METHODS TO CONTROL POLYMERIZATIONS OF DOUBLE CATALYST OLEFIN WITH AN ORGANOZINC COMPOUND

专利摘要:
methods for controlling dual catalyst olefin polymerizations with an organozinc compound. methods for controlling properties of an olefin polymer using an organozinc compound are disclosed. the hlmi/mi shear ratio of the polymer can be decreased and the mz/mw ratio of the polymer can be increased by adding the organozinc compound.
公开号:BR112015018293B1
申请号:R112015018293-3
申请日:2014-01-23
公开日:2021-06-01
发明作者:Max P. Mcdaniel；Qing Yang；Tony R. Crain；Errun Ding；Ted H. Cymbaluk；Gary L. Glass
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
[1] There are several methods that can be employed to adjust or control the melt flow properties and molecular weight characteristics of an olefin-based polymer produced using a dual metallocene catalyst system. For example, the catalyst composition and/or polymerization reaction conditions can be changed to vary the melt flow properties and molecular weight characteristics of the polymer that is produced. However, additional methods to adjust or control polymer properties are needed that do not require changes in catalyst composition or polymerization conditions. Therefore, it is to this end that the present disclosure is directed. SUMMARY OF THE INVENTION
[2] This summary is provided to introduce a selection of concepts in simplified form that are further described below in the detailed description. This summary is not intended to identify necessary or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the matter claimed.
[3] Various processes and methods related to the control of dual catalyst olefin polymerizations are disclosed here. In one embodiment, a method for controlling the polymerization reaction in a polymerization reactor system is provided herein, and in this embodiment, the method may comprise: (i) contacting a dual catalyst system with an olefin monomer and an olefin comonomer. optional olefin in the polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the dual catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and(ii) introducing an amount of an organozinc compound in the polymerization reactor system to reduce an HLMI/MI shear rate and/or increase an Mz/Mw ratio of the olefin polymer.
[4] A process for producing an olefin polymer with a target HLMI/MI shear rate and/or a target Mz/Mw ratio is presented herein, and in this embodiment, the process may comprise: (a) contacting a catalyst system dual catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions, wherein the dual catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and( b) controlling an amount of an organozinc compound introduced into the polymerization reactor system to produce the olefin polymer with the target HLMI/MI shear rate and/or target Mz/Mw ratio.
[5] In these methods and processes, the HLMI/MI shear rate of the olefin polymer may decrease and/or the Mz/Mw ratio of the olefin polymer may increase as the amount of organozinc compound added to the polymerization reactor system is increased.
[6] Both the above summary and the detailed description below provide examples and are explanatory only. In this sense, the above summary and the following detailed description should not be considered as restrictive. In addition, features or variations may be provided in addition to those set out here. For example, certain modalities can be targeted to various feature combinations and sub combinations described in the detailed description. BRIEF DESCRIPTION OF THE FIGURES
[7] FIG. 1 presents a graph of molecular weight distribution versus amount of diethylzinc (TEN) for Examples 1-5. DEFINITIONS
[8] To more clearly define the terms used here, the following definitions are provided. Unless otherwise noted, 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 Compendium of Chemical Terminology, 2nd Ed (1997) may apply, provided that such definition does not conflict with any other type of disclosure or applicable definition. here, or make any claim to which this definition applies undefined or unenabled. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.
[9] In matters of claimed transitory terms or phrases, the transitory term "comprising", which is synonymous with "including", "containing", "having", or "characterized by," is open-ended inclusive and does not exclude elements additional, unrecited steps or method steps. The transitional phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting essentially of" limits the scope of a claim to the specified material or steps and those that do not substantially affect the basic and novel features of the claimed invention. A claim “consisting essentially of” occupies a middle ground between closed claims that are written in a “consisting of” format and fully open claims that are elaborated in an “comprising” format. For example, a composition consisting essentially of material A may include impurities typically present in a commercially produced or commercially available sample of recited material A. When a claim includes different characteristics and/or classes of characteristics (eg a method step , characteristic of the composition and/or characteristics of the product, among other possibilities), the transitional terms comprising, which essentially consists of and consisting of, apply only to the class of characteristics for which it is used, and it is possible to have different terms or transition phrases used with different characteristics within a claim. For example, a method may comprise several recited steps (and other unrecited steps), but utilize a catalyst system preparation consisting of specific components; alternatively, it consists essentially of specific components; or, alternatively, comprising the specific components and other unrecited components.
[10] While compositions and methods are often described in terms of “comprising” several components or steps, compositions and methods may also “consist essentially of” or “consist of” several components or steps, unless otherwise indicated.
[11] The terms “a”, “an”, “o” and “a” are intended to include plural alternatives, for example, at least one. For example, the disclosure of "an activator," "an olefin comonomer", etc., is intended to include one, or mixtures or combinations of more than one, activator, olefin comonomer, etc., unless otherwise specified in other way.
[12] For any particular compound or group disclosed herein, any name or structure (general or specific) presented is intended to include all conformational isomers, regioisomers, stereoisomers and mixtures thereof that may arise from a particular set of substituents, unless otherwise specified. The name or structure (general or specific) also includes all enantiomers, diastereomers and other optical isomers (if any) whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a specialist, unless otherwise specified . A general reference to pentane, for example, includes n-pentane, 2-methylbutane and 2,2-dimethylpropane; and a general reference for a butyl group includes an n-butyl group, a sec-butyl group, an iso-butyl group and a t-butyl group.
[13] Also, unless otherwise specified, any carbon-containing group for which the number of carbon atoms is not specified may have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, or any range or combination of ranges between these values. For example, unless otherwise specified, any carbon-containing group or compound can have 1 to 20 carbon atoms, 1 to 18 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, of 2 to 20 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 6 carbon atoms, and the like. In addition, other identifiers or qualifying terms may be used to indicate the presence of, or absence of, a particular substituent, a particular regiochemistry and/or stereochemistry, or the presence or absence of an underlying branched structure or structure. Any group containing specific carbon is limited in accordance with the chemical and structural requirements for that specific group, as understood by an expert.
[14] Other numerical ranges are posted here. When depositors disclose or claim a range of any kind, the intention of depositors is to individually disclose or claim each possible number so that a range could reasonably be included, including range endpoints, as well as any sub-range and combinations of sub-ranges included unless otherwise specified. As a representative example, applicants disclose that a weight ratio of the highest molecular weight component to the lowest molecular weight component can be in a range of from about 1:10 to about 10:1 in certain embodiments. By a disclosure that the weight ratio of the highest molecular weight component to the lowest molecular weight component may be in a range of from about 1:10 to about 10:1, the applicant intends to recite that weight ratio can be about 1:10, about 1:9, about 1:8, about 1:7, about 1:6, about 1:5, about 1:4, about 1: 3, about 1:2, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1 or about 10:1. Also, the weight ratio can be in any range from about 1:10 to about 10:1 (for example, the weight ratio can be in a range from about 1:2 to about 2:1 ), and this also includes any range combination between about 1:10 and 10:1. Likewise, all other tracks disclosed here should be interpreted in a similar way to these examples.
[15] Depositors reserve the right to disclaim or exclude any individual members of any group, including any sub-bands or combinations of sub-bands within the group, which may be claimed according to a band or similar, if for any reason the depositor chooses to claim less than the full measure of disclosure, for example, accounting for a reference that depositors may be unaware of at the time of filing the application. In addition, applicants reserve the right to disclaim or exclude any substituents, analogues, compounds, linkers, individual structures or group thereof, or any members of a claimed group, if for any reason the applicant chooses to claim less than the full measure of disclosure, for example, accounting for a benchmark that depositors may be unaware of at the time of filing the application.
[16] The term "substituted" when used to describe a group or chain of carbon atoms, for example, when referring to a substituted analogue of a particular group or chain, is intended to describe a group or chain in which any non-hydrogen moiety formally replaces a hydrogen in that group or chain, and is intended to be non-limiting. A group or chain may be referred to herein as "unsubstituted" or by equivalent terms such as "unsubstituted," which refers to the original group or chain. "Substituted" is intended to be non-limiting and may include hydrocarbon substituents as specified and as understood by one of skill in the art.
[17] The term “hydrocarbons” whenever used in this specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers can be used to indicate the presence of particular groups in the hydrocarbon (eg, halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). The term "hydrocarbyl group" is used here in accordance with 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, and aralkyl groups, among other groups as members.
[18] The term "polymer" is used generically herein to include homopolymers, copolymers, olefin terpolymers, and so on. A copolymer can be derived from one olefin monomer and one olefin comonomer, while a terpolymer can be derived from one olefin monomer and two olefin comonomers. In this sense, "polymer" includes copolymers, terpolymers, etc., derived from any olefin monomers and comonomers disclosed herein. Likewise, an ethylene polymer would include ethylene homopolymers, ethylene copolymers, ethylene terpolymers and the like. For 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. The term "polymer" is also meant to include all molecular weights of polymers, and is inclusive of lower molecular weight polymers or oligomers. Depositors are intended by the term "polymer" to include oligomers derived from any olefin monomer disclosed herein (as well as an olefin monomer and an olefin comonomer, an olefin monomer and two olefin comonomers, and so forth).
