to, -N(SiMe3)2, -N(SiEt3)2 and the like. Unless otherwise specified, hydrocarbylaminylsilyl groups which can be an X can comprise up to about 36 carbon atoms (for example, C1 to C36, C1 to C18, C1 to C12 or C1 to C8 hydrocarbylaminylsilyl groups). In one 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 group C6 to C8 aryl, a C7 to C8 aralkyl group, etc.). Furthermore, hydrocarbylaminylsilyl is intended to cover groups - NH(SiH2R), -NH(SiHR2), -NH(SiR3), -N(SiH2R)2, -N(SiHR2)2 and -N(SiR3)2, among others , where R is a hydrocarbyl group.
[0052] In one aspect, each X can independently be -OBRX2 or -OSO2RX, where RX is a C1 to C36 hydrocarbyl group, or alternatively, a C1 to C18 hydrocarbyl group. The hydrocarbyl group in OBRX2 and/or OSO2RX can independently be any hydrocarbyl group disclosed herein, such as, for example, a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C4 to C18 cycloalkyl group, an aryl group C6 to C18, 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.
[0053] In one aspect, each X may independently be H, BH4, a halide, or a C1 to C36 hydrocarbyl group, a hydrocarboxyl group, a hydrocarbylaminyl group, a hydroarbylsilyl group, or a hydrocarbylaminylsilyl group, while in another aspect, each X can independently be H, BH4, or a C1 to C18 hydrocarboxyl group, hydrocarbylaminyl group, a hydroarbylsilyl group, or a hydrocarbylaminylsilyl group. In yet another aspect, each X can independently be a halide; alternatively a C1 to C18 hydrocarbyl group; alternatively a C1 to C18 hydrocarboxyl group; alternatively a C1 to C18 hydrocarbylaminyl group; alternatively a C1 to C18 hydrocarbylsilyl group; or alternatively a C1 to C18 hydrocarbylaminylsilyl group. In yet another aspect, both Xs 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 hydrocarboxyl group; alternatively a C1 to C18 hydrocarbylaminyl group; alternatively a C1 to C18 hydrocarbylsilyl group; or alternatively a C1 to C18 hydrocarbylaminylsilyl group.
[0054] Each X can be, independently, in some aspects, H, a halide, a methyl, a phenyl, a benzyl, an alkoxy, an aryloxy, an acetylacetonate, a formate, an acetate, a stearate, an oleate , a benzoate, an alkylaminyl, a dialkylaminyl, a trihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively H, a halide, a methyl, phenyl or benzyl; alternatively, an alkoxy, an aryloxy, or an acetylacetonate; alternatively an alkylaminyl or a dialkylaminyl; alternatively a trihydrocarbylsilyl or a hydrocarbylaminylsilyl; alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, an alkoxy, an aryloxy, an acetylacetonate, an alkylaminyl or a dialkylaminyl; alternatively, H; alternatively, a halide; alternatively, methyl; alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy; alternatively an aryloxy; alternatively an 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 may be an alkoxy, an aryloxy, an alkylaminyl, a dialkylaminyl, a trihydrocarbylsilyl, and a C18, C1 to C1 to C1 to C1 to C1 to C1 to C1 to C1 to C3 hydrocarbylaminylsilyl C1 to C12 or C1 to C8.
[0055] Furthermore, each X may independently be, in certain respects, 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 to an alkoxy, an aryloxy, an alkylaminyl, a dialkylaminyl and a C1 to C18 trihydrocarbylsilyl, or a hydrocarbylaminylsilyl group; alternatively, an alkoxy, an aryloxy, an alkylaminyl, a dialkylaminyl and a C1 to C8 trihydrocarbylsilyl, or a hydrocarbylaminylsilyl group; or alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, dekenyl, phenyl, tolyl, benzyl, naphthyl , trimethylsilyl, triisopropylsilyl, triphenylsilyl or allyldimethylsilyl.
[0056] In formula (I), Cp can be a cyclopentadienyl, indenyl or fluorenyl group. In one aspect, for example, Cp can be an unsubstituted cyclopentadienyl, indenyl or fluorenyl group, while in another aspect Cp can be a substituted cyclopentadienyl, indenyl or fluorenyl group. In yet another aspect, Cp can be an unsubstituted cyclopentadienyl group; alternatively, an unsubstituted indenyl group; or alternatively, an unsubstituted fluorenyl group. In yet another aspect, Cp can be a substituted cyclopentadienyl group; alternatively, a substituted indenyl group; or alternatively, a substituted fluorenyl group.
Accordingly, Cp may be a cyclopentadienyl, indenyl or fluorenyl group, and may have one or more substituents. Furthermore, the substituent (or the substituents) may be in any suitable (or suitable) position (or positions) in Cp that conforms to the rules of chemical valence. The substituent (or each substituent independently) may be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxyl group, or a C1 to C36 hydrocarbysilyl group. Therefore, the substituent (or each substituent independently) may 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 hydrocarboxyl group; alternatively a C1 to C18 hydrocarbylsilyl group; alternatively, a C1 to C12 hydrocarbyl group or a C1 to C12 hydrocarbylsilyl group; or alternatively a C1 to C8 alkyl group or a C3 to C8 alkenyl group. The halide, the C1 to C36 hydrocarbyl group, the C1 to C36 hydrocarbyl group and the C1 to C36 hydrocarbylsilyl group which may be a Cp substituent in the formula (I) may be any halide, a C1 to C36 hydrocarbyl group, a hydrocarboxyl group C1 to C36, and a C1 to C36 hydrocarbylsilyl group described herein (for example, so as to belong to X in formula (I)). A Cp substituent can independently be, in certain respects, a C1 to C36 halogenated hydrocarbyl group, the halogenated hydrocarbyl group indicating the presence of one or more halogen atoms replacing an equivalent amount of hydrogen atoms in the group. hydrocarbyl. 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 non-limiting halogenated hydrocarbyl groups include pentafluorophenyl, trifluoromethyl (CF3) and the like.
[0058] As a non-limiting example, a substituent (or each substituent independently) on Cp may be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (eg, 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 2,6-diisopropylphenyl group, a tolyl group (or other substituted aryl group), a benzyl group, a naphthyl group, a trimethylsilyl group, a group triisopropylsilyl, a triphenylsilyl group, an allyldimethylsilyl group, or a 1-methylcyclohexyl group; alternatively, H; alternatively, Cl; alternatively, CF3; alternatively a methyl group; alternatively, an ethyl group; alternatively, a propellant 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 group decyls; 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 2,6-diisopropylphenyl 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; alternatively, an allyldimethylsilyl group; or alternatively a 1-methylcyclohexyl group.
[0059] In one aspect, for example, a substituent (or each substituent independently) on Cp may be H or a C1 to C18 hydrocarbyl group; alternatively a C1 to C10 hydrocarbyl group; alternatively a linear or branched C1 to C6 alkyl group (for example a tert-butyl group); alternatively, H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (for example, 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 group 2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilyl group, or a 1-methylcyclohexyl group, and the like; 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, a decyl group, an ethenyl group, a group propenyl, 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 2,6-diisopropylphenyl group, a tolyl group, or a benzyl group ; alternatively, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group; alternatively a methyl group; alternatively, an ethyl group; alternatively, a propellant group; alternatively a butyl group; or alternatively a tert-butyl group.
[0060] In formula (I), L can be any phosphinimide or iminoimidazolidide linker disclosed herein. In one aspect, for example, the half metallocene titanium compound may have the structure of formula (II):

[0061] In another aspect, the half metallocene titanium compound may have the structure of formula (III):

[0062] In formulas (II) and (III), each of Cp and X may independently be any Cp and X described herein (for example, so as to belong to Cp and X in formula (I)). R 1 , R 2 , R 3 , RA and RB can independently be H or a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxyl group, or a C1 to C36 hydrocarbysilyl group. The halide, the C1 to C36 hydrocarbyl group, the C1 to C36 halogenated hydrocarbyl group, the C1 to C36 hydrocarboxyl group, or the C1 to C36 hydrocarbylsilyl group which can be R1, R2, R3, RA and/or RB can be any halide , C1 to C36 hydrocarbyl group, C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxyl group, or C1 to C36 hydrocarbylsilyl group described herein (for example, so as to belong to substituent options for Cp in formula (I)).
[0063] In formula (II), R1, R2, and R3 can be either the same substituent group or a different substituent group. In one aspect, R1, R2 and R3 can independently be H, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarbylsilyl group. In another aspect, R1, R2 and R3 can independently be H or a C1 to C18 hydrocarbyl group. In yet another aspect, R 1 , R 2 and R 3 can independently be a linear or branched C1 to C6 alkyl group (for example an isopropyl group, a tert-butyl group) or a C3 to C8 alkenyl group (for example an alkenyl group terminal). In yet another aspect, R1, R2, and R3 can independently be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a group hexyl, 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 2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilyl group, or a 1-methylcyclohexyl group , and the like. In some aspects, at least one of R1, R2 and R3 can be an alkenyl group, such as a C3 to C12 alkenyl group or a terminal C3 to C8 alkenyl group.
[0064] In formula (III), RA and RB can be either the same substituent group or a different substituent group. In one aspect, RA and RB can independently be H, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarbylsilyl group. In another aspect, RA and RB can independently be H or a C1 to C18 hydrocarbyl group. In yet another aspect, RA and RB can independently be a linear or branched C1 to C6 alkyl group (for example, a methyl group, an isopropyl group, a tert-butyl group). In yet another aspect, RA and RB may independently 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 phenyl group, a 2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilyl group, or a 1- methylcyclohexyl, and the like. In some aspects, the heterocyclic carbene group may be saturated, while in other aspects, the heterocyclic carbene group may be unsaturated.
[0065] Illustrative and non-limiting examples of half metallocene titanium compounds - which have the structure of formula (I), formula (II) and/or formula (III) - suitable for use in catalyst systems and processes Polymers covered herein may include the following compounds (tBu = tert-butyl; Ph = phenyl; Cy = cyclohexyl; iPr = isopropyl; X = monoanionic ligand such as Cl):
and the like.
The methods for making the half metallocene titanium phosphinimide and half metallocene titanium iminoimidazolidide compounds of the present invention are also encompassed herein. Such metallocene medium complexes can be synthesized by various suitable procedures, such as those described in Organometallics 2001, 20, 4,424, the disclosure of which is incorporated herein by reference in its entirety.
[0067] Using analogous synthesis schemes, middle metallocene complexes with substituents on the phosphorus atom other than tert-butyl or pentenyl can be derived, and complexes with cyclopentadienyl or indenyl groups with various hydrocarbyls and other substituents can be derived. Furthermore, using analogous synthesis schemes, complexes of metallocene medium with non-Cl monoanionic ligands (eg, hydrocarbyl, hydrocarbylaminyl, hydrocarbylsilyl, etc.) can be derived. SECOND METALOCENE COMPOUNDS
[0068] In certain aspects of this invention, the catalyst system may contain a second metallocene compound, in addition to the titanium half metallocene compound. For example, the second metallocene compound can comprise a bridged metallocene compound. In one aspect, the second metallocene compound can comprise a bridged zirconium or hafnium based metallocene compound. In another aspect, the second metallocene compound can comprise a metallocene compound based on hafnium or zirconium bridged with an alkenyl substituent. In yet another aspect, the second metallocene compound can comprise a metallocene compound based on hafnium or zirconium bridged to an alkenyl substituent and a fluorenyl group. In still another aspect, the second metallocene compound may comprise a metallocene compound based on hafnium or zirconium bridged with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent of the bridging group and/or not. cyclopentadienyl group.
[0069] In one aspect, the second metallocene compound may comprise a metallocene compound bonded in a single atom bridged with a fluorenyl group. In another aspect, the second metallocene compound can comprise a metallocene compound bridged single-atom with a fluorenyl group and either a cyclopentadienyl group or an indenyl group. In yet another aspect, the second metallocene compound can comprise a metallocene compound bridged single atom with a fluorenyl group and a cyclopentadienyl group. In yet another aspect, the second metallocene compound can comprise a metallocene compound bridged single-atom with a fluorenyl group and an indenyl group.
In these and other aspects, the bridged metallocene compound may contain an aryl substituent (eg, a phenyl group) on the bridged atom. Additionally or alternatively, the bridged metallocene compound may contain an alkenyl substituent, for example, on the bridging atom, and/or on the fluorenyl group and/or on the cyclopentadienyl or indenyl group.
[0071] Illustrative and non-limiting examples of bridged metallocene compounds that are suitable for use as a second metallocene compound may include the following compounds (Me = methyl, Ph = phenyl; t-Bu = tert-butyl) :

and the like, as well as combinations thereof.
[0072] Additional examples of bridged metallocene compounds that are suitable for use as a second metallocene compound may include, but are not limited to, the following compounds:
and the like, as well as combinations thereof.
[0073] The second metallocene compound is not limited only to bridged metallocene compounds as described above. Other suitable bridged metallocene compounds are disclosed in patent document US 7,026,494, US 7,041,617, US 7,226,886, US 7,312,283 , US 7,517,939 and US 7,619,047. which are incorporated herein by reference in their entirety.
[0074] In certain aspects of this invention, the catalyst system may contain a second metallocene compound, in addition to the titanium half metallocene compound, and the second metallocene compound may comprise an unbridged metallocene compound. In one aspect, the second metallocene compound can comprise an unbridged zirconium or hafnium based metallocene compound and/or an unbridged zirconium or hafnium based dinuclear metallocene compound. In another aspect, the second metallocene compound can comprise an unbridged zirconium or hafnium based metallocene compound that contains two cyclopentadienyl groups, two indenyl groups or a cyclopentadienyl and indenyl group. In another aspect, the second metallocene compound can comprise an unbridged zirconium or hafnium based metallocene compound that contains two cyclopentadienyl groups. In yet another aspect, the second metallocene compound can comprise an unbridged zirconium or hafnium based metallocene compound that contains two indenyl groups. In yet another aspect, the second metallocene compound can comprise an unbridged zirconium or hafnium based metallocene compound that contains a cyclopentadienyl and indenyl group.
[0075] In one aspect, the second metallocene compound may comprise an unalloyed zirconium-based metallocene compound that contains two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and indenyl group, while in another aspect, the second compound of metallocene may comprise a non-dinuclear bridged metallocene compound with an alkenyl linking group.
[0076] Illustrative and non-limiting examples of unbridged metallocene compounds that are suitable for use as the second metallocene compound may include the following compounds (Ph = phenyl):
and the like, as well as combinations thereof.
[0077] The second metallocene compound is not limited only to unbridged metallocene compounds as described above, or to suitable unbridged metallocene compounds in patent document no. , US 7,312,283 and US 7,619,047, which are incorporated herein by reference in their entirety. For example, the second metallocene compound may comprise an unbridged dinuclear metallocene compound such as those described in patent documents US 7,919,639 and US 8,080,681, the disclosures of which are incorporated herein by way of reference in its entirety. Illustrative and non-limiting examples of dinuclear metallocene compounds suitable for use as the second catalyst compound include the following compounds:
and the like, as well as combinations thereof. ACTIVATOR SUPPORTS
[0078] The present invention encompasses various catalyst compositions that contain an activator support. In one aspect, the activator support can comprise a solid oxide treated with an electron withdrawing anion. Alternatively, in another aspect, the activator support may comprise a solid oxide treated with an electron withdrawing anion, the solid oxide containing a Lewis acid metal ion. Non-limiting examples of suitable activator supports are disclosed, for example, in patent documents US 7,294,599, US 7,601,665, US 7,884,163, US 8,309,485, US 8,623,973 and in the US 8,703,886, which are incorporated herein by reference in their entirety.
[0079] Solid oxide can encompass oxide materials such as alumina, "mixed oxides" thereof such as silica-alumina, coatings of one oxide on another, and combinations and mixtures thereof. Mixed oxides such as silica-alumina can be one or multiple chemical phases with more than one metal combined with oxygen to form the solid oxide. Examples of mixed oxides that can be used to form an activator support, either singly or in combination, may include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, alumina-titania, alumina -zirconia, zinc aluminate, alumina boria, silica boria, aluminophosphate silica, titania-zirconia and the like. The solid oxide used herein may also encompass oxide materials such as silica coated alumina as described in U.S. patent document 7,884,163.
[0080] Consequently, in one aspect, solid oxide may comprise silica, alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria , zinc oxide, any mixed oxide thereof, or any combination thereof. In another aspect, the solid oxide may comprise alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria or zinc oxide, as well as any mixed oxides thereof, or any mixtures thereof. In another aspect, the solid oxide may comprise silica, alumina, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or any combination thereof. In yet another aspect, the solid oxide may comprise silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boria or any combination thereof. In yet another aspect, the solid oxide can comprise alumina, silica-alumina, silica coated alumina, or any mixture thereof; alternatively, alumina; alternatively, silica-alumina; or alternatively, silica coated alumina.
[0081] The silica-coated solid aluminum oxide or silica-alumina materials that can be used can have a silica content of about 5 to about 95% by weight. In one aspect, the silica content of these solid oxides can be from about 10 to about 80%, or from about 20% to about 70%, silica by weight. In another aspect, such materials can have silica contents in the range of from about 15% to about 60%, or from about 25% to about 50%, silica by weight. The solid oxides contemplated herein may have any suitable surface area, pore volume and particle size as would be recognized by those skilled in the art.
[0082] The electron withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide upon treatment (compared to solid oxide that is not treated with at least one anion of electron withdrawal). According to one aspect, 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, which serves as a source or a precursor for that anion. Examples of electron withdrawing anions may include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, tungstate , molybdate, and the like, including mixtures and combinations thereof. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions can also be employed. 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 provided herein. 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. In still other aspects, the electron withdrawing anion may comprise fluoride and/or sulfate.
[0083] The activator support can generally contain from about 1 to about 25% by weight of the electron withdrawn anion, based on the weight of the activator support. In particular aspects provided herein, the activator support may contain from about 1 to about 20% by weight, from about 2 to about 20% by weight, from about 3 to about 20% by weight from about 2 to about 15% by weight, from about 3 to about 15% by weight, from about 3 to about 12% by weight, or from about 4 to about 10% by weight, of the electron-withdrawal anion, based on the total weight of the activator bracket.
[0084] In one aspect, the activator support may comprise fluorinated amine, chlorinated amine, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-coated alumina, and the like, as well as any mixture or combination thereof. In another aspect, the activator support employed in the catalyst systems described herein can be, or can comprise, a fluorinated solid oxide and/or a sulfated solid oxide, non-limiting examples of which may include fluoridated amine, sulfated alumina, silica- fluorinated alumina, sulfated silica-alumina, fluorinated silica-zirconia, fluorinated silica coated alumina, sulfated silica coated alumina, and the like, as well as combinations thereof. In yet another aspect, the activator support can comprise fluorinated amine; alternatively, chlorinated amine; alternatively, sulfated alumina; alternatively, fluorinated silica-alumina; alternatively, sulfated silica-alumina; alternatively, fluorinated silica-zirconia; alternatively, chlorinated silica-zirconia; alternatively, sulfated silica coated alumina; or alternatively, alumina coated with fluorinated silica. In some aspects, the activator support can comprise a fluoridated solid oxide, while in other aspects the activator support can comprise a sulfated solid oxide.
[0085] Various processes can be used to form activator supports useful in the present invention. Methods of contacting the solid oxide with the electron withdrawing component, suitable electron withdrawing components and amounts of addition, impregnation with metals or metal ions (eg, zinc, nickel, vanadium, titanium, silver, copper , gallium, tin, tungsten, molybdenum, zirconium, and the like, or combinations thereof), and various calcination procedures and conditions are disclosed, for example, in patent documents US 6,107,230, US 6,165,929, in the US 6,294,494, in the US 6,300,271, in the US 6,316,553, in the US 6,355,594 in the US 6,376,415 in the US 6,388,017 in the US 6,391,816 in the US 6,395,666 in the US 6,524,987, in US 6,548,441, in US 6,548,442, in US 6,576,583, in US 6,613,712, in US 6,632,894, in US 6,667,274, in US 6,750,302, in US 7,294. 599, US 7,601,665, US 7,884,163, and US8,309,485, which are incorporated herein by reference in their entirety. Other suitable processes and procedures for preparing activator supports (e.g., fluorinated solid oxides, sulfated solid oxides, etc.) as well known to those skilled in the art. COCATALYST
[0086] In certain aspects directed to catalyst compositions that contain a cocatalyst, the cocatalyst may comprise a metal hydrocarbyl compound, examples of which include non-halide metal hydrocarbyl compounds, metal hydrocarbyl halide compounds, metal alkyl compounds, non-halide metal, metal alkyl halide compounds, and so on. The hydrocarbyl group (or alkyl group) can be any hydrocarbyl (or alkyl) group disclosed herein. Furthermore, in some aspects, the metal of the metal hydrocarbyl may be a group 1, 2, 11, 12, 13 or 14 metal; alternatively a group 13 or 14 metal; or alternatively, a group 13 metal. Therefore, in some aspects, the metal of the metal hydrocarbyl (a metal hydrocarbyl halide or non-halide metal hydrocarbyl) may 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 hydrocarbyl metal or alkyl metal, with or without a halide, may comprise a lithium alkyl or hydocarbyl, a magnesium alkyl or hydocarbyl, a boron alkyl or hydocarbyl, a zinc alkyl or hydocarbyl or an alkyl or aluminum hydrocarbyl.
[0087] In particular aspects directed to catalyst compositions that contain a cocatalyst (for example, the activator may comprise a solid oxide treated with an electron withdrawing anion), the cocatalyst may comprise an aluminoxane compound, an organoboron compound or organoborate, an ionizing ionic compound, an organoaluminium compound, an organozinc compound, an organomagnesium compound, or an organolithium compound, and this includes any combinations of these materials. In one aspect, the cocatalyst can comprise an organoaluminium compound. In another aspect, the cocatalyst may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof. In yet another aspect, the cocatalyst 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.