[19] In a similar way, the scope of the term “polymerization” includes homopolymerization, copolymerization, terpolymerization, etc., as well as processes that may also be referred to as oligomerization processes. Therefore, a copolymerization process would involve contacting an olefin monomer (eg ethylene) and an olefin comonomer (eg 1-hexene) to produce an olefin copolymer.
[20] The terms "catalyst composition", "catalyst mixture", "catalyst system" and the like do not depend on the actual product or composition resulting from contact or reaction of the initial components of the disclosed composition/mixture/catalyst system or claimed, the nature of the active catalytic site, or the fate of the cocatalyst, the metallocene compounds, any olefin monomer used to prepare a pre-contacted mixture, or the activator (eg, activator-support), after combining these components . Therefore, the terms "catalyst composition," "catalyst mixture", "catalyst system" and the like include the initial starting components of the composition, as well as any product that may be the result of contact with these initial starting components, and this is inclusive of catalyst systems or heterogeneous or homogeneous compositions. The terms "catalyst composition," "catalyst mixture," "catalyst system" and the like may be used interchangeably throughout this disclosure.
[21] The terms "contact the product," "contact" and the like are used here to describe compositions in which the components are contacted together in any order, in any manner and for any length of time. For example, components can be contacted by beating or mixing. Furthermore, unless otherwise specified, contact of any component may occur in the presence or absence of any other component of the compositions described herein. Combining additional materials or components can be done by any suitable method. In addition, the term "contact product" includes mixtures, shakes, solutions, pastes, reaction products, and the like, or combinations thereof. Although “contacting product” can and often does include reaction products, it is not required that the respective components react with each other. Likewise, “contacting” two or more components can result in a reaction product or a reaction mixture. Consequently, depending on the circumstances, a “contact product” can be a mixture, a reaction mixture, or a reaction product.
[22] Although any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention, typical methods and materials are described herein.
[23] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which may be used in connection with the invention described herein. The publications discussed throughout the text are provided solely for your disclosures prior to the filing date of the present order. Nothing contained herein should be construed as an admission that the invention is not entitled to predate this disclosure by virtue of a prior invention. DETAILED DESCRIPTION OF THE INVENTION
[24] Methods and processes directed to controlling dual catalyst olefin polymerizations in a polymerization reactor system through the addition of an organozinc compound are disclosed herein. In these methods and processes, the amount of organozinc added to the reactor system can be used to increase or decrease the HLMI/MI shear rate of the olefin polymer, and additionally or alternatively, can be used to increase or decrease the Mz/ Mw of the olefin polymer. The polymerization reaction can be carried out in a reactor system which can contain one reactor, or alternatively, two or more reactors in series or parallel.
[25] For example, in one embodiment, a method for controlling the polymerization reaction in a polymerization reactor system is disclosed. In this embodiment, the method may comprise: [i] contacting a dual catalyst system with an olefin monomer and an optional olefin comonomer in the polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst system dual comprises a first metallocene catalyst component and a second metallocene catalyst component, and [ii] introducing an amount of an organozinc compound into the polymerization reactor system to reduce an HLMI/MI shear rate and/or increase a ratio Mz/Mw of the olefin polymer.
[26] Thus, the addition of the organozinc compound (eg, increasing the amount of the organozinc compound) can decrease the HLMI/MI shear rate of the olefin polymer. Alternatively, the addition of the organozinc compound (eg by increasing the amount of the organozinc compound) can increase the Mz/Mw ratio of the olefin polymer, or alternatively, the addition of the organozinc compound (eg by increasing the amount of the organozinc compound) can decrease the HLMI/MI shear rate and increase the Mz/Mw ratio of the olefin polymer.
[27] In another embodiment, a process for producing an olefin polymer with a target HLMI/MI shear rate and/or a target Mz/Mw ratio is disclosed. In this embodiment, the process may comprise: (a) contacting a dual catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions, wherein the dual catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and (b) controlling an amount of an organozinc compound introduced into the polymerization reactor system to produce the olefin polymer with the target HLMI/MI shear rate and/ or the target Mz/Mw ratio.
[28] Thus, the addition of the organozinc compound (eg, increasing the amount of the organozinc compound) can be used to produce an olefin polymer with a target HLMI/MI shear rate, or a target Mz/Mw ratio, or both . MI is an abbreviation for melt index (g/10 min), HLMI is an abbreviation for high charge melt index (g/10 min), Mw is an abbreviation for weight-average molecular weight (g/ mol) and Mz is an abbreviation for z-average molecular weight (g/mol).
[29] In these methods and processes, the organozinc compound can be introduced (eg, added, injected, etc.) into the polymerization reactor system by any suitable means, eg alone, or with a carrier (eg , a carrier gas, a liquid carrier, etc.). The organozinc compound can be introduced into the polymerization reactor system at any suitable location within the reactor system. In one embodiment, the organozinc compound can be added directly into a polymerization reactor within the polymerization reactor system, while in another embodiment, the organozinc compound can be introduced into the polymerization reaction system at a feed site or input other than directly into a polymerization reactor, for example, into a recycling stream. In some embodiments, the organozinc compound can be added to the reactor alone, while in other embodiments, the organozinc compound can be added to the reactor with a carrier or solvent, non-limiting examples of which may include, among others, isobutane , n-butane, n-pentane, isopentane, neopentane, n-hexane, heptane, octane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, benzene, toluene, xylene, ethylbenzene and the like, or combinations thereof. In particular embodiments contemplated herein, the organozinc compound can be added to the polymerization reactor system with the dual catalyst system.
[30] Generally, the characteristics of the methods and processes disclosed here (eg, the dual catalyst system, the first metallocene catalyst component, the second metallocene component, the olefin monomer, the olefin comonomer, the conditions of polymerization, the polymerization reactor system, the organozinc compound, the amount of the organozinc compound, the HLMI/MI shear rate, the Mz/Mw ratio, among others) are independently described herein, and these characteristics can be combined in any combination to further describe the disclosed processes and methods.
[31] In certain methods and processes disclosed herein, a dual catalyst system may be contacted with an olefin monomer and optionally an olefin comonomer in the polymerization reactor system, and an organozinc compound may be added to the reactor system. As would be recognized by one of skill in the art, additional components can be introduced into the polymerization reactor system in addition to these recited components, and such unrecited components are included here. For example, in the operation of a polymerization reactor system - depending, of course, on the type of polymerization reactor, the desired olefin polymer, etc., among other factors - solvents and/or diluents and/or fluidizing gases, flows recycling etc. can also be added or introduced into the polymerization reactor and polymerization reactor system.
[32] The weight ratio of the first metallocene catalyst component to the second metallocene catalyst component in the dual catalyst system is generally not limited to any particular range of weight ratios. However, in some embodiments, the weight ratio of the first metallocene catalyst component to the second metallocene catalyst component can be in a range of from about 1:100 to about 100:1, from about 1:50 to about 50:1, from about 1:25 to about 25:1, from about 1:10 to about 10:1, or from about 1:5 to about 5:1. Accordingly, suitable ranges for weight ratio of first metallocene catalyst component to second metallocene catalyst component may include, among others, from about 1:15 to about 15:1, from about 1:10 to about 10:1, from about 1:8 to about 8:1, from about 1:5 to about 5:1, from about 1:4 to about 4:1, from about 1: 3 to about 3:1, from about 1:2 to about 2:1, from about 1:1.8 to about 1.8:1, from about 1:1.5 to about 1 .5:1, from about 1:1.3 to about 1.3:1, from about 1:1.25 to about 1.25:1, from about 1:1.2 to about 1.2:1, from about 1:1.15 to about 1.15:1, from about 1:1.1 to about 1.1:1, or from about 1:1.05 to about 1.05:1, and the like.
[33] Consistent with modalities disclosed herein, the weight ratio of the first metallocene catalyst component to the second metallocene catalyst component can be kept substantially constant (e.g., within +/-5%), e.g., to the production of a particular polymer grade. Under these circumstances, the addition of the organozinc compound can be used to control, adjust, improve, etc., the production and properties of that particular polymer grade, without the need to vary the catalyst composition.
[34] Optionally, if additional control parameters for the dual catalyst polymerization process are desired other than the use of an organozinc compound, the methods and processes disclosed herein may further comprise a step of adjusting the weight ratio of the first component of metallocene catalyst to the second metallocene catalyst component.
[35] In some embodiments, polymerization conditions can be kept substantially constant (eg, within +/-5%.), for example, for producing a particular polymer grade. Representative polymerization conditions include temperature, pressure, residence time, % solids, and the like. As above, under these circumstances, the addition of the organozinc compound can be used to control, adjust, improve, etc., the production and properties of that particular grade of polymer.
[36] Optionally, if additional control parameters for the dual catalyst polymerization process are desired other than the use of organozinc compounds, the methods and processes disclosed herein may further comprise a step of adjusting at least one polymerization condition (e.g. , temperature, pressure, residence time, etc.).
[37] Unexpectedly, in these methods and processes, the HLMI/MI shear rate of the olefin polymer may decrease as the amount of organozinc compound added to the polymerization reactor system is increased. Also unexpectedly, the Mz/Mw ratio of the olefin polymer can increase as the amount of organozinc compound added to the polymerization reactor system is increased. The organozinc compound can be added to the polymerization reactor system (eg in a polymerization reactor) alone, with a carrier, with the double catalyst system, etc. The amount of organozinc compounds added to the reactor system is not particularly limited, as long as the amount of organozinc compounds added to the reactor system is sufficient to affect the HLMI/MI shear rate and/or the Mz/Mw ratio of the polymer of olefin as described herein. However, while not limited thereto, the amount of organozinc compound added typically can be in a range of moles of organozinc compound to the total moles of the first metallocene catalyst component and the second metallocene catalyst component of about 5:1 to about 250:1. This molar ratio is based on the respective amounts of the organozinc compound, the first metallocene catalyst component, and the second metallocene catalyst component fed into the reactor system (eg, into a polymerization reactor). As a non-limiting example of a 50:1 molar ratio in a continuous polymerization reactor system, the total amount of first and second metallocene catalyst components fed into the reactors per time interval can be "Y" moles/hour ; thus, the amount of organozinc compound fed into the reactors would equal “50Y” moles/hour for a molar ratio of 50:1.
[38] In some embodiments, this molar ratio (moles of organozinc compound to total moles of metallocene components) can be in a range from about 5:1 to about 200:1, from about 10:1 to about 250:1, from about 10:1 to about 200:1, from about 20:1 to about 200:1, from about 10:1 to about 180:1, from about 15:1 to about from about 180:1, from about 10:1 to about 150:1, from about 15:1 to about 150:1, or from about 10:1 to about 125:1. In particular embodiments considered herein, the molar ratio can range from about 25:1 to about 120:1, from about to about 30:1 to about 120:1, from about 40:1 to about 120:1, from about 30:1 to about 100:1, from about 30:1 to about 90:1, or from about 40:1 to about 80:1.
[39] In one embodiment, the organozinc compound can be added to the polymerization reactor system continuously. For example, the organozinc compound can be added to the reactor whenever the olefin monomer or metallocene catalyst components, or both, are added to the reactor. alternatively, the organozinc compound can be added periodically, on an as-needed basis, or pulsed into the reactor. Intermittent addition of a polymerization reactor is disclosed, for example, in US Patent 5,739,220 and US Patent Publication 2004/0059070, the disclosures of which are incorporated herein by reference in their entirety.
[40] The addition of organozinc compound can be used to produce olefin polymers having various melt flow rates and molecular weight properties. For example, the melt index (MI) of the olefin polymer (for example, an ethylene/α-olefin copolymer) can be less than about 50, less than about 25, less than about 10, or less than about 5 g/10 min. Contemplated ranges for the MI of olefin polymers produced by the methods and processes disclosed herein may include, among others, from 0 to about 25 g/10 min, from 0 to about 5 g/10 min, from about 0.005 to about 5 g/10 min, from about 0.005 to about 2 g/10 min, from about 0.005 to about 1 g/10 min, from about 0.01 to about 5 g/10 min, from about from 0.01 to about 2 g/10 min, from about 0.01 to about 1 g/10 min, from about 0.05 to about 5 g/10 min, from about 0.05 to about 2 g/10 min, from about 0.05 to about 1 g/10 min, from about 0.05 to about 0.5 g/10 min, from about 0.1 to about 2 g/10 min, from about 0.1 to about 1 g/10 min, or from about 0.1 to about 0.8 g/10 min.
[41] In some embodiments, the average weight molecular weight (Mw) of the olefin polymer produced by the methods and processes disclosed herein can be in a range of from about 50,000 to about 500,000 g/mol, from about 75,000 to about 400,000 g/mol, or from about 100,000 to about 350,000 g/mol. In other embodiments, the Mw can be in the range from about 100,000 to about 300,000 g/mol, from about 100,000 to about 275,000 g/mol, from about 100,000 to about 250,000 g/mol, from about 125,000 to about from 300,000 g/mol, from about 125,000, to about 250,000 g/mol, or from about 150,000 to about 250,000 g/mol. Suitable ranges for the number average molecular weight (Mn) of the olefin polymer may include, among others, from about 5,000 to about 50,000 g/mol, from about 5,000 to about 40,000 g/mol, from about from 5,000 to about 30,000 g/mol, from about 5,000 to about 25,000 g/mol, from about 5,000 to about 20,000 g/mol, from about 6,000 to about 30,000 g/mol, from about 6,000 to about 25,000 g/mol, from about 6,000 to about 20,000 g/mol, or from about 7,000 to about 18,000 g/mol.
[42] In some embodiments, the Mw/Mn ratio of the olefin polymer produced by the methods and processes disclosed herein can be in a range of from about 4 to about 50, from about 5 to about 40, from about 5 to about 35, from about 5 to about 30, from about 6 to about 40, from about 6 to about 35, from about 6 to about 30, from about 6 to about 25, from about 7 to about 40, from about 7 to about 35, from about 7 to about 30, from about 7 to about 28, from about 8 to about 30, from about 8 to about 28, from about 10 to about 40, or from about 10 to about 30.
[43] In one embodiment, no hydrogen is added to the polymerization reactor system. As one skilled in the art would recognize, hydrogen can be generated in situ by the first and/or second metallocene catalyst component during the dual catalyst olefin polymerization process. In this mode, there is no “added hydrogen” to the reactor system.
[44] Although not necessary, however, hydrogen can be added to the polymerization reactor system in certain modalities. Optionally, for example, the methods and processes provided herein may further comprise a step of adding hydrogen to the polymerization reactor system to adjust a molecular weight parameter (e.g., Mw, Mn, Mw/Mn, etc.) of the olefin polymer, and/or to adjust the MI of the olefin polymer, if desired. Generally, the hydrogen addition step can decrease the Mw (and/or Mn), and/or increase the MI of the polymer.
[45] In embodiments where hydrogen is added to the polymerization reactor system, the hydrogen addition can be kept substantially constant (eg, within +/-20%.), eg, to produce a grade of particular polymer. For example, the ratio of hydrogen to olefin monomer in the polymerization process can be controlled, often by the feed rate of hydrogen to olefin monomer entering the reactor. Furthermore, the addition of comonomer (or comonomer) can be, and usually is, substantially constant throughout the run of polymerization for a particular copolymer grade. However, in other embodiments, it is contemplated that the monomer, comonomer (or comonomers), and/or hydrogen may be periodically pulsed into the reactor, for example, in a manner similar to that employed in US Patent 5,739,220 and Patent Publication US 2004/0059070, the disclosures of which are incorporated herein by reference in their entirety.
[46] Olefin polymer produced using the dual catalyst system may contain a higher molecular weight component and a lower molecular weight component in certain embodiments disclosed herein. The weight ratio of the highest molecular weight component to the lowest molecular weight component is generally not limited to any particular range of weight ratios. However, in some embodiments, the weight ratio of the highest molecular weight component to the lowest molecular weight component can be in a range from about 1:100 to about 100:1, from about 1:50 to about 50:1, from about 1:25 to about 25:1, from about 1:10 to about 10:1, or from about 1:5 to about 5:1. Accordingly, suitable ranges for weight ratio of the highest molecular weight component to the lowest molecular weight component may include, among others, from about 1:15 to about 15:1, from about 1:10 to about 10:1, from about 1:8 to about 8:1, from about 1:5 to about 5:1, from about 1:4 to about 4:1, from about 1: 3 to about 3:1, from about 1:2 to about 2:1, from about 1:1.8 to about 1.8:1, from about 1:1.5 to about 1 .5:1, from about 1:1.3 to about 1.3:1, from about 1:1.25 to about 1.25:1, from about 1:1.2 to about 1.2:1, from about 1:1.15 to about 1.15:1, from about 1:1.1 to about 1.1:1, or from about 1:1.05 to about 1.05:1, and the like.
[47] In the disclosed methods and processes, the HLMI/MI shear rate of the olefin polymer may decrease and/or the Mz/Mw ratio of the olefin polymer may increase as the amount of organozinc compound added to the polymerization reactor system is increased. For olefin polymers having a higher molecular weight component and a lower molecular weight component, unexpectedly introducing the organozinc compound into the polymerization reactor system can reduce the weight ratio of the higher molecular weight component to the lower molecular weight component.
[48] In addition, the addition of the organozinc compound into the polymerization reactor system can increase the peak molecular weight (Mp) of the lower molecular weight component of the olefin polymer. However, in certain embodiments, the addition of the organozinc compound into the polymerization reactor system can have substantially no effect on the peak molecular weight (Mp) of the higher molecular weight component of the olefin polymer. In this regard, "substantially" no effect (substantially no change in Mp) means that the peak molecular weight after addition of organozinc compound is within +/-15% of the peak molecular weight before addition of organozinc compound. In some embodiments, peak molecular weights can be within +/-10% or, alternatively, +/-5%.
[49] For the production of a particular grade of an olefin polymer, with certain desired polymer properties, a target HLMI/MI shear rate ratio of the olefin polymer can be established. Thus, when the particular polymer grade is produced, the variables can be adjusted in order to achieve the target HLMI/MI shear rate. Accordingly, in some embodiments, the processes and methods provided herein may optionally further comprise the steps of determining (or measuring) the HLMI/MI shear rate of the olefin polymer, and then adjusting the amount of organozinc compound introduced into the polymerization reactor system based on the difference between the measured HLMI/MI shear rate and the target HLMI/MI shear rate. As a representative example, if the measured HLMI/MI shear rate is greater than the target HLMI/MI shear rate for the production of a particular grade of olefin polymer, then the organozinc compound can be added in a suitable amount to make the measured HLMI/MI shear rate equivalent to the target HLMI/MI shear rate. For example, the organozinc compound feed rate can be increased to reduce the HLMI/MI shear rate of the olefin polymer.
[50] Likewise, for the production of a particular grade of an olefin polymer with certain desired polymer properties, a target Mz/Mw ratio of the olefin polymer can be established. Thus, when the particular polymer grade is produced, variables can be adjusted to achieve the target Mz/Mw ratio. Accordingly, in some embodiments, the processes and methods provided herein, optionally, may further comprise the steps of determining (or measuring) the Mz/Mw ratio of the olefin polymer, and then adjusting the amount of organozinc compound introduced into the polymerization reactor based on the difference between the measured Mz/Mw ratio and the target Mz/Mw ratio. As a representative example, if the measured Mz/Mw ratio is greater than the target Mz/Mw ratio for producing a particular grade of olefin polymer, then the organozinc compound can be added in a suitable amount to make the ratio Mz/Mw measured equivalent to the target Mz/Mw ratio. For example, the feed rate of the organozinc compound can be increased to increase the Mz/Mw ratio of the olefin polymer.
[51] Consistent with modalities disclosed herein, optionally, as needed, various polymerization conditions or process variables may be adjusted and/or controlled during operation of a polymerization reactor system, and such conditions or variables may include, among others , reaction temperature, reactor pressure, residence time, flow rate of catalyst system in the reactor, flow rate of monomer (and comonomer, if employed) in the reactor, outflow rate of olefin polymer, recycling rate, hydrogen flow rate (if employed), reactor cooling status, slurry density, pump circulation force, and the like.
[52] In each of the methods and processes disclosed herein, the HLMI/MI shear rate of the olefin polymer may decrease and/or the Mz/Mw ratio of the olefin polymer may increase as the amount of organozinc compound added to the system of polymerization reactor is increased. ORGANOZINC COMPOUNDS