Specific non-limiting examples of suitable organoaluminum compounds may include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri- n-hexylaluminum, tri-n-octylaluminum, diethylaluminum ethoxide hydride, diethylaluminum chloride, and combinations thereof. Representative examples are pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Representative and non-limiting examples of organoboron/organoborate compounds include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, tetrakis[3,5-bis(trifluoromethyl) )N,N-dimethylanilinium phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixtures thereof.
[0089] Examples of ionic ionizing compounds may include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(m-tolyl)tetrakis(m-tolyl)borate n-butyl)ammonium, tetrakis(2,4-dimethylphenyl)tri(n-butyl)ammonium borate, tetrakis(3,5-dimethylphenyl)tri(n-butyl)ammonium borate, tetrakis[3,5-bis( tri(n-butyl)ammonium trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, tetrakis(m-tolyl)borate N,N-dimethylanilinium, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, tetrakis[3,5-bis(trifluoromethyl)phenyl] N,N-dimethylanilinium borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, tetrakis(2,4-dimethylphenyl)borate triphenylcarbenium, tetrakis(3,5-dimethylphenyl) triphenylcarbenium borate, tetrakis[3,5- triphenylcarbenium bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropium tetrakis(p-tolyl) borate, tropium tetrakis(m-tolyl) borate, tetrakis(2,4-dimethylphenyl) tropium borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, tetrakis( lithium p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, tetrakis(pentafluorophenyl) sodium 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, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetraphenylborate, potassium tetrakis(p-tolyl)borate, and trakis(m-tolyl)potassium borate, 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, tetrakis( sodium pentafluorophenyl)aluminate, sodium tetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, tetrakis(3,5-dimethylphenyl) sodium aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, tetrakis(2,4-dimethylphenyl)aluminate potassium, potassium tetrakis (3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate o, and the like, or combinations thereof.
Exemplary organozinc compounds that can be used as cocatalysts may include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dynepentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di(triisopropylsilyl)zinc , di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc and the like, or combinations thereof.
Similarly, exemplary organomagnesium compounds may include, but are not limited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dinepentylmagnesium, di(trimethylsilylmethyl)magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, of butylmagnesium, neopentylmagnesium chloride, trimethylsilylmethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesium bromide, trimethylsilylmethylmagnesium bromide, butylmagnesium methylmagnesium bromide, methylmagnesium propylmagnesium bromide, methylmagnesium iodide, iodide , neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide, methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesium ethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide, trimethylsilylmethylmagnesium ethoxide, methyl propylmagnesium propoxide,magnesium oxide, io, butylmagnesium propoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesium propoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide, propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesium phenoxide, trimethylsilyl phenoxide or any similar combinations thereof.
[0092] Likewise, exemplary organolithium compounds may include, but not limited to, methyllithium, ethyllithium, propyllithium, butyllithium (eg, t-butyllithium), neopentyllithium , trimethylsilylmethyllithium, phenyllithium, tolyllithium, xylyllithium, benzyllithium, (dimethylphenyl)methyllithium, allyllithium, and the like, or combinations thereof.
[0093] The cocatalysts that can be used in the catalyst compositions of this invention are not limited to the cocatalysts described above. Other suitable cocatalysts as well known to those skilled in the art including, for example, the same in patent document US 3,242,099, US 4,794,096, US 4,808,561, US 5,576,259, US 5,807. 938, US 5,919,983, US 7,294,599, US 7,601,665, US 7,884,163, US 8,114,946, and US 8,309,485, which are incorporated herein by reference to its entirety. OLEFIN MONOMERS
[0094] The unsaturated reagents that can be employed with the catalyst compositions and polymerization processes of this invention typically can include olefin compounds that have from 2 to 30 carbon atoms per molecule and that have at least one olefinic double bond. This invention encompasses homopolymerization processes with the use of a single olefin such as ethylene or propylene, as well as copolymerization reactions, terpolymerization, etc., with the use of an olefin monomer with at least one different olefinic compound. For example, the resulting ethylene copolymers, terpolymers, etc., can generally contain a greater amount of ethylene (>50 mole percent) and a smaller amount of a comonomer (<50 mole percent), although this is not a requirement. . Comonomers that can be copolymerized with ethylene often can have 3 to 20 carbon atoms, or 3 to 10 carbon atoms, in their molecular chain.
[0095] Acyclic, cyclic, polycyclic, terminal (), internal, linear, branched, substituted, unsubstituted, functionalized, and unfunctionalized olefins may be employed in this invention. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention may include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1 - pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene , 3-heptene, the four normal octenes (eg, 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, can also be polymerized as described herein. Styrene can also be employed as a monomer in the present invention. In one aspect, the olefin monomer can comprise a C2 to C20 olefin; alternatively a C2 to C20 alpha-olefin; alternatively a C2 to C10 olefin; alternatively a C2 to C10 alpha-olefin; alternatively, the olefin monomer may comprise ethylene; or alternatively, the olefin monomer can comprise propylene.
[0096] When a copolymer (or alternatively a thermopolymer) is desired, the olefin monomer and the olefin comonomer may independently comprise, for example, a C2 to C20 alpha-olefin. In some aspects, the olefin monomer can comprise ethylene or propylene, which is copolymerized with at least one comonomer (e.g., a C2 to C20 alpha-olefin, a C3 to C20 alpha-olefin, etc.). According to one aspect of this invention, the olefin monomer used in the polymerization process may comprise ethylene. In that regard, examples of suitable olefin comonomers may include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl -1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene , and the like, or combinations thereof. According to another aspect of the present invention, the olefin monomer can comprise ethylene, and the comonomer can comprise a C3 to C10 alpha-olefin; alternatively, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may comprise 1-butene; alternatively, the comonomer may comprise 1-hexene; or alternatively, the comonomer may comprise 1-octene.
[0097] Generally, the amount of a comonomer introduced into a polymerization reactor system in order to produce a copolymer can be from about 0.01 to about 50 percent by weight of the comonomer based on the total weight of the monomer and comonomer. According to another aspect of the present invention, the amount of a comonomer introduced into a polymerization reactor system can be from about 0.01 to about 40 percent by weight of a comonomer based on the total weight of the monomer and comonomer . In yet another aspect, the amount of a comonomer introduced into a polymerization reactor system can be from about 0.1 to about 35 percent by weight of a comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of a comonomer introduced into a polymerization reactor system can be from about 0.5 to about 20 percent by weight of a comonomer based on the total weight of the monomer and comonomer.
[0098] Although not intended to be limited by this theory, as branched, substituted or functionalized olefins are used as reactants, it is believed that a steric obstacle can impede and/or slow down the polymerization process. Thus, it would not be expected that the branched (or branched) and/or cyclic (or cyclic) portion (or portions) of the olefin that removed some of the carbon-carbon double bond would impair the reaction in the way that the same situated olefin substituents closer to the carbon-carbon double bond can.
[0099] According to one aspect of the present invention, at least one monomer/reagent can be ethylene (or propylene), then the polymerization reaction can be a homopolymerization involving only ethylene (or propylene), or a copolymerization with an olefin acyclic, cyclic, terminal, internal, linear, branched, substituted or unsubstituted different. Furthermore, 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 that contain a half metallocene titanium compound (optionally, a second metallocene compound) and an activator support (one or more than one). These catalyst compositions can be used to produce polyolefins - homopolymers, copolymers, and the like - for a variety of end use applications. Half metallocene titanium compounds and optional second metallocene compounds are discussed herein above. In aspects of the present invention, it is contemplated that the catalyst composition may contain more than one half metallocene titanium compound and/or more than one second metallocene compound. In addition, additional catalyst compounds - other than those specified as a half metallocene titanium compound or a second metallocene compound - may be employed in catalyst compositions and/or polymerization processes, provided the additional catalyst compound does not deviate from the advantages revealed in this document. Additionally, more than one activator support can also be used.
[00101] Generally, the catalyst compositions of the present invention comprise a half metallocene titanium compound having the formula (I) (for example, the formula (II) or (III)) and an activator support (for example, a solid oxide treated with an electron withdrawing anion). Activator supports useful in the present invention are disclosed herein. Optionally, such catalyst compositions may further comprise one or more than one second metallocene compound (or second compounds), and/or may additionally comprise one or more than one cocatalyst compound (or compounds) (suitable cocatalysts such as organoaluminium compounds are also discussed in this document). Thus, a catalyst composition of this invention can comprise a half metallocene titanium compound, an activator support and an organoaluminum compound (and optionally, a second metallocene compound). For example, the activator support may comprise (or consist essentially of, or consist of) fluorinated amine, chlorinated amine, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina , fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated-silica-coated alumina, phosphate-coated alumina, and the like or combinations of same; or alternatively, a fluorinated solid oxide and/or a sulfated solid oxide. Additionally, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, hydride. diisobutylaluminum, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof. Accordingly, a catalyst composition consistent with aspects of the invention may comprise (or consist essentially of, or consist of) a half metallocene titanium compound; sulfated alumina (or silica-fluorinated alumina, or alumina coated with fluorinated silica); and triethylaluminum (or triisobutylaluminum). Optionally, dual catalyst systems can contain a half metallocene titanium compound and a second metallocene compound as described herein.
[00102] In one aspect, a catalyst composition of the present invention may comprise a half metallocene titanium compound having the formula (II) or (III), a fluorinated solid oxide, and optionally, a cocatalyst, such as a compound of organoaluminium. In yet another aspect, a catalyst composition of the present invention may comprise a half metallocene titanium compound having formula (II) or (III), a sulfated solid oxide, and optionally, a cocatalyst, such as a compound of organoaluminium. Additionally, a second metallocene compound can be included in such catalyst compositions, if desired.
[00103] In another aspect of the present invention, there is provided a catalyst composition comprising a half metallocene titanium compound, an activator support and an organoaluminum compound, wherein such catalyst composition is substantially free of aluminoxanes, compounds of organoboron or organoborate, ionic ionizing compounds, and/or other similar materials; alternatively, substantially free of aluminoxanes; alternatively substantially free or organoboron or organoborate compounds; or alternatively, substantially free of ionic ionizing compounds. In these aspects, the catalyst composition has a catalyst activity, discussed below, in the absence of these additional materials. For example, a catalyst composition of the present invention may consist essentially of a half metallocene titanium compound, an activator support and an organoaluminum compound, wherein no other material is present in the catalyst composition that can increase/decrease activity of the catalyst composition to greater than about 10% of the catalyst activity of the catalyst composition in the absence of said materials.
[00104] However, in other aspects of this invention, these cocatalysts may be employed. For example, a catalyst composition comprising a half metallocene titanium compound and an activator support can further comprise an optional cocatalyst. Suitable cocatalysts in this regard may include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionic ionizing compounds, organoaluminium compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, or any combination of them; or alternatively, organoaluminium compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, or any combination thereof. More than one cocatalyst can be present in the catalyst composition.