[53] Suitable organozinc compounds for use herein may include, among others, compounds having the formula: Zn(X10)(X11)(I).
[54] Generally, the selections of X10 and X11 in formula (I) are independently described herein, and these selections may be combined in any combination to further describe the organozinc compound having formula (I). In some embodiments, X10 can be a C1 to C18 hydrocarbyl group, and X11 can be H, a halide, or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarboxy group. It is contemplated in these and other embodiments that X10 and X11 may be the same, or that X10 and X11 may be different.
[55] In one embodiment, X10 and X11 independently can be a C1 to C18 hydrocarbyl group, while in another embodiment, X10 and X11 independently can be a C1 to C12 hydrocarbyl group. In yet another embodiment, X10 and X11 independently may be a C1 to C8 hydrocarbyl group or a C1 to C5 hydrocarbyl group. In yet another embodiment, X10 and X11 independently may be a C1 to C18 alkyl group, a C2 to C18 alkenyl group, an aryl group C6 to C18, or a C7 to C18 aralkyl group. In these and other embodiments, X10 and X11 independently can be a C1 to C12 alkyl group, a C2 to C12 alkenyl group, a C6 to C15 aryl group, or a C7 to C15 aralkyl group; alternatively, X10 and X11 independently may be a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C6 to C12 aryl group, or a C7 to C12 aralkyl group; alternatively, X10 and X11 independently may be a C1 to C8 alkyl group, a C2 to C8 alkenyl group, a C6 to C10 aryl group, or a C7 to C10 aralkyl group; or alternatively, X10 and X11 independently may be a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C6 to C8 aryl group, or a C7 to C8 aralkyl group.
[56] In this sense, in some embodiments, the alkyl group that can be X10 and/or X11 in formula (I) can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a group hexyl, a heptyl group, 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 other embodiments, the alkyl group which may be X10 and/or X11 in formula (I) may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a group iso-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, an n-butyl 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 an n-butyl group; alternatively a tert-butyl group; or, alternatively, a neopentyl group.
[57] Illustrative alkenyl groups which may be X10 and/or X11 in formula (I) may include, among others, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a 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. In one embodiment, X10 and/or X11 in formula (I) can be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group or a group decenyl, while in another embodiment, X10 and/or X11 can be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, or a hexenyl group. For example, X10 and/or X11 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 embodiment, X10 and/or X11 can be an acyclic terminal alkenyl group, such as a C3 to C10 terminal alkenyl group, or a C3 to C8.
[58] In some embodiments, the aryl group that can be X10 and/or X11 in formula (I) can be a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. In one embodiment, 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; or, alternatively, a substituted phenyl group or a substituted naphthyl group. Substituents that can be used for the substituted phenyl group or substituted naphthyl group are independently disclosed herein and can be used without limitation to further describe the substituted phenyl group or substituted naphthyl group that can be X10 and/or X11 in formula (I).
[59] In one embodiment, the substituted phenyl group that can be X10 and/or X11 can be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group , a 2,6-disubstituted phenyl group, 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group. In other embodiments, the substituted phenyl group can be a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group; alternatively a 3-substituted phenyl group or a 3,5-disubstituted phenyl group; alternatively a 2-substituted phenyl group or a 4-substituted phenyl group; alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group; alternatively, a 2-substituted phenyl group; alternatively, a 3-substituted phenyl group; alternatively, a 4-substituted phenyl group; 2,4-disubstituted phenyl group; alternatively, a 2,6-disubstituted phenyl group; alternatively, 3,5-disubstituted phenyl group; or, alternatively, a 2,4,6-trisubstituted phenyl group. Substituents which may be used for these specific substituted phenyl groups are independently disclosed herein and may be used without limitation to further describe these substituted phenyl groups which may be the X10 group and /or X11 of formula (I).
[60] In some embodiments, the aralkyl group that can be used as X10 and/or X11 of formula (I) can be a benzyl group or a substituted aralkyl group, such as a substituted benzyl group. Substituents that can be used for these substituted aralkyl groups are independently disclosed herein and can be used without limitation to further describe these substituted aralkyl groups which can be the X10 and/or X11 group of formula (I).
[61] In one embodiment, each non-hydrogen substituent for the substituted aryl group or substituted aralkyl group which may be X10 and/or X11 in formula (I) independently may be a C1 to C10 hydrocarbyl group; alternatively, a C1 to C8 hydrocarbyl group; or alternatively, a C1 to C5 hydrocarbyl group. Specific hydrocarbyl groups are independently disclosed herein and can be used without limitation to further describe such substituted aryl group or substituted aralkyl group substituents which may be X10 and/or X11 of formula (I). The number of substituents and their respective number of carbon atoms in any substituted aryl group or substituted aralkyl group is limited so that X10 and X11 of formula (I) have a maximum of 24 carbon atoms. Exemplary hydrocarbyl substituents may include, among others, 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, an tert-butyl, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a 3-methyl-1-butyl group, a group 3-methyl-2-butyl, or a neo-pentyl group and the like, including combinations thereof.
[62] In one embodiment, X10 and X11 independently can be a C1 to C12 alkyl group, a C2 to C12 alkenyl group, a C6 to C15 aryl group, or a C7 to C15 aralkyl group; or alternatively, a C1 to C8 alkyl group, a C2 to C8 alkenyl group, a C6 to C10 aryl group, or a C7 to C10 aralkyl group. In another embodiment, X10 and X11 independently can be a C1 to C12 alkyl group or a C2 to C12 alkenyl group. In yet another embodiment, X10 and X11 independently can be methyl, ethyl, propyl, butyl, pentyl (e.g., neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, or tolyl; alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, benzyl, or tolyl; alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, phenyl, benzyl, or tolyl; or alternatively, methyl, ethyl, propyl, butyl, pentyl, ethenyl, propenyl, butenyl, or pentenyl. In yet another embodiment, X10 and X11 independently can be methyl, ethyl, propyl, butyl, or pentyl (e.g. neopentyl), or X10 and X11 can be methyl, or ethyl, or propyl, or butyl, or pentyl (e.g. , neopentyl).
[63] In some embodiments, X11 can be a C1 to C18 hydrocarboxy group. A hydrocarboxy 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)-(hydrogen or aralkyl) groups. hydrocarbyl) and those groups which are suitable for X11 typically may comprise up to about 18 carbon atoms (for example, C1 to C18, C1 to C12, C1 to C10, or C1 to C8) hydrocarboxy groups. Illustrative and non-limiting examples of hydrocarboxy groups, which may be X11 in formula (I) may include, among others, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a group sec-butoxy, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a group 3-methyl-1-butoxy, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group, a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, a benzoxy group, an acetylacetonate (acac) group, a formate group, an acetate group, a stearate group, an oleate group, a benzoate group, and the like. In one embodiment, the hydrocarboxy group which may be X11 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 neo-pentoxy group; alternatively, a phenoxy group; alternatively, a toloxy group; alternatively a xyloxy group; alternatively a 2,4,6-trimethylphenoxy group; alternatively, a benzoxy group; alternatively, an acetylacetonate group; alternatively, a formate group; alternatively an acetate group; alternatively, a stearate group; alternatively, an oleate group; or, alternatively, a benzoate group.
[64] X11 can be H, a halide, or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarboxy group. In some embodiments, X11 can be H, a halide (e.g., Cl), or a C1 to C12 hydrocarbyl or C1 to C12 hydrocarboxy group; alternatively, H, a halide, or a C1 to C8 hydrocarbyl or C1 to C8 hydrocarboxy group; or alternatively, H, Br, Cl, F, I, methyl, ethyl, propyl, butyl, pentyl (e.g. neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl , octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, phenoxy, toloxy, xyloxy, or benzoxy.
[65] In certain embodiments, the organozinc compound can be a di(hydrocarbylsilyl)zinc compound. Each hydrocarbyl (one or more) of the hydrocarbylsilyl group can be any hydrocarbyl group disclosed herein (for example, a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C6 to C18 aryl group, a C7 to C18 aralkyl group, etc. .). Illustrative and non-limiting examples of hydrocarbylsilyl groups can include, but are not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, trimethylsilylmethyl and the like.
[66] In other embodiments, the organozinc compound can be 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; alternatively, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dynepentylzinc, di(trimethylsilylmethyl)zinc, or combinations thereof; alternatively, dimethylzinc; alternatively, diethylzinc; alternatively, dipropylzinc; alternatively, dibutylzinc; alternatively, dinepentylzinc; or alternatively, di(trimethylsilylmethyl)zinc. CATALYST SYSTEMS
[67] In some embodiments, the dual catalyst system may comprise a first metallocene catalyst component and a second metallocene catalyst component. The first metallocene catalyst component and the second metallocene catalyst component independently may comprise, for example, a transition metal (one or more than one) from Groups IIIB-VIIIB of the Periodic Table of Elements. In one embodiment, the first metallocene catalyst component and the second metallocene catalyst component independently can comprise a Group III, IV, V, or VI transition metal, or a combination of two or more transition metals. The first metallocene catalyst component and the second metallocene catalyst component independently may comprise chromium, titanium, zirconium, hafnium, vanadium or a combination thereof, or may comprise titanium, zirconium, hafnium or a combination thereof, in other embodiments . Accordingly, the first metallocene catalyst component and the second metallocene catalyst component independently may comprise titanium, or zirconium, or hafnium, alone or in combination.
[68] In one embodiment, the first metallocene catalyst component can produce the lowest molecular weight component of the olefin polymer, and the second metallocene catalyst component can produce the highest molecular weight component of the olefin polymer. These component terms are relative, are used in reference to each other, and are not limited to the actual molecular weights of the respective components. While not limited thereto, the first metallocene catalyst component may comprise an unbridged metallocene compound (e.g., with zirconium or hafnium) such as those described in US Patent 7,619,047, the disclosure of which is incorporated herein by reference in its entirety. .
[69] In another embodiment, the first metallocene catalyst component can produce the lowest molecular weight component of the olefin polymer, and the first metallocene catalyst component can comprise zirconium, or alternatively, hafnium. Representative and non-limiting examples of metallocene compounds that can be employed as the first metallocene compound may include, among others, the following (Ph = phenyl):

and the like, as well as combinations thereof.
[70] In addition, the first metallocene catalyst component may comprise an unbridged dinuclear metallocene such as those described in US Pat. 7,919,639 and 8,080,681; which disclosures are incorporated herein by reference in their entirety. Representative non-limiting dinuclear compounds may include the following:



and the like, as well as combinations thereof.
[71] While not limited thereto, the second metallocene catalyst component may comprise a bridged metallocene (e.g., with titanium, zirconium, or hafnium) such as those described in US Patents 7,226,886 and 7,619,047; which disclosures are incorporated herein by reference in their entirety.
[72] In another embodiment, the second metallocene catalyst component can produce the higher molecular weight component of the olefin polymer, and the second metallocene catalyst component can comprise zirconium and/or hafnium. Representative and non-limiting examples of metallocene compounds that can be employed as the second metallocene compound may include, among others, the following (Ph = phenyl, Me = methyl, and t-Bu = tert-butyl):


[73] In some embodiments, the dual catalyst system may comprise an activator. For example, the dual catalyst system may comprise a first metallocene catalyst component and a second metallocene catalyst component, and an activator such as a support-activator, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, and the like or any combination thereof. The catalyst system can contain one or more activators.
[74] In one embodiment, the dual catalyst system may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionic ionizing compound, and the like or a combination thereof. Examples of such activators are disclosed in, for example, US Patents 3,242,099. 4,794,096. 4,808,561. 5,576,259. 5,807,938. 5,919,983. and 8,114,946; which disclosures are incorporated herein by reference in their entirety. In another embodiment, the dual catalyst system can comprise an aluminoxane compound. In yet another embodiment, the dual catalyst system can comprise an organoboron or organoborate compound. In yet another embodiment, the dual catalyst system can comprise an ionic ionizing compound.
[75] In other embodiments, the dual catalyst system may comprise a support activator, for example, a support activator comprising a solid oxide treated with an electron withdrawing anion. Examples of such materials are disclosed in, for example, U.S. Patent Nos. 7,294,599 and 7,601,665; which disclosures are incorporated herein by reference in their entirety.
[76] The solid oxide used to produce the support-activator may comprise oxygen and one or more elements from Groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table, or comprising oxygen and one or more elements of the lanthanides or actinides (see for example, Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley & Sons, 1995; Cotton, FA, Wilkinson, G., Murillo, CA, and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, the solid oxide may comprise oxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr.
[77] In this regard, suitable examples of solid oxide materials that can be used to form the activator-supports may include, among others, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3 , Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including mixed oxides thereof, and combinations thereof. This includes cogels or coprecipitates from different solid oxide materials. Solid oxide can include 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 single or multiple chemical phase with more than one metal combined with oxygen to form a solid oxide. Examples of mixed oxides that can be used to form activator-support, alone 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 include oxide materials such as silica coated alumina as described in US Patent 7,884,163, the disclosure of which is incorporated herein by reference in its entirety.
[78] In this sense, in one modality, solid oxide may comprise silica, alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, any oxides mixtures thereof, or any combination thereof. In another embodiment, the solid oxide may comprise silica, alumina, zirconia, magnesia, boria, zinc oxide, any mixed oxides thereof, or any combination thereof. In yet another embodiment, the solid oxide may comprise silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boria, or any combination thereof. In yet another embodiment, the solid oxide can comprise silica; alternatively, alumina; alternatively, silica-alumina; or alternatively, silica coated alumina.
[79] The silica-alumina that can be used typically can have an alumina content of about 5 to about 95% by weight. In one embodiment, the alumina content of silica-alumina can be from about 5 to about 50%, or from about 8% to about 30% alumina by weight. In another embodiment, silica-alumina materials with a high alumina content can be employed, wherein the alumina content of these silica-alumina materials can normally range from about 60% to about 90%, or from about 65% to about 80% alumina by weight. According to yet another embodiment, the solid oxide component can comprise alumina without silica, and according to another embodiment, the solid oxide component can comprise silica without alumina. Furthermore, as provided above, the solid oxide may comprise a silica coated alumina. The solid oxide can have any suitable surface area, pore volume, and particle size, as would be recognized by those skilled in the art.
[80] The electron withdrawing component used to treat solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide after treatment (compared to solid oxide that is not treated with at least one electron withdrawing anion ). In one embodiment, the electron withdrawing component can be an electron withdrawing anion derived from a salt, an acid, or another compound, such as a volatile organic compound, that serves as a source or precursor for the anion. Examples of electron withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluozirconate, fluorotitanate, phospho-tungstate and the like, including mixtures and combinations of the same. In addition, other ionic or non-ionic compounds that serve as sources for these electron withdrawing anions can also be employed. It is envisioned 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 embodiments provided herein. In other embodiments, electron withdrawing anions can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, triflate, fluozirconate, fluorotitanate, and the like, or any combination thereof.
[81] In one embodiment, the dual catalyst system may comprise a support-activator and the support-activator may comprise, fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, silica- brominated 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 mixtures or combinations thereof. In another embodiment, the dual catalyst system may comprise a support activator, and the support activator may comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated zirconia-silica, fluorinated silica coated alumina, alumina coated with sulfated silica, and the like, as well as any mixture or combination thereof.
[82] As described here, the organozinc compound can be added to the polymerization reactor system (eg, in a polymerization reactor) alone, with a carrier, with the dual catalyst system, etc. and the amount of organozinc compound added to the reactor system is not particularly limited, as long as the amount of organozinc compound added to the reactor system is sufficient to impact the HLMI/MI shear rate and/or the Mz/Mw ratio of the polymer of olefin as described herein. Nevertheless, while not limited thereto, the amount of organozinc compounds added typically can be in a range from the weight of the organozinc compound to the weight of the activator-support from about 2 to about 100% by weight (ie, for catalyst systems where a support activator is employed, such as a solid oxide treated with an electron withdrawing anion, fluorinated silica-alumina, sulfated alumina, etc.). This weight ratio is based on the respective amounts of the organozinc compound and the supporting activator fed into the reactor system (eg, in a polymerization reactor). As a non-limiting example of 25% by weight, in a continuous polymerization reactor system, the total amount of activator-support component fed into the reactors per time interval may be “W” lb/h; thus, the amount of organozinc compounds fed into the reactors would equal “0.25W” lb/hour for a 25% weight addition.
[83] In some embodiments, the weight percentage (weight of organozinc compound fed into the reactor system based on the weight of the support-activator fed into the reactor system) can be in a range of from about 2 to about 80% by weight, from about 3 to about 80% by weight, from about 4 to about 80% by weight, or from about 5 to about 75% by weight. In particular embodiments considered herein, the percentage by weight can be in a range of from about 7 to about 70% by weight, from about 7 to about 60% by weight, from about 10 to about 70% by weight. , from about 10 to about 60% by weight, from about 10 to about 50% by weight, from about 15 to about 75% by weight, from about 15 to about 50% by weight, of from about 10 to about 40% by weight, from about 20 to about 60% by weight, or from about 20 to about 40% by weight.
[84] Commonly used polymerization cocatalysts may include, but are not limited to, alkyl metal, or organometal, cocatalysts, with the metal including boron, aluminum, and the like. Dual catalyst systems provided herein may comprise a cocatalyst, or a combination of cocatalysts. For example, alkyl boron and/or alkyl aluminum compounds can often be used as cocatalysts in such catalyst systems. Representative boron compounds can include, among others, tri-n-butyl borane, tripropylborane, triethylborane, and the like, and this includes combinations of two or more of these materials. While not limited to the same, representative aluminum compounds (eg, organoaluminum compounds) may include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, as well as any combination thereof. Thus, a dual catalyst system provided herein may comprise a first metallocene catalyst component, a second metallocene catalyst component, an activator, and a cocatalyst. Therefore, the cocatalyst may comprise an organoaluminum compound such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, of diethylaluminum, or any combination thereof; and the activator can comprise fluorinated alumina, sulfated alumina, silica-fluorinated alumina, silica-sulfated alumina, fluorinated silica-zirconia, fluorinated silica coated alumina, sulfated silica coated alumina, or any combination thereof, in certain embodiments. OLEFIN MONOMERS AND OLEFIN POLYMERS
[85] Olefin monomers contemplated herein typically include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. Homopolymerization processes using a simple olefin such as ethylene, propylene, butene, hexene, octene and the like are included, as well as copolymerization, terpolymerization, etc., reactions using an olefin monomer with at least one different olefin compound. As previously disclosed, polymerization processes are intended to also include oligomerization processes.
[86] As an example, any resulting copolymers, terpolymers of ethylene, etc., generally may contain a large amount of ethylene (>50 mole percent) and a smaller amount of comonomer (<50 mole percent). Comonomers that can be copolymerized with ethylene often have 3 to 20 carbon atoms, or 3 to 10 carbon atoms, in their molecular chain.
[87] Acyclic, cyclic, polycyclic, terminal(α), internal, linear, branched, substituted, unsubstituted, functionalized, and unfunctionalized olefins can be employed. For example, typical unsaturated compounds that can be polymerized to produce olefin polymers may comprise, among others, 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, os 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 used as a monomer or a comonomer. In one embodiment, the olefin monomer can comprise a C2-C20 olefin; alternatively, a C2-C20 α-olefin; alternatively, a C2-C12 olefin; alternatively, a C2-C10 α-olefin; alternatively, ethylene, propylene, 1-butene, 1-hexene or 1-octene; alternatively, ethylene or propylene; alternatively, ethylene; or alternatively, propylene.
[88] When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer can be, for example, ethylene or propylene, which is copolymerized with at least one comonomer (eg, a C2-C20 α-olefin, an α-C3-C20 olefin, etc.). According to one embodiment, the olefin monomer in the polymerization process can be ethylene. In this embodiment, examples of suitable olefin comonomers may include, among others, 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. In one embodiment, the comonomer may comprise α-olefins (eg, a C3-C10 α-olefin), while in another embodiment, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene , 1-decene, styrene or any combination thereof. For example, the comonomer can comprise 1-butene, 1-hexene, 1-octene or a combination thereof.
[89] Generally, the amount of comonomer introduced into a polymerization reactor to produce the copolymer can be from about 0.01 to about 50% of the comonomer weight based on the total weight of the monomer and comonomer. In another embodiment, the amount of comonomer introduced into a polymerization reactor can be from about 0.01 to about 40% by weight of the comonomer based on the total weight of the monomer and comonomer. In yet another embodiment, the amount of comonomer introduced into a polymerization reactor can be from about 0.1 to about 35% by weight of the comonomer based on the total weight of the monomer and comonomer. In yet another embodiment, the amount of comonomer introduced into a polymerization reactor can be from about 0.5 to about 20% by weight of the comonomer based on the total weight of the monomer and comonomer.
[90] While not intended to be bound by this theory, where branched, substituted, or functionalized olefins are used as reactants, it is believed that a steric hindrance can impede and/or retard the polymerization reaction. Thus, branched and/or cyclic portions of the olefin removed from the carbon-carbon double bond would not be expected to impede the reaction in the way that the same olefin substituents situated closer to the carbon-carbon double bond would.
[91] According to one embodiment, at least one monomer/reagent can be ethylene, therefore, the polymerization reaction can be a homopolymerization involving only ethylene, or a copolymerization with an acyclic, cyclic, terminal, internal, linear, branched olefin , replaced or not replaced different. In addition, the methods disclosed herein are intended for olefin to also include diolefin compounds which include, among others, 1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and the like.
[92] Olefin polymers included herein may include any polymer (or oligomer) produced from any olefin monomer (and optional comonomers) described herein. For example, the olefin polymer may comprise an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer (e.g., ethylene/α-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. Furthermore, additional polymer components may be present in the olefin polymer in addition to the higher molecular weight component and the lower molecular weight component. Accordingly, in one embodiment, the olefin polymer may have a bimodal molecular weight distribution, while in another embodiment, the olefin polymer may have a multimodal molecular weight distribution. In yet another embodiment, the olefin polymer can have a unimodal molecular weight distribution. POLYMERIZATION REACTOR SYSTEMS
[93] The disclosed processes and methods are intended for any olefin polymerization process using various types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing (including oligomerizing) olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers and the like. The various types of polymerization reactors include those that may be referred to as a batch reactor, slurry reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations of the same. Appropriate polymerization conditions are used for the various reactor types. Gas phase reactors can comprise fluidized bed reactors or horizontal phase reactors. Paste reactors can comprise vertical or horizontal handles. 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. Polymerization reactor systems and processes may also include the direct partial or complete recycling of unreacted monomer, unreacted comonomer, and/or diluent.
[94] A polymerization reactor system can comprise a single reactor or multiple reactors (2 reactors, more than 2 reactors, etc.) of the same or different type. For example, the polymerization reactor system can comprise a slurry reactor, a gas phase reactor, a solution reactor, or a combination of two or more of these reactors. The production of polymers in multiple reactors can include several stages in at least two separate polymerization reactors, interconnected by a transfer system, making it possible to transfer the resulting polymers from the first polymerization reactor into the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. alternatively, polymerization in multiple reactors can include manual transfer from one reactor to subsequent reactors for continued polymerization. Multiple reactor systems can include any combination, including but not limited to multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure reactors. pressure with handle and/or gas. Multiple reactors can be operated in series, in parallel, or both.
[95] According to an embodiment, the polymerization reactor system may comprise at least one loop slurry reactor comprising vertical or horizontal loops. Monomer, diluent, catalyst, and comonomer can be continuously fed into a loop reactor where polymerization takes place. Generally, continuous processes may comprise continuously introducing a monomer/comonomer, a catalyst, and a diluent into a polymerization reactor and continuously removing this reactor from a suspension comprising polymer particles and the diluent. Reactor effluent can be sprayed 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 pressure reduction and heat addition, cyclonic separation in a cyclone or hydrocyclone, or centrifugal separation.
[96] A typical slurry polymerization process (also known as the particulate form process) is disclosed, for example, in US Patents 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415, each of which is incorporated herein by reference in their entirety.
[97] Suitable diluents used in slurry polymerization include, among others, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, among others, 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 propylene monomer polymerization as disclosed in U.S. Patent Nos. 5,455,314, which is incorporated herein by reference in its entirety.
[98] According to another embodiment, the polymerization reactor system may comprise at least one gas-phase reactor (e.g., a fluidized bed reactor). These systems can employ a continuous recycle stream that contains one or more monomers continuously recycled through a fluidized bed in the presence of catalyst under polymerization conditions. A recycle stream can be taken from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product can be withdrawn from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors may comprise a process for a multi-step gas phase polymerization of olefins, wherein olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in US Patents 5,352,749, 4,588,790, and 5,436,304, each of which is incorporated herein by reference in its entirety.
[99] According to yet another embodiment, a polymerization reactor system may comprise a high pressure polymerization reactor, for example, it may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have multiple zones where fresh monomer, initiators, or catalysts are added. The monomer can be entrained in an inert gaseous 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. Gaseous streams can be mixed for polymerization. Heat and pressure can be properly employed to obtain optimal polymerization reaction conditions.
[100] According to another embodiment, the polymerization reactor may comprise a solution polymerization reactor in which the monomer/comonomer is contacted with the catalyst composition by suitable agitation or other means. A carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer/comonomer can be brought into the vapor phase in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone can be 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 the best temperature control and to maintain uniform polymerization mixtures throughout the entire polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
[101] The polymerization reactor system can further comprise any combination of at least one feedstock feed system, at least one feed system for catalyst or catalyst components, and/or at least one polymer recovery system . Suitable reactor systems may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor refrigeration, polymer recovery, fractionation, recycling, storage, offloading, laboratory analysis and process control. Depending on the desired properties of the olefin polymer, hydrogen can be added to the polymerization reactor as needed (eg, continuously, pulsed, etc.) and as discussed above.
[102] Polymerization conditions that can be controlled for efficiency and to provide desired polymer properties can include temperature, pressure, and concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. Suitable polymerization temperatures can be any temperatures 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. In some reactor systems, the polymerization temperature can generally be within the range of about 70°C to about 110°C, or from about 75°C to about 95°C.
[103] Appropriate pressures will also vary by reactor and type of polymerization. Pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig. The gas phase polymerization pressure can be in the range of 200 to 500 psig. High pressure polymerization in tubular or autoclave reactors can generally be performed at about 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region generally occurring at higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) can offer advantages.EXAMPLES
[104] Modalities of the invention are further illustrated by the following examples, which should not be considered to impose limitations on the scope of this invention described herein. Various other aspects, modalities, modifications and equivalents thereof which, after reading the description herein, may suggest to one skilled in the art without departing from the spirit of the present invention or the scope of the appended claims.
[105] The melt index (MI, g/10 min) was determined in accordance with ASTM D1238 at 190°C, with a weight of 2,160 grams. The high load melt index (HLMI, g/10 min) was determined in accordance with ASTM D1238 at 190°C, with a weight of 21,600 grams.
[106] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent Company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA ) running at 145°C. The flow rate of the 1,2,4-trichlorobenzene (TCB) mobile phase containing 0.5 g/L 2,6-di-t-butyl-4-methylphenol (BHT) was set to 1 mL/min, and the polymer solution concentrations were in the range of 1.0-1.5 mg/ml, depending on molecular weight. Sample preparation was performed at 150 °C for nominally 4 hr with occasional gentle shaking, before the solutions were transferred to sample vials for injection. The integral calibration method was used to deduce molecular weights and molecular weight distributions using Chevron Phillips Chemicals Company's HDPE polyethylene resin, MARLEX BHB5003, as a broad standard. The integral table of the broad pattern was predetermined in a separate experiment with SEC-MALS. Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, and Mp is the peak molecular weight.
[107] Sulphated alumina-support activators were prepared as follows. Bohmite was obtained from W.R. Grace and Company, under the designation "Alumina A" and having a surface of about 300 m2 /g and a pore volume of about 1.3 ml/g. This material was obtained as a powder having an average particle size of about 100 microns. This material was impregnated with incipient moisture with an aqueous solution of ammonium sulfate equal to about 15% sulfate. This mixture was then placed in a flat pan and dried under vacuum at approximately 110 °C for about 16 hours. To calcine the resulting powder mixture, the material was fluidized in a flow of dry air at about 550 °C for about 6 hours. Thereafter, the sulfated alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.EXAMPLES 1-5Impact of the addition of diethyl zinc (TEN) on the melt flow properties and molecular weight of an ethylene/1 copolymer -hexene.
[108] The polymerization experiments of Examples 1-5 were performed in a one-gallon stainless reactor (3.8-L) with 2 L of isobutane. Metallocene solutions (nominal 1 mg/ml) of MET-A and MET-B were prepared by dissolving 15 mg of the respective metallocene in 15 ml of toluene. Metallocene compounds MET-A and MET-B had the following structures:

[109] Approximately 2 mg of MET-A and 2 mg of MET-B (a 1:1 weight ratio) were used in Examples 1-5, and the metallocene MET-A and MET-B solutions were premixed to be loaded into the reactor.
[110] The polymerization experiments were carried out as follows. First, 0.9 mmol triisobutylaluminum (TIBA), 300 mg sulfated alumina, and the pre-mixed metallocene solution containing MET-A and MET-B were added in that order through a charging port while slowly venting steam of isobutane. Then TEN was added. The loading port was closed and 2L of isobutane was added. The reactor contents were stirred and heated to the desired polymerization reaction temperature of 95°C, and ethylene was then introduced into the reactor with 10 g of 1-hexene and hydrogen (H2) in 300 ppm by weight of ethylene. Ethylene and hydrogen were fed on demand at the specified weight ratio to maintain a target pressure of 420 psig pressure for the 45 minute duration of each polymerization experiment. The reactor was maintained at the desired reaction temperature throughout the experiment by an automated heating-cooling system.
[111] Table I summarizes the amount of TEN added, the amount of polymer produced, and the melt flow and molecular weight characteristics of the polymers from Examples 1-5. As shown in Table I, and unexpectedly, the addition of DEZ decreased the HLMI/MI shear rate and increased the Mz/Mw ratio of the polymer.
[112] The impact of the addition of DEZ on the molecular weight distributions (amount of polymer versus the log of molecular weight) of polymers from Examples 1-5 is graphically illustrated in FIG. 1. As shown in FIG. 1 and unexpectedly, the addition of DEZ decreased the weight ratio of the higher molecular weight component (HMW) to the lower molecular weight component (e.g. relatively more lower molecular weight material was produced). Furthermore, the peak molecular weight of the lower molecular weight component increased with the addition of DEZ, while the peak molecular weight of the higher molecular weight component was not substantially affected.