[00105] In a particular aspect contemplated herein, the catalyst composition is a catalyst composition comprising an activator support (one or more than one) and only one half metallocene titanium compound. In these and other aspects, the catalyst composition may comprise an activator support comprising a solid oxide treated with an electron withdrawing anion, only a half metallocene titanium compound, and a cocatalyst (one or more than one) , such as an organoaluminium compound.
[00106] This invention further encompasses methods for making such catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence. In one aspect, the catalyst composition can be produced by a process comprising contacting the half metallocene titanium compound and the activator support, while in another aspect, the catalyst composition can be produced by a process comprising contact, in any order, the half metallocene titanium compound, the activator holder and the cocatalyst.
[00107] Generally, the weight ratio of organoaluminium compound to activator support can be in a range from about 10:1 to about 1:1000. If more than one organoaluminium compound and/or more than one activator bracket are employed, this rate is based on the total weight of each respective component. In another aspect, the weight ratio of organoaluminium compound to activator support can be in a range of from about 3:1 to about 1:100, or from about 1:1 to about 1:50.
[00108] In some aspects of this invention, the weight ratio of half metallocene titanium compound to activator support can be in a range from about 1:1 to about 1:1,000,000. If more than one half metallocene titanium compound and/or more than one activator support is/are employed, this ratio is based on the total weights of the respective components. In another aspect, this one weight ratio can range from about 1:5 to about 1:100,000, or from about 1:10 to about 1:10,000. In yet another aspect, the weight ratio of the half metallocene titanium compound to the activator support can range from about 1:20 to about 1:1,000.
[00109] The catalyst compositions of the present invention generally have a catalyst activity greater than about 10 kg of ethylene polymer (homopolymer or copolymer, as the context requires) per gram of half metallocene titanium compound per hour (abbreviated kg/g/h). In another aspect, the catalyst activity can be greater than about 25, greater than about 35, or greater than about 40 kg/g/h. In yet another aspect, the catalyst compositions of this invention can be characterized by the fact that they have a catalyst activity greater than about 50, greater than about 100, or greater than about 150 kg/g/h, and it can often be in the range of up to 400, up to 500, or up to 750 kg/g/h. These activities are measured under slurry polymerization conditions, with a triisobutylaluminum cocatalyst, using dibutane as the diluent, at a polymerization temperature of 80 °C and a reactor pressure of about 2.34 MPa (340 psig). Additionally, in some aspects, the activator support may comprise, but not limited to, sulfated alumina, silica-fluorinated alumina, or alumina coated with fluorinated silica.
[00110] In aspects of this invention where the catalyst composition contains a second metallocene compound, the weight ratio of the titanium compound of half metallocene to the second metallocene compound (e.g., a bridged metallocene, a non-metallocene bridged) in the catalyst composition can be in a range of from about 10:1 to about 1:10, from about 8:1 to about 1:8, 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. POLYMERIZATION PROCESSES
[00111] The catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers and the like. Such a process for polymerizing olefins in the presence of a catalyst composition of the present invention may comprise contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer (one or more) in a polymerization reactor system under conditions of polymerization to produce an olefin polymer, wherein the catalyst composition may comprise a half metallocene titanium compound, an activator support and an optional cocatalyst, and an optional second metallocene compound. Half metallocene titanium compounds, second metallocene compounds, activator supports, and suitable cocatalysts are discussed herein.
[00112] According to one aspect of the invention, the polymerization process may employ a catalyst composition comprising a half metallocene titanium compound having formula (II) or (III) and an activator support. The catalyst composition optionally may further comprise one or more than one organoaluminium compound or compounds (or other suitable cocatalyst), and/or may additionally comprise one or more than one second metallocene compound (or second compounds). Thus, a process for polymerizing olefins in the presence of a catalyst composition can employ a catalyst composition comprising a half metallocene titanium compound, an activator support, and an organoaluminum compound. In some aspects, the activator support may comprise (or consist essentially of, or consist of) fluorinated amine, chlorinated amine, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica-alumina sulfated silica, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated-silica-coated alumina, phosphate-coated alumina, and the like, or combinations of the same; alternatively, a fluorinated solid oxide and/or a sulfated solid oxide; alternatively, a fluorinated solid oxide; or alternatively, a sulfated solid oxide. In some aspects, the organoaluminum compound may 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. Optionally, polymerization processes consistent with aspects of this invention can employ a dual catalyst system that contains a half metallocene titanium compound and a second metallocene compound, as described herein.
[00113] According to another aspect of the invention, the polymerization process may employ a catalyst composition comprising a half metallocene titanium compound, an activator support, and an optional cocatalyst, wherein the cocatalyst may comprise a compound of aluminoxane, an organoboron or organoborate compound, an ionic ionizing compound, an organoaluminium compound, an organozinc compound, an organomagnesium compound, or an organolithium compound, or any combination thereof. Therefore, aspects of this invention are directed to a process for polymerizing olefins in the presence of a catalyst composition, the process 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 may comprise a half metallocene titanium compound, an activator support, and an aluminoxane compound; alternatively, a half metallocene titanium compound, an activator support, and an organoboron or organoborate compound; alternatively, a half metallocene titanium compound, an activator support, and an ionizing ionic compound; alternatively, a half metallocene titanium compound, an activator support, and an organoaluminium compound; alternatively, a half metallocene titanium compound, an activator support, and an organozinc compound; alternatively, a half metallocene titanium compound, an activator support, and an organomagnesium compound; or alternatively, a half metallocene titanium compound, an activator support, and an organolithium compound. Furthermore, more than one cocatalyst can be employed, for example, an organoaluminium compound and an aluminoxane compound, an organoaluminium compound and an ionizing ionic compound, etc.
[00114] According to another aspect of the invention, the polymerization process can employ a catalyst composition comprising only a half metallocene titanium compound, an activator support and an organoaluminium compound.
[00115] The catalyst compositions of the present invention are intended for any method of polymerization of olefin with the use of various types of polymerization reactor systems and reactors. The polymerization reactor system can include any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of reactors include the same ones that can be called as a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, and the like, or combinations thereof. Appropriate polymerization conditions are used for the various reactor types. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Slurry reactors can comprise vertical or horizontal circuits. High pressure reactors can comprise autoclave or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes can use intermittent or continuous product discharge. Processes can also include a direct partial or complete recycling of an unreacted monomer, unreacted comonomer and/or a diluent.
[00116] The 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 (for example, a single reactor, double reactor, more than two reactors). Polymer production in multiple reactors can include many stages in at least two separate polymerization reactors interconnected by a transfer device that makes it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactor (or other reactors). Alternatively, polymerization in multiple reactors can include manual transfer of a 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 high pressure reactors with circuit and/or gas phase. Multiple reactors can be operated in series, in parallel, or both. Accordingly, the present invention encompasses polymerization reactor systems which comprise a single reactor, which comprise two reactors, and which comprise more than two reactors. The polymerization reactor system may comprise a slurry reactor, a gas phase reactor, a solution reactor, in certain aspects of this invention, as well as combinations of multiple reactors thereof.
[00117] According to one aspect of the invention, the polymerization reactor system may comprise at least one loop slurry reactor comprising vertical or horizontal loops. A monomer, diluent, catalyst and comonomer can be continuously fed into a loop reactor where a polymerization takes place. Generally, continuous processes can comprise continuously introducing monomer/comonomer, a catalyst, and a diluent into a polymerization reactor and continuously removing that reactor from a suspension comprising polymer particles and the diluent. The reactor effluent can be vaporized to remove solid polymer from liquids comprising the diluent, monomer and/or comonomer. Various technologies can be used for this separation step including, but not limited to, vaporization which can include any combination of heat addition and pressure reduction, separation by cyclonic action either in a cyclone or in a hydrocyclone, or separation by centrifugation.
[00118] A typical slurry polymerization process (also known as the particle formation process) is disclosed, for example, in patent documents in US 3,248,179, in US 4,501,885, in US 5,565,175, US 5,575,979, US 6,239,235, US 6,262,191, and US 6,833,415, each of which is incorporated herein by reference in their entirety.
[00119] Suitable diluents used in slurry polymerization include, but are not limited to, monomer that is polymerized and hydrocarbons that are liquid under polymerization conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions can occur under bulk conditions where no diluent is used. One example is the polymerization of propylene monomer as in U.S. patent document 5,455,314, which is incorporated by reference herein in its entirety.
[00120] According to yet another aspect of this invention, the polymerization reactor system may comprise at least one gas phase reactor. Such systems can employ a continuous recycle stream that contains one or more monomers continuously cycled through a fluidized bed in the presence of catalyst under polymerization conditions. A recycle stream can be withdrawn from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product can be withdrawn from the reactor and a new monomer or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors may comprise a process for a multi-step gas phase polymerization of olefins, wherein the olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is in US 5,352,749, US 4,588,790, and US 5,436,304, each of which is incorporated by reference in its entirety herein. .
[00121] According to yet another aspect of the invention, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have many zones where fresh monomers, initiators or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a reactor zone. Initiators, catalysts and/or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. Gas sources can be intermixed for polymerization. Heat and pressure can be appropriately employed to obtain optimum polymerization reaction conditions.
[00122] According to yet another aspect of the invention, the polymerization reactor system may comprise a solution polymerization reactor in which the monomer (and a comonomer, if used) is brought into contact with the catalyst composition through a suitable agitation or other means. A carrier comprising an inert organic diluent or excess monomer may 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 keep the polymerization mixtures uniform throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
[00123] Polymerization reactor systems suitable for the present invention may further comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components, and/or at least one system of polymer recovery. Reactor systems suitable for the present invention may further comprise systems for raw material purification, catalyst preparation and storage, extrusion, reactor cooling, polymer recovery, fractionation, recycle, storage, loading, laboratory analysis and process control .
[00124] Polymerization conditions that are controlled for efficiency and to provide desired polymer properties can include temperature, pressure and concentrations of various reactants. Polymerization temperature can affect a catalyst productivity, a polymer molecular weight, and a molecular weight distribution. A suitable polymerization temperature can be any temperature below the depolymerization 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 on the type of polymerization reactor (or reactors). In some reactor systems, the polymerization temperature can generally be in a range from about 65°C to about 110°C, from about 70°C to about 100°C, from about 70°C to about from 95°C, or from about 75°C to about 95°C. Various polymerization conditions can be kept substantially constant, for example, for producing a particular grade of olefin polymer.
[00125] Appropriate pressures will also vary according to reactor and type of polymerization. The pressure for liquid phase polymerizations in a loop reactor is typically less than 1,000 psig (6.9 MPa). The pressure for a gas phase polymerization is typically about 200 to 500 psig (1.4 MPa to 3.4 MPa). A high pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also be operated in a supercritical region that generally occurs at higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) can offer advantages.
[00126] In a particular aspect, and unexpectedly, a polymerization process may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions in order to produce a polymer of olefin (eg, a homopolymer or copolymer of ethylene) characterized by a ratio of Mw/Mn in a range of about 4 to about 10 (or about 5 to about 9), an HLMI/MI ratio in a range of about 15 to about 75 (or about 25 to about 55), a density in a range of about 0.89 to about 0.97 g/cm3 (or about 0. 92 to about 0.94 g/cm3), less than or equal to about 0.008 long chain branches (LCB) per 1,000 total carbon atoms (or less than or equal to about 0.003 LCB), and a conventional comonomer distribution (eg the amount of short chain branches (SCB) per 1000 total polymer carbon atoms in Mn is greater than in Mz). The catalyst composition used in this process may comprise a half metallocene titanium compound, a fluorinated solid oxide (eg, fluorinated silica-alumina, fluorinated silica coated alumina, etc.) or a solid sulfate oxide (eg, alumina sulfate, etc.), and an optional cocatalyst (eg an organoaluminium compound).
[00127] Aspects of this invention are also directed to olefin polymerization processes conducted in the absence of added hydrogen. An olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise a half metallocene titanium compound, an activator support, and an optional cocatalyst, and wherein the polymerization process is conducted in the absence of added hydrogen (no hydrogen is added to the polymerization reactor system) . As a person of ordinary skill in the art can recognize, hydrogen can be generated in situ by transition metal-based catalyst compositions in various olefin polymerization processes, and the amount generated can vary depending on the catalyst composition and the compound of specific transition metal employed, the type of polymerization process used, the polymerization reaction conditions used, and so on.
[00128] In other respects, 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 may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions in order to produce an olefin polymer, wherein the catalyst composition comprises a half metallocene titanium compound, an activator support, and an optional cocatalyst, and wherein the polymerization process is conducted in the presence of added hydrogen (hydrogen is added to the polymerization reactor system) . For example, the rate of hydrogen to olefin monomer in the polymerization process can be controlled, often by the feed rate of hydrogen to the olefin monomer entering the reactor. The rate of hydrogen monomer to olefin added in the process can be controlled at a weight rate that is in a range from about 25 ppm to about 1500 ppm, from about 50 to about 1,000 ppm, or from about 100 ppm to about 750 ppm.
[00129] Unexpectedly, the catalyst compositions and polymerization processes of the present invention may be much more sensitive to hydrogen than comparable catalyst systems and processes employing Ziegler catalysts. In one aspect, for example, an increase in the melt index of the olefin polymer with the addition of 150 ppm by weight of hydrogen (from 0 to 150 ppm by weight of hydrogen based on the olefin monomer, using the compositions of catalyst and polymerization processes described herein) may be greater than the increase in melt index of an olefin polymer obtained using a Ziegler-type catalyst system under the same polymerization conditions. For example, the melt index of the olefin polymer (eg, an ethylene/1-hexene copolymer) produced by the process can have a melt index increase of at least about 1 g/10 min, based on a increasing a hydrogen:monomer weight ratio (eg, a hydrogen:ethylene weight ratio) from 0 to 150 ppm by weight. In some respects, this hydrogen increase can result in a melt index increase of at least about 1.2 g/10 min, at least about 1.5 g/10 min, or at least about 2 g/10 min, and in some cases up to about 3 g/10 min or up to about 5 g/10 min.
[00130] In some aspects of this invention, the feed or reactant rate of hydrogen to olefin monomer can be kept substantially constant during a polymerization run for a particular polymer grade. That is, the hydrogen:olefin monomer ratio can be selected at a particular rate in a range from about 5 ppm to about 1000 ppm or so, and maintained at the rate of about +/-25% during a run. of polymerization. For example, if the target rate is 100ppm, then keeping the hydrogen:olefin monomer ratio substantially constant would imply keeping the feed rate between about 75ppm and about 125ppm. Furthermore, the addition of a comonomer (or comonomer) can be, and usually is, substantially constant throughout every polymerization run for a particular polymer grade.
[00131] However, in other respects, it is contemplated that a monomer, a comonomer (or comonomers) and/or hydrogen may be periodically pulsed in the reactor, for example, in a manner similar to that employed in the patent document in US 5,739 220 and patent publication no. US 2004/0059070, the disclosures of which are incorporated herein by reference in their entirety.
[00132] In a particular aspect, and unexpectedly, the Mw/Mn rate of the olefin polymer produced by the process may decrease depending on the amount of an organozinc compound (eg diethylzinc) added to the polymerization reactor system increases. For example, the Mw/Mn ratio of the polymer produced by the process in the absence of the organozinc compound may be greater than the Mw/Mn of a polymer produced by the process in the presence of the organozinc compound, under the same polymerization conditions. Additionally or alternatively, the z-average molecular weight (Mz) of the olefin polymer produced by the process may decrease as the amount of an organozinc compound (eg, diethylzinc) added to the polymerization reactor system increases. For example, the Mz of the polymer produced by the process in the absence of the organozinc compound may be greater than the Mz of a polymer produced by the process in the presence of the organozinc compound, under the same polymerization conditions. The same polymerization conditions mean that all components used to prepare the catalyst systems are kept constant (eg same quality/same type of medium metallocene compound, same quality/same type of cocatalyst, same quality/same type of activator , such as alumina coated with fluorinated silica, etc.) and all polymerization conditions are kept constant (eg same polymerization temperature, same pressure, etc.). Therefore, the only difference is the amount of organozinc compound present during polymerization.
[00133] The concentration of reactants entering the polymerization reactor system can be controlled in order 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 for forming the same product can ultimately determine the desired polymer properties and attributes. Mechanical properties include tension, flexural, impact, creep, stress and relaxation, and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, melting temperature of crystallization, density, stereoregularity, increased breakage, long-chain branching, and rheological measurements .
This invention is also directed to, and encompasses, polymers (e.g., ethylene/-olefin copolymers, ethylene homopolymers, etc.) produced by any of the polymerization processes disclosed herein. Articles of manufacture can be formed from the polymers, and/or comprise the same, produced in accordance with this invention. POLYMERS AND ARTICLES
[00135] Olefin polymers covered herein may include any polymer produced from any olefin monomer and comonomer described herein. For example, the olefin polymer may comprise an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer (for example, ethylene/-olefin, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), a propylene copolymer, an ethylene terpolymer, a propylene terpolymer, and the like, including combinations thereof. In one aspect, the olefin polymer can be an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer, while in another aspect, the olefin polymer can be an ethylene/1-hexene copolymer.
[00136] If the resulting polymer produced according to the present invention is, for example, an ethylene polymer, its properties may be characterized by various analytical techniques known and used in the polyolefin industry. Articles of manufacture may be formed from, and/or comprise the same, ethylene polymers of this invention, the typical properties of which are given below.
[00137] Densities of ethylene-based polymers (eg, ethylene homopolymers, ethylene copolymers) produced using the catalyst systems and processes disclosed herein are often greater than or equal to about 0. 89 g/cm3, for example, greater than or equal to about 0.91 g/cm3, or greater than or equal to about 0.92 g/cm3. Still, in particular aspects, the density may be in a range of from about 0.89 to about 0.97, such as, for example, from about 0.91 to about 0.97, from about 0 from about 0.91 to about 0.94, from about 0.92 to about 0.94, or from about 0.925 to about 0.945 g/cc. Unexpectedly, ethylene/-olefin copolymers (eg, ethylene/1-hexene copolymers) produced using the catalyst systems and polymerization processes described herein may have enhanced comonomer incorporation, for example , which has a density decrease of at least about 0.008 g/cm3, of at least about 0.01 g/cm3, of at least about 0.015 g/cm3, or of at least about 0.02 g/cm3. cm3, and in some cases, up to about 0.025 g/cm3, or up to about 0.035 g/cm3, based on an increase in comonomer:monomer molar ratio (for example, a molar ratio of 1-hexene:ethylene) from 0 (no comonomer) to a comonomer:monomer molar ratio (eg, a 1-hexene:ethylene molar ratio) of 0.0176:1.
[00138] In some aspects, the ethylene polymers described herein may have a Mw/Mn ratio, or polydispersity index, in a range of from about 4 to about 10, from about 4 to about 9 , from about 5 to about 10, from about 4.5 to about 9.5, from about 4.5 to about 9, or from about 5 to about 9, and the like.
[00139] In one aspect, the polymers described herein may have an HLMI/MI ratio in a range of about 10 to about 80, such as, for example, from about 15 to about 75, of about from about 20 to about 70, from about 20 to about 65, from about 20 to about 60, or from about 25 to about 55, and the like.
[00140] Generally, polymers produced in aspects of the present invention are essentially linear or have very low levels of long chain branching, with typically less than about 0.01 long chain branching (LCB) per 1,000 total carbon atoms , and similar in LCB content for the polymers shown, for example, in patent document no. US 7,517,939, no. totality. In other aspects, the amount of LCB per 1,000 total carbon atoms may be less than or equal to about 0.008, less than or equal to about 0.007, less than or equal to about 0.005, or less than or equal to about 0.003 LCB per 1,000 total carbon atoms.
[00141] Ethylene copolymers, for example, produced using the polymerization processes and catalyst systems described above herein, in some respects, may have a conventional comonomer distribution; generally, the higher molecular weight components of the polymer have less comonomer incorporation than the lower molecular weight components. Typically, there is a decrease in comonomer incorporation with an increase in molecular weight. In one aspect, the amount of short chain branches (SCB) per 1,000 total polymer carbon atoms may be greater in Mn than in Mw. In another aspect, the amount of SCB per 1,000 total polymer carbon atoms may be greater in Mn than in Mz. In yet another aspect, the amount of SCB per 1,000 total polymer carbon atoms may be greater in Mw than in Mz. In yet another aspect, the amount of SCB per 1,000 total polymer carbon atoms at a molecular weight of 106 may be less than at a molecular weight of 105.
[00142] Olefin polymers, whether homopolymers, copolymers, and so on, can be formed into various articles of manufacture. Articles that may comprise polymers of this invention include, but are not limited to, an agricultural film, an automobile part, a bottle, a chemical container, a drum, a fiber or fabric, a film or a packaging container. of food, a food service article, a fuel tank, a geomembrane, a homemade container, a liner, a molded product, a medical device or material, an external storage product, an external leisure equipment, a pipe, a blade or tape, a toy, or a traffic barrier, and the like. Various processes can be used to form these articles. Non-limiting examples of these processes include injection molding, blow molding, spin 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 the documents Modern Plastics Encyclopedia, Mid-November 1995 edition, Vol. 72, No. 12; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992; which disclosures are incorporated herein by reference in their entirety. In some aspects of this invention, an article of manufacture can comprise any of the ethylene polymers described herein, and the article of manufacture can be a film product or a molded product.
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 example, a method may comprise (i) contacting a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions in a polymerization reactor system to produce an olefin polymer, wherein the catalyst composition may comprise a half metallocene titanium compound, an activator support comprising a solid oxide treated with an electron withdrawing anion, and an optional cocatalyst (e.g., an organoaluminum compound); and (ii) forming an article of manufacture comprising the olefin polymer. The forming step may comprise blending, melt processing, extrusion, molding, or thermoforming, and the like, including combinations thereof.