[113] The invention has been described above with reference to several specific embodiments and examples. Many variations will suggest to those 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:
[114] Modality 1. A method of controlling the polymerization reaction in a polymerization reactor system, the method comprising: (i) contacting a dual catalyst system with an olefin monomer and an optional olefin comonomer in the reactor system of polymerization under polymerization conditions to produce an olefin polymer, wherein the dual catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and (ii) introducing an amount of an organozinc compound into the polymerization reactor to reduce an HLMI/MI shear rate and/or increase an Mz/Mw ratio of the olefin polymer.
[115] Modality 2. A process for producing an olefin polymer with a target HLMI/MI shear rate and/or a target Mz/Mw ratio, the process comprising: (a) contacting a dual catalyst system with a monomer of olefin and an optional olefin comonomer in a polymerization reactor system under polymerization conditions, wherein the dual catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and (b) controlling an amount of one organozinc compound introduced into the polymerization reactor system to produce the olefin polymer with the target HLMI/MI shear rate and/or target Mz/Mw ratio.
[116] Modality 3. The method or process defined in modality 1 or 2, wherein the amount of the organozinc compound is in any range of molar ratios disclosed herein, based on the moles of the organozinc compound to the total moles of the first component of metallocene catalyst and the second component of the metallocene catalyst, for example, from about 5:1 to about 200:1, from about 10:1 to about 150:1, from about 30:1 to about 120:1, etc.
[117] Modality 4. The method or process defined in any one of embodiments 1-3, wherein the organozinc compound comprises any organozinc compound disclosed herein, for example, a compound having the formula: Zn(X10)(X11) ; on what:
[118] X10 is a C1 to C18 hydrocarbyl group; and
[119] X11 is H, a halide, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarboxy group.
[120] Modality 5. The method or process defined in any one of embodiments 1-4, wherein the organozinc compound comprises dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dynepentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di (triisopropylsilyl)zinc, di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc, or a combination thereof.
[121] Modality 6. The method or process defined in any one of embodiments 1-5, wherein the organozinc compound comprises diethylzinc.
[122] Modality 7. The method or process defined in any one of embodiments 1-6, wherein the catalyst system comprises any first metallocene catalyst component, any second metallocene catalyst component, and any activator disclosed herein by example, an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionic ionizing compound, etc., or any combination thereof.
[123] Modality 8. The method or process defined in modality 7, wherein the activator comprises an aluminoxane compound.
[124] Modality 9. The method or process defined in modality 7, wherein the activator comprises an organoboron or organoborate compound.
[125] Modality 10. The method or process defined in modality 7, wherein the activator comprises an ionizing ionic compound.
[126] Modality 11. The method or process defined in modality 7, wherein the activator comprises a support activator comprising a solid oxide treated with an electron withdrawing anion, e.g. a support activator comprising any solid oxide treated with any electron withdrawn anion disclosed here.
[127] Modality 12. The method or process defined in modality 11, wherein the solid oxide comprises silica, alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof or combinations thereof; and the electron withdrawing anion comprises sulfate, bisulfate, fluorine, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluozirconate, fluorotitanate, phospho-tungstate, or combinations thereof.
[128] Modality 13. The method or process defined in modality 11, wherein the support activator comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica -sulfated 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 or any combination of same.
[129] Modality 14. The method or process defined in modality 11, wherein the support activator comprises fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, fluorinated silica coated alumina, alumina coated with sulfated silica, or any combination thereof.
[130] Modality 15. The method or process defined in any one of embodiments 11-14, wherein the amount of organozinc compounds is in any range of weight percentages disclosed herein, based on the weight of the organozinc compound to the weight of the added support-activator, for example, from about 2 to about 100% by weight, from about 4 to about 80% by weight, from about 10 to about 60% by weight, etc.
[131] Modality 16. The method or process defined in any one of embodiments 1-15, wherein the catalyst system comprises any first metallocene catalyst component, any second metallocene catalyst component, any activator, and any compound of organoaluminium disclosed here.
[132] Modality 17. The method or process defined in modality 16, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n- octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.
[133] Modality 18. The method or process defined in modality 16 or 17, wherein the activator comprises fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, fluorinated silica coated alumina, alumina coated with sulfated silica, or any combination thereof.
[134] Modality 19. The method or process defined in any one of modalities 1-18, 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.
[135] Modality 20. The method or process defined in any one of embodiments 1-19, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof .
[136] Modality 21. The method or process defined in any one of embodiments 1-20, wherein the polymerization reactor system comprises a loop paste reactor.
[137] Modality 22. The method or process defined in any one of embodiments 1-21, wherein the polymerization reactor system comprises a single reactor.
[138] Modality 23. The method or process defined in any of the embodiments 1-21, wherein the polymerization reactor system comprises 2 reactors.
[139] Modality 24. The method or process defined in any one of embodiments 1-21, wherein the polymerization reactor system comprises more than 2 reactors.
[140] Modality 25. The method or process defined in any one of embodiments 1-24, wherein the olefin monomer comprises a C2-C20 olefin.
[141] Modality 26. The method or process defined in any one of embodiments 1-25, wherein the olefin monomer and the optional olefin comonomer independently comprise a C2-C20 alpha-olefin.
[142] Modality 27. The method or process defined in any one of embodiments 1-26, wherein the olefin monomer comprises ethylene.
[143] Modality 28. The method or process defined in any of modality 1-27, wherein the catalyst system is contacted with ethylene and a C3-C10 alpha-olefin comonomer.
[144] Modality 29. The method or process defined in any one of modalities 1-28, wherein the catalyst system is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a mixture of the same.
[145] Modality 30. The method or process defined in any one of embodiments 1-29, wherein the olefin polymer in step (ii) and/or step (b) has a multimodal molecular weight distribution.
[146] Modality 31. The method or process defined in any one of embodiments 1-29, wherein the olefin polymer in step (ii) and/or step (b) has a bimodal molecular weight distribution.
[147] Modality 32. The method or process defined in any one of embodiments 1-29, wherein the olefin polymer in step (ii) and/or step (b) has a unimodal molecular weight distribution.
[148] Modality 33. The method or process defined in any one of embodiments 1-32, wherein the melt index (MI) of the olefin polymer in step (ii) and/or step (b) is in any disclosed range here, for example, from about 0.005 to about 2 g/10 min, from about 0.01 to about 1 g/10 min, from about 0.05 to about 0.5 g/10 min, etc.
[149] Modality 34. The method or process defined in any one of embodiments 1-33, wherein the number average molecular weight (Mn) of the olefin polymer in step (ii) and/or step (b) is in any range disclosed herein, for example, from about 5,000 to about 25,000 g/mol, from about 6,000 to about 20,000 g/mol, from about 7,000 to about 18,000 g/mol, etc.
[150] Modality 35. The method or process defined in any one of embodiments 1-34, wherein the weight-average molecular weight (Mw) of the olefin polymer in step (ii) and/or step (b) is in any range disclosed herein, for example, from about 100,000 to about 300,000 g/mol, from about 100,000 to about 275,000 g/mol, or from about 125,000 to about 250,000 g/mol.
[151] Modality 36. The method or process defined in any one of embodiments 1-35, wherein the Mw/Mn ratio of the olefin polymer in step (ii) and/or step (b) is in any range disclosed herein, for example, from about 5 to about 40, from about 6 to about 35, from about 7 to about 30, from about 8 to about 28, etc.
[152] Modality 37. The method or process defined in any one of embodiments 1-36, wherein the olefin polymer is an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene copolymer /1-octene.
[153] Modality 38. The method or process defined in any one of embodiments 1-37, wherein the olefin polymer is an ethylene/1-hexene copolymer.
[154] Modality 39. The method or process defined in any one of embodiments 1-38, wherein the first metallocene catalyst component and the second metallocene catalyst component independently comprise chromium, vanadium, titanium, zirconium, hafnium, or a combination of them.
[155] Modality 40. The method or process defined in any one of embodiments 1-39, wherein the first metallocene catalyst component and the second metallocene catalyst component independently comprise titanium, zirconium, hafnium, or a combination thereof.
[156] Modality 41. The method or process defined in any one of embodiments 1-40, wherein the first metallocene catalyst component comprises any first metallocene catalyst component disclosed herein, e.g., an unbridged metallocene compound, an unbridged dinuclear metallocene compound, etc.
[157] Modality 42. The method or process defined in any one of embodiments 1-41, wherein the first metallocene catalyst component comprises zirconium.
[158] Modality 43. The method or process defined in any one of embodiments 1-42, wherein the second metallocene catalyst component comprises any second metallocene catalyst component disclosed herein, e.g., a bridged metallocene compound, etc.
[159] Modality 44. The method or process defined in any one of embodiments 1-43, wherein the second metallocene catalyst component comprises zirconium and/or hafnium.
[160] Modality 45. The method or process defined in any one of embodiments 1-44, wherein a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component is substantially constant, e.g., for one grade of particular polymer.
[161] Modality 46. The method or process defined in any one of embodiments 1-44, further comprising a step of adjusting a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component.
[162] Modality 47. The method or process defined in any one of modalities 1-46, and that 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 1000 psig (about 1.4 to about 6.9 MPa).
[163] Modality 48. The method or process defined in any one of embodiments 1-47, wherein the polymerization conditions are substantially constant, e.g., for a particular polymer grade.
[164] Modality 49. The method or process defined in any one of embodiments 1-47, further comprising a step of adjusting at least one polymerization condition, e.g., temperature, pressure, residence time, etc.
[165] Modality 50. The method or process defined in any one of Modalities 1-49, in which no hydrogen is added to the polymerization reactor system.
[166] Modality 51. The method or process defined in any one of modalities 1-49, wherein hydrogen is added to the polymerization reactor system, and the hydrogen addition is substantially constant, eg for a particular polymer grade .
[167] Modality 52. The method or process defined in any one of embodiments 1-49, further comprising a step of adding hydrogen to the polymerization reactor system to adjust the weight-average molecular weight (Mw) of the polymer.
[168] Modality 53. The method or process defined in any one of embodiments 1-49, further comprising a step of adding hydrogen to the polymerization reactor system to adjust the melt index (MI) of the polymer.
[169] Modality 54. The method or process defined in any one of embodiments 51-53, wherein the step of adding hydrogen decreases the Mw and/or increases the melt index of the polymer.
[170] Modality 55. The method or process defined in any of the modality 1-54, further comprising the steps of determining (or measuring) the HLMI/MI shear rate, and adjusting the amount of organozinc compound introduced into the polymerization reactor based on the difference between the measured HLMI/MI shear rate and the target HLMI/MI shear rate.
[171] Modality 56. The method or process defined in any one of embodiments 1-55, further comprising the steps of determining (or measuring) the Mz/Mw ratio, and adjusting the amount of organozinc compound introduced into the reactor system. polymerization based on the difference between the measured Mz/Mw ratio and the target Mz/Mw ratio.
[172] Modality 57. The method or process defined in any one of embodiments 1-56, wherein the olefin polymer comprises a higher molecular weight component and a lower molecular weight component.
[173] Modality 58. The method or process defined in modality 57, wherein introducing the organozinc compound into the polymerization reactor system reduces the weight ratio of the higher molecular weight component to the lower molecular weight component.
[174] Modality 59. The method or process defined in modality 57 or 58, wherein introducing the organozinc compound into the polymerization reactor system increases the peak molecular weight of the lower molecular weight component.
[175] Modality 60. The method or process defined in any one of embodiments 57-59, wherein introducing the organozinc compound into the polymerization reactor system has substantially no effect on the peak molecular weight of the higher molecular weight component .
[176] Modality 61. The method or process defined in any one of embodiments 57-60, wherein the first metallocene catalyst component produces the lowest molecular weight component.
[177] Modality 62. The method or process defined in any one of embodiments 57-61, wherein the second metallocene catalyst component produces the higher molecular weight component.
[178] Modality 63. The method or process defined in any one of embodiments 1-62, wherein the organozinc compound is introduced into the polymerization reactor system continuously.
[179] Modality 64. The method or process defined in any one of embodiments 1-62, wherein the organozinc compound is introduced into the polymerization reactor system periodically.
[180] Modality 65. The method or process defined in any one of embodiments 1-64, wherein the weight ratio of the first metallocene catalyst component to the second metallocene catalyst component is in any range of disclosed weight ratios here, for example, from about 1:100 to about 100:1, from about 1:5 to about 5:1, from about 1:2 to about 2:1, etc.
[181] Modality 66. The method or process defined in any one of Modalities 1-66, wherein the HLMI/MI shear rate of the olefin polymer may decrease as the amount of organozinc compound added to the polymerization reactor system increases .
[182] Modality 67. The method or process defined in any one of embodiments 1-66, wherein the Mz/Mw ratio of the olefin polymer increases as the amount of organozinc compound added to the polymerization reactor system increases.