[00144] The invention is further illustrated by the following examples, which should not be interpreted in any way to impose limitations on the scope of this invention. Various other aspects, other modalities, modifications, and equivalents thereof which, upon reading the description herein, may suggest to a person of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims.
[00145] The melt index (MI, g/10 min) was determined according to ASTM D1238 at 190 °C with a weight of 2,160 grams, and the high charge melt index (HLMI, g/10 min) was determined in accordance with ASTM D1238 at 190°C with a weight of 21,600 grams. Polymer density was determined in grams per cubic centimeter (g/cm3) on a compression molded sample, cooled to about 15 °C per hour, and conditioner for about 40 hours at room temperature in accordance with ASTM D1505 and ASTM D4703.
[00146] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 system (Polimer Labs, an Agilent company) equipped with an IR4 detector (Polimer Char, Spain) and three Styragel HMW-6E columns GPC (Waters, MA) run at 145 °C. The flow rate of mobile phase 1,2,4-trichlorobenzene (TCB) containing 0.5 g/L of 2,6-di-t-butyl-4-methylphenol (BHT) was set to 1 ml/min , and polymer solution concentrations were in the range of 1.0 to 1.5 mg/ml, depending on molecular weight. Sample preparation was conducted at 150 °C for nominally 4 h with occasional gentle agitation, before the solutions were transferred to sample vials for injection. An injection volume of about 400 l was used. The integral calibration method was used to deduce molecular weights and molecular weight distributions using a Chevron Phillips Chemical Company HDPE polyethylene resin, MARLEX® BHB5003, as the broad standard. The comprehensive broad pattern table was predetermined in a separate SEC-MALS experiment. Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z average molecular weight.
[00147] SEC-MALS combines the methods of size exclusion chromatography (SEC) with multiple angle light scattering (MALS) detection. A DAWN EOS 18-angle light scattering photometer (Wyatt Technology, Santa Barbara, CA) was attached to a SEC PL-210 system (Polimer Labs, now Agilent) or a Waters 150 CV Plus system (Milford, MA) via a heat transfer line, thermally controlled at the same temperature as the SEC columns and its differential refractive index (DRI) detector (145 °C). At a flow rate setting of 0.7 ml/min, the mobile phase, 1,2,4-trichlorobenzene (TCB), was eluted through three 7.5 mm x 300 mm Mixed A-LS columns of 20 m (Polimer Labs, now Agilent). Polyethylene (PE) solutions with concentrations of ~1.2 mg/ml, depending on samples, were prepared at 150 °C for 4 h before being transferred to SEC injection vials located on a carousel heated to 145 °C. For higher molecular weight polymers, longer heating times were needed in order to obtain true homogeneous solutions. In addition to acquiring a concentration chromatogram, seventeen different angle light scattering chromatograms were also acquired for each injection using Wyatt's Astra® software. In each chromatographic slice, both the absolute molecular weight (M) and the root mean square radius (RMS), also known as the radius of rotation (Rg) were obtained from an intercept and a slope of the Debye plot, respectively. Methods for this process are detailed in the paper Wyatt, P.J., Anal. Chim. Acta, 272, 1 (1993), which is incorporated herein by reference in its entirety.
[00148] The Zimm-Stockmayer approach was used to determine the amount of LCB in Figure 3. Since SEC-MALS measures M and Rg in each slice of a chromatogram simultaneously, the branching indices, gM, as a function of M can be determined on each slice directly by determining the mean square ratio Rg of branched molecules to the same of linear ones, in the same M, as shown in the following equation (subscripts br and lin represent branched and linear polymers, respectively).

[00149] In a given gM, the average weight number of LCB per molecule (B3w) was computed using the Zimm-Stockmayer equation, shown in the equation below, assuming that the branches were trifunctional, or in the form of Y.

[00150] The LCB frequency (LCBMi), the amount of LCB per 1,000 C, of the ith slice was then computed in advance using the following equation (Mi is the MW of the ith slice):

[00151] The distribution of LCB (LCBD) through molecular weight distribution (MWD) was thus established for a complete polymer.
[00152] The content of short chain branching (SCB) and the distribution of short chain branching (SCBD) through the molecular weight distribution were determined by means of a GPC system detected in IR5 (IR5-GPC), in which the GPC system was a GPC/SEC PL220 system (Polimer Labs, an Agilent company) equipped with three Styragel HMW-6E columns (Waters, MA) for a polymer separation. A thermoelectric cooled MCT IR5 detector (IR5) (Polimer Char, Spain) was connected to the GPC columns via a hot transfer line. Chromatographic data were obtained from two output ports of the IR5 detector. First, the analog signal goes from the analog output port to a digitizer before connecting to computer “A” for molecular weight determinations via Cirrus software (Polimer Labs, now an Agilent company) and the integral calibration method with use of a Marlex™ BHB5003 HDPE wide MWD resin (Chevron Phillips Chemical) as the standard broad molecular weight. Digital signals, on the other hand, go via a USB cable directly to computer “B” and are collected by a LabView data collection software provided by Polimer Char. The chromatographic conditions were defined as follows: column oven temperature of 145 °C; 1 ml/min flow rate; injection volume of 0.4 ml; and polymer concentration of about 2 mg/ml, depending on sample molecular weight. The temperatures for both the hot transfer line and the IR5 detector sample cell were set at 150 °C, while the temperature of the IR5 detector electronics was set at 60 °C. The short chain branching content was determined by a house method using the intensity ratio of CH3 (ICH3) to CH2 (ICH2) coupled with a calibration curve. The calibration curve was a plot of SCB content (xSCB) as a function of ICH3/ICH2 intensity ratio. To obtain a calibration curve, a group of polyethylene resins (not less than 5) of the SCB level in the range of zero to about 32 SCB/1,000 total carbons (SCB Standards) was used. All of these SCB standards met SCB levels and flat SCBD profiles predetermined separately by NMR and solvent-gradient fractionation coupled with NMR methods (SGF-NMR). Using the SCB calibration curves thus established, short chain branching distribution profiles through molecular weight distribution were obtained for resins fractionated by the IR5-GPC system under exactly the same chromatographic conditions as for these SCB standards. A relationship between intensity rate and elution volume was converted to SCB distribution as a function of MWD using a predetermined SCB calibration curve (eg ICH3/ICH2 intensity rate vs. SCB content) and MW calibration curve (e.g. molecular weight vs. elution time) to convert the ICH3/ICH2 intensity rate and elution time to SCB content and molecular weight, respectively.
[00153] The rheological fusion characterizations were performed as follows. Small strain (10%) oscillatory shear measurements were performed on an ARES rheometer from Rheometrics Scientific, Inc. using parallel plate geometry. All rheological tests were performed at 190 °C. Complex Viscosity Data | n* against frequency (a) were then curve-fitted using the modified three-parameter Carreau-Yasuda (CY) empirical model to obtain the zero shear viscosity - no, the characteristic viscous relaxation time - Tn, and the parameter of amplitude - a. The simplified empirical model Carreau-Yasuda (CY) is as follows:
where: | if(®)| = magnitude of complex shear viscosity; no = zero shear viscosity; Tn = viscous relaxation time (Tau(q)); a = "amplitude" parameter (CY-a parameter); n = fix the final power law slope, set at 2/11 ; and a> = angular frequency of oscillatory shear strain.
[00154] Details of the significance and interpretation of the CY model and derived parameters can be found in: C.A. Hieber and H.H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polim. Eng. Sci., 32, 931 (1992); and R.B. Bird, R.C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety.
[00155] The long chain branches (LCB) per 1,000,000 total carbon atoms of Figure 4 were calculated using the method of Janzen and Colby (J. Mol. Struct., 485/486, 569 to 584 ( 1999)), from zero shear viscosity values, o (determined from the Carreau-Yasuda model), and measured Mw values obtained using a Dawn EOS multi-angle light scattering detector (Wyatt). See also U.S. patent document 8,114,946; J. Phys. Chem. 1980, 84, 649; and Y. Yu, D.C. Rohlfing, G.R Hawley, and P.J. DesLauriers, Polimer Preprint, 44, 50, (2003). These references are incorporated herein by reference in their entirety.
[00156] Alumina activator supports coated with fluorinated silica were prepared as follows. Boehmite was obtained from W.R. Grace & Company under the designation "Alumina A" and which has a surface area of about 300 m2/g, a pore volume of about 1.3 ml/g, and an average particle size of about 100 microns . The alumina was first calcined in dry air at about 600°C for approximately 6 hours, cooled to room temperature, and then placed in contact with tetraethylorthosilicate in isopropanol to equal 25% by weight of SiO2. After drying, the silica coated alumina was calcined at 600 oC for 3 hours. The fluorinated silica coated alumina (7% by weight F) was prepared by impregnating the calcined silica coated alumina with a solution of ammonium bifluoride in methanol, drying, and calcining for 3 hours at 600 oC in dry air. Soon after, the alumina coated with fluorinated silica (FSCA) was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
[00157] Examples 1 to 22 were produced using the following polymerization procedure (table I and table II summarize certain information regarding the polymerization experiments of examples 1 to 22). Polymerization runs were conducted in a 2.2 l stainless steel reactor, and isobutane (1.2 l) was used in all runs. Solutions of the half metallocene compounds and the metallocene compounds were prepared at about 1 mg/ml in toluene. The activator support (fluorinated silica coated alumina, FSCA), triisobutylaluminum (TIBA), and the metallocene medium solution and/or the metallocene solution were added in that order through a charging port while slowly venting an isobutane vapor. The loading port was closed and isobutane added. The reactor contents were stirred and heated to the desired running temperature of 80°C, and the ethylene was then introduced into the reactor with 1-hexene (grams) and hydrogen (based on ppm by weight of ethylene), as indicated in table I and in table II. Ethylene and hydrogen were fed on demand at the specified weight rate to maintain a target pressure of 2.34 MPa (340 psig) of pressure for the specified length of the polymerization run. The reactor was maintained at the desired running temperature throughout the entire run through an automated cooling-heating system. The half metallocene titanium compounds and the following metallocene compounds were used in examples 1 to 22 (tBu = tert-butyl; Me = methyl; Ph = phenyl):
EXAMPLES 1 to 22
[00158] As shown in Table I, the catalyst compositions used in examples 1 to 14 employed a half metallocene titanium compound, and the polymerization processes used various amounts of hydrogen and a 1-hexene comonomer. Catalyst activities were relatively high, in the range of about 50 to about 550 kg of polymer produced per gram of half metallocene titanium per hour. For the polymers of Examples 1 to 8 in which an analytical test was performed, as shown in Table III, the HLMI/MI rates which ranged from about 27 to about 53, and the Mw/Mn rates which ranged from about from 4.8 to about 9.1. Figure 1 illustrates the molecular weight distributions (amount of polymer versus log molecular weight) for the polymers of example 4, example C2 and example C3. Unexpectedly, the polymer produced using the half metallocene titanium compound had a broad molecular weight distribution, more similar to a traditional Ziegler catalyst than a traditional metallocene catalyst. Despite the relatively broad molecular weight distribution, the half metallocene titanium catalyst was surprisingly sensitive to the addition of hydrogen (see eg examples 1 and 4 versus examples 2 and 5), more similar to a traditional metallocene catalyst than a traditional Ziegler catalyst. Additionally, catalyst systems utilizing the half metallocene titanium compound were efficient incorporations of a comonomer, as evidenced by the sharp decrease in density as the addition of a 1-hexene comonomer increased (see Table I and Table III).