权利要求:
Claims (19)
[0001]
1. Method for controlling the polymerization reaction in a polymerization reactor system, the method comprising: (I) contacting a dual catalyst system with an olefin monomer and an optional olefin comonomer in the polymerization reactor system under polymerization conditions for producing an olefin polymer, wherein the dual catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component; and(II) introducing an amount of an organozinc compound into the polymerization reactor system to reduce an HLMI/MI shear rate and/or increase an Mz/Mw ratio of the olefin polymer, wherein the organozinc compound comprises a compound having the formula: Zn(X10)(X11)wherein:X10 is a C1 to C18 hydrocarbyl group; and (XII) is H, a halide, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarboxy group.
[0002]
2. The method of claim 1, wherein the dual catalyst system comprises: a first metallocene catalyst component comprising an unbridged metallocene compound containing zirconium or an unbridged dinuclear metallocene compound containing zirconium; a second metallocene catalyst component comprising a bridged metallocene compound containing zirconium or hafnium; and an activator comprising an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionic ionizing compound, or any combination thereof.
[0003]
3. Method according to claim 2, characterized in that: the activator comprises a support activator comprising fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, silica-alumina brominated, 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, or any combination thereof; and the amount of organozinc compound introduced into the polymerization reactor system is in the range of about 2 to about 100% by weight, based on the weight of support-activator added to the polymerization reactor system.
[0004]
4. Method 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.
[0005]
5. Method according to claim 1, characterized in that the polymerization reactor system comprises a single reactor.
[0006]
6. Method according to claim 1, characterized in that the olefin monomer comprises ethylene and the olefin comonomer comprises a C3-C10 alpha-olefin.
[0007]
7. Method according to claim 1, characterized in that it further comprises: determining the HLMI/MI shear rate, and adjusting the amount of organozinc compound introduced into the polymerization reactor system based on the difference between the rate determined HLMI/MI shear rate and a target HLMI/MI shear rate; or determining the Mz/Mw ratio, and adjusting the amount of organozinc compound introduced into the polymerization reactor system based on the difference between the determined Mz/Mw ratio and a target Mz/Mw ratio; or both.
[0008]
8. The method of claim 1, characterized in that a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component is in a range from about 1:10 to about 10:1 .
[0009]
9. Method according to claim 1, characterized in that a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component is substantially constant.
[0010]
10. Method according to claim 1, characterized in that the amount of organozinc compound introduced into the polymerization reactor system is in a molar ratio range from about 5:1 to about 200:1 based in the ratio of the moles of the organozinc compound to the total moles of the first metallocene catalyst component and the second metallocene catalyst component added to the polymerization reactor system.
[0011]
11. The method of claim 1, further comprising: a step of adjusting a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component; or a step of adding hydrogen to the polymerization reactor system to adjust a molecular weight parameter and/or a melt index of the olefin polymer; or both.
[0012]
12. A process for producing an olefin polymer having a target HLMI/MI shear rate and/or a target Mz/Mw ratio, the process comprising: (a) contacting a dual catalyst system with an olefin monomer and a comonomer of optional olefin in a polymerization reactor system under polymerization conditions, wherein the dual catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component; and (b) controlling an amount of an organozinc compound introduced into the polymerization reactor system to produce the olefin polymer with the target HLMI/MI shear rate and/or target Mz/Mw ratio, wherein the organozinc compound comprises a compound having the formula: Zn(X10)(X11)wherein:X10 is a C1 to C18 hydrocarbyl group; and (c) is H, a halide, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarboxy group.
[0013]
13. Process according to claim 12, characterized in that the olefin polymer has: a melt index (MI) of less than about 10 g/10min; a number average molecular weight (Mn) in a range from about 5,000 to about 40,000 g/mol; a weight-average molecular weight (Mw) in a range from about 100,000 to about 350,000 g/mol; or a ratio of Mw/Mn in a range of about 5 to about 40; or any combination thereof.
[0014]
14. Process according to claim 13, characterized in that the organozinc compound comprises diethylzinc, and the olefin polymer is an ethylene/α-olefin copolymer.
[0015]
15. Process according to claim 12, characterized in that the HLMI/MI shear rate of the olefin polymer decreases as the amount of organozinc compound added to the polymerization reactor system increases.
[0016]
16. Process according to claim 12, characterized in that the Mz/Mw ratio of the olefin polymer increases as the amount of organozinc compound added to the polymerization reactor system increases.
[0017]
17. Process according to claim 12, characterized in that the olefin polymer comprises a higher molecular weight component and a lower molecular weight component, and in which: a weight ratio of the molecular weight component higher for the lower molecular weight component decreases as the amount of organozinc compound added to the polymerization reactor system increases; a peak molecular weight of the lower molecular weight component increases as the amount of organozinc compound added to the polymerization reactor system increases; or a peak molecular weight of the higher molecular weight component is substantially unchanged as the amount of organozinc compound added to the polymerization reactor system increases; or any combination thereof.
[0018]
18. Process according to claim 12, characterized in that: the polymerization reactor system comprises a loop paste reactor; the organozinc compound comprises diethylzinc; and the olefin polymer is an ethylene/1-hexene copolymer.
[0019]
19. Process according to claim 18, characterized in that the dual catalyst system comprises: a first metallocene catalyst component comprising an unbridged metallocene compound containing zirconium or an unbridged dinuclear metallocene compound containing zirconium; a second metallocene catalyst component comprising a bridged metallocene compound containing zirconium or hafnium; a support activator comprising a solid oxide treated with an electron withdrawing anion; and an organoaluminium compound.

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同族专利:

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公开号 | 公开日

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US8680218B1|2014-03-25|

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SG11201505971TA|2015-08-28|

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WO2014120542A1|2014-08-07|

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CN103965379B|2018-07-13|

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CN103965379A|2014-08-06|

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EP2951218B1|2021-03-17|

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ES2870714T3|2021-10-27|

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/01/2014, 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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US13/753,556|2013-01-30|

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US13/753,556|US8680218B1|2013-01-30|2013-01-30|Methods for controlling dual catalyst olefin polymerizations with an organozinc compound|

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