[00159] Figure 2 illustrates the broad MWD characteristics of a polymer produced using the same experimental conditions as in example 2, as well as, unexpectedly, the amount of SCBs that generally decreases as a molecular weight increases. Figure 3 illustrates the low LCB levels of polymers produced using the half metallocene titanium compound. The radius of rotation against the logarithm of molecular weight for a linear pattern and polymers produced using the same experimental conditions as in example 6, with SEC-MALS data, is given in Figure 3. These polymers were substantially linear with minimal amounts of LCB, for example, less than about 0.01 LCB, or less than about 0.008 LCB, etc., per 1,000 total carbon atoms in the molecular weight range of 200,000 to 5,000,000 g/mol , or in the molecular weight range of 500,000 to 2,000,000 g/mol, of the polymer. Very low levels of long-chain branching (LCB), eg less than 5 per 1,000,000 total carbon atoms (or less than 2 per 1,000,000 total carbon atoms) is also illustrated in Figure 4, which shows the very low amount of LCB from polymers produced using the same experimental conditions as in example 6 as a function of polymer molecular weight.
[00160] As shown in Table II and Table III, the dual catalyst compositions used in examples 15 to 20 employed a half metallocene titanium compound and a bridged or unbridged metallocene compound, and the polymerization processes used various amounts of hydrogen and a comonomer of 1-hexene. Unlike Ziegler catalysts in combination with traditional metallocenes, examples 15 to 20 unexpectedly demonstrated high catalyst productivity, and produced polymers that have a wide range of melt flow characteristics, density and molecular weight.
[00161] Examples 21 to 22 were conducted by adding diethylzinc (TEN) along with TIBA to the initial reactor charge. Unexpectedly, as shown in Table III, the dynamic rheology properties at 190 oC in Figure 5, and the molecular weight distributions in Figure 6, the addition of DEZ reduced the Mz and Mw/Mn ratio of the polymer.
[00162] Comparative examples C1 to C4 are shown in table II and the respective polymer properties for C2 to C4 are shown in table III. C1 used a catalyst composition containing a half metallocene titanium compound and MAO in toluene; this catalyst system resulted in reactor inoperability due to reactor failure. C2 employed a representative bridged metallocene-based catalyst system, and resulted in a narrow polymer molecular weight distribution (Mw/Mn of 2.2). C3 was a representative Ziegler catalyst system with triethylaluminum, which contains di-n-butyl magnesium and TiCl4 (Mg:Ti > 2:1), and C4 was a representative Ziegler catalyst system with triethylaluminum, which contains a titanium catalyst /prepolymerized magnesium.




[00163] The invention is described above with reference to numerous aspects and numerous embodiments, and specific examples. Many variations will suggest to individuals skilled in the art in light of the detailed description above. All such obvious variations are within the full intended scope of the appended claims. Other embodiments of the invention may include, but are not limited to, the following (modalities are described as "comprising", but alternatively may "consist essentially of" or "consist of"):
[00164] Modality 1. A catalyst composition comprising any half metallocene titanium compound disclosed herein, any activator support disclosed herein, and optionally, any cocatalyst disclosed herein, wherein the titanium compound of half metallocene has the formula:
Cp is any cyclopentadienyl, indenyl or fluorenyl group disclosed herein; each X is independently any monoanionic ligand disclosed herein; eL is any phosphinimide or iminoimidazolidide linker disclosed herein.
[00165] Modality 2. The composition defined in modality 1, wherein the activator support comprises any solid oxide disclosed herein treated with any electron withdrawing anion disclosed herein.
[00166] Modality 3. The composition defined in modality 1, wherein the activator support comprises fluorinated amine, chlorinated amine, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica-alumina sulfated silica, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated-silica-coated alumina, phosphate-coated alumina, or any combination thereof .
[00167] Modality 4. The composition defined in modality 1, wherein the activator support comprises a fluorinated solid oxide, for example, fluorinated amine, fluorinated silica-alumina, alumina coated with fluorinated silica, etc., or any combination thereof .
[00168] Modality 5. The composition defined in modality 1, wherein the activator support comprises a sulfated solid oxide, for example, sulfated alumina, sulfated silica-alumina, sulfated silica coated alumina, etc., or any combination thereof .
[00169] Modality 6. The composition defined in any one of embodiments 1 to 5, wherein the activator support further comprises any metal or metal ion disclosed herein, for example, zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, etc., or any combination thereof.
[00170] Modality 7. The composition defined in any one of embodiments 1 to 6, wherein the catalyst composition comprises a cocatalyst, e.g. any cocatalyst disclosed herein.
[00171] Modality 8. The composition defined in any one of embodiments 1 to 7, wherein the cocatalyst comprises any organoaluminum compound disclosed herein.
[00172] Modality 9. The composition defined in modality 8, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, or a combination thereof.
[00173] Modality 10. The composition defined in any one of embodiments 1 to 9, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionic ionizing compounds, or combinations thereof .
[00174] Modality 11. The composition defined in any one of the modes 1 to 10, wherein the catalyst composition is produced by a process comprising contacting, in any order, the titanium compound having the formula (I) , the activator support, and the cocatalyst (if used).
[00175] Modality 12. The composition defined in any one of embodiments 1 to 11, wherein the half metallocene titanium compound having the formula (I) has the structure of the formula (II):
Cp is any cyclopentadienyl, indenyl or fluorenyl group disclosed herein; each X is independently any monoanionic ligand disclosed herein; and R1, R2 and R3 are independently H or any halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxyl group, or a C1 to C36 hydrocarbylysilyl group disclosed herein.
[00176] Modality 13. The composition defined in modality 12, wherein R1, R2 and R3 are independently H or a C1 to C18 hydrocarbyl group.
[00177] Modality 14. The composition defined in modality 12, wherein at least one of R1, R2, and R3 is a C3 to C12 alkenyl group.
[00178] Modality 15. The composition defined in modality 12, wherein R1, R2 and R3 are independently H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (eg, 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 2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or a allyldimethylsilyl group.
[00179] Modality 16. The composition defined in any one of embodiments 1 to 11, wherein the half metallocene titanium compound having the formula (I) has the structure of the formula (III):
Cp is any cyclopentadienyl, indenyl or fluorenyl group disclosed herein; each X is independently any monoanionic ligand disclosed herein; eRA and RB are independently H or any halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxyl group, or a C1 to C36 hydrocarbylsilyl group disclosed herein.
[00180] Modality 17. The composition defined in modality 16, wherein RA and RB are independently H or a C1 to C18 hydrocarbyl group.
[00181] Modality 18. The composition defined in modality 16, wherein RA and RB are independently H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (eg 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, a group octenyl, a nonenyl group, a decenyl group, a phenyl group, a 2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group .
[00182] Modality 19. The composition defined in any one of modality 16 to 18, wherein the heterocyclic carbene group is unsaturated.
Modality 20. The composition defined in any one of embodiments 1 to 19, wherein each X is independently H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxyl group, a C1 to C1 to hydrocarbylaminyl group C36, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, OBRX2, or OSO2RX, where RX is a C1 to C36 hydrocarbyl group.
Modality 21. The composition defined in any one of embodiments 1 to 20, wherein each X is independently any halide (eg Cl) or a C1 to C18 hydrocarbyl group (eg benzyl) disclosed herein.
Modality 22. The composition defined in any one of embodiments 1 to 21, wherein each X is independently Cl, methyl, phenyl or benzyl.
[00186] Modality 23. The composition defined in any one of embodiments 1 to 22, wherein Cp is an unsubstituted cyclopentadienyl, indenyl or fluorenyl group.
[00187] Modality 24. The composition defined in any one of embodiments 1 to 23, wherein Cp is an unsubstituted indenyl group.
[00188] Modality 25. The composition defined in any one of embodiments 1 to 22, wherein Cp is a substituted cyclopentadienyl, indenyl or fluorenyl group.
[00189] Modality 26. The composition defined in modality 25, wherein each substituent (one or more) on the substituted cyclopentadienyl, indenyl or fluorenyl group is independently H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C1 to halogenated hydrocarbyl group C36, a C1 to C36 hydrocarboxyl group, or a C1 to C36 hydrocarbysilyl group.
[00190] Modality 27. The composition defined in modality 25, wherein each substituent (one or more) on the substituted cyclopentadienyl, indenyl or fluorenyl group is independently H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (eg 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 group pentenyl, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a 2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group.
[00191] Modality 28. The composition defined in any one of embodiments 1 to 27, wherein a catalyst activity of the catalyst composition is in any range disclosed herein, for example, from about 25,000 to about 750,000, of from about 50,000 to about 500,000, from about 100,000 to about 400,000 grams, etc., of ethylene polymer per gram of half metallocene titanium compound per hour, under slurry polymerization conditions, with a triisobutylaluminum cocatalyst , with the use of dibutane as a diluent, and with a polymerization temperature of 80°C and a reactor pressure of 2.34 MPa (340 psig).
[00192] Embodiment 29. The composition defined in any one of embodiments 1 to 28, wherein the catalyst composition further comprises any bridged metallocene compound disclosed herein.
[00193] Modality 30. The composition defined in any one of embodiments 1 to 28, wherein the catalyst composition further comprises any single atom metallocene compound bridged with a fluorenyl group disclosed herein.
Modality 31. The composition defined in any one of embodiments 1 to 28, wherein the catalyst composition further comprises any metallocene compound bridged with an alkenyl substituent disclosed herein.
[00195] Modality 32. The composition defined in any one of embodiments 1 to 28, wherein the catalyst composition further comprises any unbridged metallocene compound disclosed herein.
[00196] Modality 33. The composition defined in any one of embodiments 1 to 28, wherein the catalyst composition further comprises any unbridged metallocene having a cyclopentadienyl group and an indenyl group disclosed herein.
[00197] Embodiment 34. The composition defined in any one of embodiments 1 to 28, wherein the catalyst composition further comprises any unbridged metallocene compound having an alkenyl substituent disclosed herein.
Modality 35. The composition defined in any one of embodiments 29 to 34, wherein a weight ratio of the half metallocene titanium compound to the bridged metallocene compound (or to the unbridged metallocene compound ) in the catalyst composition is in any range of weight ratios disclosed herein, for example, from about 1:10 to about 10:1, from about 3:1 to about 1:3, from about 1.5:1 to about 1:1.5, etc.
[00199] Modality 36. An olefin polymerization process, the process comprising contacting the catalyst composition defined in any one of modes 1 to 35 with an olefin monomer and an optional olefin comonomer in a reactor system of polymerization under polymerization conditions to produce an olefin polymer.
[00200] Modality 37. The process defined in modality 36, wherein the olefin monomer comprises any olefin monomer disclosed herein, for example any C2 to C20 olefin.
Modality 38. The process defined in modality 36 or 37, wherein the olefin monomer and the optional olefin comonomer independently comprise a C2 to C20 alpha-olefin.
Modality 39. The process defined in any one of embodiments 36 to 38, wherein the olefin monomer comprises ethylene.
Modality 40. The process defined in any one of embodiments 36 to 39, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising a C3 to C10 alpha-olefin.
[00204] Modality 41. The process defined in any one of embodiments 36-40, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene or a mixture of them.
Modality 42. The process defined in any one of embodiments 36 to 38, wherein the olefin monomer comprises propylene.
[00206] Modality 43. The process defined in any one of modalities 36 to 42, wherein the polymerization reactor system comprises a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, or a combination thereof.
[00207] Modality 44. The process defined in any one of embodiments 36 to 43, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof .
Modality 45. The process defined in any one of embodiments 36 to 44, wherein the polymerization reactor system comprises a slurry reactor.
Modality 46. The process defined in any one of embodiments 36 to 45, wherein the polymerization reactor system comprises a loop slurry reactor.
[00210] Modality 47. The process defined in any one of embodiments 36 to 46, wherein the polymerization reactor system comprises a single reactor.
Modality 48. The process defined in any one of embodiments 36 to 46, wherein the polymerization reactor system comprises 2 reactors.
[00212] Modality 49. The process defined in any one of the modalities 36 to 46, wherein the polymerization reactor system comprises more than 2 reactors.
Modality 50. The process defined in any one of embodiments 36 to 49, wherein the olefin polymer comprises any olefin polymer disclosed herein.
Modality 51. The process defined in any one of embodiments 36 to 41 and 43 to 50, wherein the olefin polymer is an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-copolymer. hexene, or an ethylene/1-octene copolymer.
Modality 52. The process defined in any one of embodiments 36 to 41 and 43 to 51, wherein the olefin polymer is an ethylene/1-hexene copolymer.
Modality 53. The process defined in any one of embodiments 36 to 38 and 42 to 50, wherein the olefin polymer is a polypropylene homopolymer or a propylene-based copolymer.
[00217] Modality 54. The process defined in any one of embodiments 36 to 53, wherein the polymerization conditions comprise a polymerization reaction temperature in a range from about 60 °C to about 120 °C and a pressure of reaction in a range of about 200 to about 1,000 psig (about 1.4 to about 6.9 MPa).
[00218] Modality 55. The process defined in any one of embodiments 36 to 54, wherein the polymerization conditions comprise a polymerization reaction temperature in a range from about 65 °C to about 110 °C, from about 70°C to about 100°C, or from about 70°C to about 95°C.
[00219] Modality 56. The process defined in any one of embodiments 36 to 55, wherein the polymerization conditions are substantially constant, for example, for a particular polymer grade.
[00220] Modality 57. The process defined in any one of modalities 36 to 56, in which no hydrogen is added to the polymerization reactor system.
[00221] Modality 58. The process defined in any one of modalities 36 to 56, in which hydrogen is added to the polymerization reactor system.
[00222] Modality 59. The process defined in modality 58, wherein the olefin polymer (for example, an ethylene/1-hexene copolymer) has a melt index increase in any range disclosed herein, based on an increase of a hydrogen:monomer weight ratio (eg hydrogen:ethylene weight ratio) from 0 to 150 ppm by weight, for example an increase of at least about 1 g/10 min (up to about 3 to 5 g/10 min), at least about 1.2 g/10 min, at least about 1.5 g/10 min, at least about 2 g/10 min, etc.
[00223] Modality 60. The process defined in any one of modalities 36 to 59, wherein an organozinc compound is added to the polymerization reactor system.
[00224] Modality 61. The process defined in modality 60, wherein the organozinc compound comprises diethylzinc.
Modality 62. The process defined in modality 60 or 61, wherein the addition of the organozinc compound reduces the Mw/Mn of the olefin polymer.
Modality 63. The process defined in any one of embodiments 60 to 62, wherein the addition of the organozinc compound reduces the z-average molecular weight (Mz) of the olefin polymer.
[00227] Modality 64. The process defined in any one of embodiments 36 to 63, wherein the olefin polymer (for example, an ethylene/1-hexene copolymer) has a density decrease in any range disclosed herein, based on an increase in comonomer:monomer molar ratio (eg 1-hexene:ethylene molar ratio) from 0 to 0.0176, eg a density decrease of at least about 0.008 g/cm3 (up to about 0.025 to 0.035 g/cm 3 , at least about 0.01 g/cm 3 , at least about 0.015 g/cm 3 , at least about 0.02 g/cm 3 , etc.
[00228] Modality 65. The process defined in any one of embodiments 36 to 64, wherein the olefin polymer has a ratio of Mw/Mn in any range disclosed herein, for example, from about 4 to about 10 , from about 4 to about 9, from about 5 to about 10, from about 4.5 to about 9.5, from about 5 to about 9, etc.
[00229] Modality 66. The process defined in any one of embodiments 36 to 65, wherein the olefin polymer has an HLMI/MI ratio in any range disclosed herein, for example, from about 15 to about 75 , from about 20 to about 70, from about 20 to about 65, from about 20 to about 60, from about 25 to about 55, etc.
[00230] Modality 67. The process defined in any one of embodiments 36 to 66, wherein the olefin polymer has a density in any range disclosed herein, for example, from about 0.89 to about 0.97 from about 0.91 to about 0.965, from about 0.91 to about 0.94, from about 0.92 to about 0.94 g/cc, etc.
[00231] Modality 68. The process defined in any one of modalities 36 to 67, wherein the olefin polymer has a conventional comonomer distribution, for example, the amount of short chain branches (SCB) per 1,000 total carbon atoms of polymer in Mn is greater than in Mz, the amount of SCB per 1000 total carbon atoms in Mn is greater than in Mw, etc.
[00232] Modality 69. The process defined in any one of embodiments 36 to 68, wherein the olefin polymer has less than or equal to about 0.008 long chain branches (LCB) per 1,000 total carbon atoms, e.g., less or equal to about 0.005 LCB, less than or equal to about 0.003 LCB, etc.
Modality 70. An olefin polymer produced by the polymerization process defined in any one of embodiments 36 to 69.
[00234] Modality 71. An article comprising the olefin polymer defined in modality 70.
[00235] Modality 72. A method for 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 36 to 69 in order to producing the olefin polymer, and (ii) forming the article of manufacture comprising the olefin polymer, for example, by any technique disclosed herein.
[00236] Modality 73. The article defined in modality 71 or 72, wherein the article is an agricultural film, an automobile part, a bottle, a drum, a fiber or a fabric, a film or a packaging container. food, 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 blade or tape, or a toy.

权利要求:
Claims (15)
[0001]
1. Olefin polymerization process comprising: bringing a catalyst composition into contact with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions, in order to produce an olefin polymer, wherein the catalyst composition comprises: (i) a half metallocene titanium compound; (ii) an activator support comprising a solid oxide treated with an electron withdrawing anion; and (iii) an organoaluminium cocatalyst; wherein the half metallocene titanium compound has the formula:
[0002]
Process according to claim 1, characterized in that the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor or a combination thereof.
[0003]
Process according to claim 1, characterized in that the olefin monomer comprises ethylene or propylene.
[0004]
Process according to claim 1, characterized in that: the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene or a mixture thereof; a polymerization reactor comprising a loop slurry reactor; and the polymerization conditions comprise a polymerization temperature in a range of 65 oC to 110 oC.
[0005]
5. Process according to claim 1, characterized in that the olefin polymer is an ethylene polymer that has: a ratio of Mw/Mn in a range of 4 to 10; a ratio of HLMI/MI in one range from 15 to 75; and a density in a range of 0.90 to 0.96 g/cm3.
[0006]
Process according to claim 1, characterized in that the half metallocene titanium compound having formula (I) has the structure of formula (II):
[0007]
Process according to claim 6, characterized in that, in formula (II):Cp is a substituted or unsubstituted cyclopentadienyl or indenyl group; each X is independently a halide or a C1 to C18 hydrocarbyl group; and R1, R2 and R3 are independently H or a C1 to C18 hydrocarbyl group.
[0008]
Process according to claim 7, characterized in that R1, R2 and R3 are independently a C1 to C12 alkyl group or a C3 to C12 alkenyl group.
[0009]
9. Process according to claim 1, characterized in that the olefin polymer is an ethylene/-olefin copolymer that has: a ratio of Mw/Mn in a range from 5 to 9; a ratio of HLMI/ MI in a range of 25 to 55; a density in a range of 0.92 to 0.95 g/cm3; less than or equal to 0.003 long chain branches (LCB) per 1,000 total carbon atoms; and a conventional comonomer distribution.
[0010]
Process according to claim 1, characterized in that: the olefin polymer has a melt index increase of at least 1 g/10 min, based on an increase in a hydrogen:monomer weight ratio of 0 at 150 ppm by weight; and the olefin polymer has a density decrease of at least 0.01 g/cm3 based on an increase in a comonomer:monomer molar ratio from 0 to 0.0176:1.
[0011]
Process according to claim 1, characterized in that an organozinc compound is added to the polymerization reactor system, and the addition of the organozinc compound reduces the Mw/Mn of the olefin polymer and/or reduces the average molecular weight z (Mz) of the olefin polymer.
[0012]
12. Catalyst composition characterized by comprising: (i) a half metallocene titanium compound; (ii) an activator support comprising a solid oxide treated with an electron withdrawing anion; and (iii) an organoaluminium cocatalyst; wherein the half metallocene titanium compound has the formula:
[0013]
The composition of claim 12, characterized in that: the activator support comprises a fluorinated solid oxide and/or a sulfated solid oxide; and a catalyst activity of the catalyst composition is greater than 25,000 grams of ethylene polymer per gram of half metallocene titanium compound per hour, under slurry polymerization conditions, with a triisobutylaluminum cocatalyst, using isobutane as a diluent, and with a polymerization temperature of 80°C and a reactor pressure of 2.34 MPa (340 psig).
[0014]
The composition of claim 12, further comprising: a metallocene compound based on zirconium not bonded with a cyclopentadienyl group and an indenyl group; or a metallocene compound based on hafnium or zirconium bridged with a cyclopentadienyl group and a fluorenyl group.
[0015]
Composition according to claim 12, characterized in that the half metallocene titanium compound comprises: or any combination thereof.

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法律状态:
2018-07-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-02-18| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/09/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US14/510,153|2014-10-09|

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US14/510,153|US9441063B2|2014-10-09|2014-10-09|Titanium phosphinimide and titanium iminoimidazolidide catalyst systems with activator-supports|

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PCT/US2015/052873|WO2016057270A2|2014-10-09|2015-09-29|Titanium phosphinimide and titanium iminoimidazolidide catalyst systems with activator-supports|

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