methods for controlling double metallocene catalyst olefin polymerizations with an alcohol compound

专利摘要:
METHODS TO CONTROL DOUBLE METALOCENE CATALYST OIL POLYMERIZATIONS WITH AN ALCOHOL COMPOUND. Methods for controlling properties of an olefin polymer using an alcohol compound are disclosed. MI and HLMI of the polymer can be decreased and the Mw and Mz of the polymer can be increased by adding the alcohol compound.
公开号:BR112016002782B1
申请号:R112016002782-5
申请日:2014-08-05
公开日:2020-12-29
发明作者:Max P. Mcdaniel；Albert P. Masino；Tony R. Crain；Qing Yang；Ted H. Cymbaluk；John D. Stewart
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 double metallocene catalyst system. For example, the composition of the catalyst and / or the polymerization reaction conditions can be changed to vary the melt flow properties and the molecular weight characteristics of the polymer that is produced. However, additional methods for adjusting or controlling the properties of the polymer are necessary that do not require changes in the composition of the catalyst or the polymerization conditions. Therefore, it is for this purpose that the present disclosure is directed. SUMMARY OF THE INVENTION
[2] This summary is provided to introduce a selection of concepts in a simplified way that are still described below in the detailed description. This summary is not intended to identify necessary or essential characteristics of the claimed matter. Nor is this summary intended to be used to limit the scope of the claimed matter.
[3] Various processes and methods related to the control of double 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 a carbon monomer. 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, a second metallocene catalyst component, an activator, and a cocatalyst; and (ii) introducing an amount of an alcohol compound into the polymerization reactor system to reduce a melt index parameter (e.g., melt index (MI), high charge melt index (HLMI), etc.). ) of the olefin polymer, to increase a molecular weight parameter (for example, weight average molecular weight (Mw), average molecular weight z (Mz), etc.) of the olefin polymer, or to reduce a weight index parameter melting and increasing a molecular weight parameter of the olefin polymer.
[4] A process for producing an olefin polymer with a target melt index parameter (for example, MI, HLMI, etc.), a target molecular weight parameter (for example, Mw, Mz, etc.), or a target melt index parameter and a target molecular weight parameter, is provided here, and in that embodiment, the process may comprise: (a) contacting a dual catalyst system with an olefin monomer and an optional olefin comonomer in one polymerization reactor system under polymerization conditions, wherein the dual catalyst system comprises a first metallocene catalyst component, a second metallocene catalyst component, an activator, and a cocatalyst; and (b) controlling an amount of an alcohol compound introduced into the polymerization reactor system to produce the olefin polymer with the target melt index parameter (e.g., MI, HLMI, etc.), the molecular weight parameter target (e.g., Mw, Mz, etc.), or the target melt index parameter and the target molecular weight parameter.
[5] In these methods and processes, the melt index parameters, such as MI and HLMI, of the olefin polymer may decrease as the amount of alcohol compound added to the polymerization reactor system is increased. In addition, the molecular weight parameters, such as Mw and Mz, of the olefin polymer may increase as the amount of alcohol compound added to the polymerization reactor system is increased.
[6] Both the above summary and the detailed description below provide examples and are for explanation 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 forth here. For example, certain modalities can be directed to various combinations and sub-combinations of characteristics described in the detailed description. BRIEF DESCRIPTION OF THE FIGURE
[7] The figure shows a graph of the molecular weight distribution as a function of the amount of isopropanol for Examples 1-4. DEFINITIONS
[8] To define more clearly the terms used here, the following definitions are provided. Unless otherwise stated, the following definitions apply to this disclosure. If a term is used in this disclosure, but is not specifically defined here, the definition of IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) can be applied, provided that this definition does not conflict with any other type of disclosure or definition applied here, or make any claim to which that definition is applied indefinite or not enabled. Insofar as any definition or use provided by any document incorporated herein as a reference conflicts with the definition or use provided here, the definition or use provided here controls.
[9] Although compositions and methods are often described in terms of "comprising" various components or steps, compositions and methods can also "consist essentially of" or "consist of" various components or steps, unless otherwise stated.
[10] The terms "one", "one", "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. other way.
[11] For any particular compound or group disclosed here, 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, diastereoisomers 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 for pentane, for example, includes n-pentane, 2-methyl-butane 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.
[12] 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 those values. For example, unless otherwise specified, any carbon-containing group or compound may have 1 to 20 carbon atoms, 1 to 18 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 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 qualifying identifiers or terms can be used to indicate the presence or absence of a particular substituent, a particular regiochemistry, or stereochemistry, or the presence or absence of an underlying branched structure. Any group containing specific carbon is limited according to the chemical and structural requirements for that specific group, as understood by an expert.
[13] Other numerical ranges are disclosed here. When Depositors disclose or claim a range of any kind, it is the intention of Depositors to individually disclose or claim each possible number so that a range could reasonably be included, including the end points of the range, as well as any sub-range and sub-range combinations. included in these, unless otherwise specified. As a representative example, Depositors disclose that a weight ratio of the highest molecular weight component to the lowest molecular weight component can be in the range of about 1:10 to about 10: 1 in certain embodiments. By disclosing that the weight ratio of the highest molecular weight component to the lowest molecular weight component can be in the range of about 1:10 to about 10: 1, the depositor intends to recite that the weight can be any weight ratio within the range and, for example, it can be about 1:10, about 1: 9, about 1: 8, about 1: 7, about 1: 6, about 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. In addition, the weight ratio can be within 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 combination of the range between about 1:10 and 10: 1. Likewise, all the other tracks published here must be interpreted in a similar way to these examples.
[14] Depositors reserve the right to reserve or exclude any individual members of any group, including any sub-bands or combinations of sub-bands within the group, which may be claimed under a band or in a similar manner, if for any reason. Depositor chooses to claim less than the full disclosure measure, for example, accounting for a reference that Depositors may be unaware of at the time of filing the application. In addition, Depositors reserve the right to reserve or exclude any substituents, analogs, compounds, binders, structures or groups thereof, or any members of a claimed group, if for any reason the Depositor chooses to claim less than the full measure disclosure, for example, accounting for a reference that Depositors may be unaware of at the time of filing the application.
[15] The term "substituted" when used to describe a group or chain of carbon atoms, for example, when referring to a substituted analog of a particular group or chain, is intended to describe either group or chain in which any non-hydrogen fraction formally replaces a hydrogen in that group or chain, and is intended to be non-limiting. A group or chain can be referred to here as "unsubstituted" or by equivalent terms like "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 skilled in the art.
[16] The term "hydrocarbon", 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 (for example, halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). The term "hydrocarbon group" is used here, in accordance with the definition specified by 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 hydrocarbon groups include groups, alkyl, alkenyl, and aralkyl, among other groups as members.
[17] The term "polymer" is used here generically to include homopolymers, copolymers, olefin terpolymers, and so on. A copolymer can be derived from an olefin monomer and an olefin comonomer, while a terpolymer can be derived from an olefin monomer and two olefin comonomers. Accordingly, the "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" should also include all molecular weights of polymers, and is inclusive of lower molecular weight polymers or oligomers. Depositors intend with 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 on).
[18] In a similar way, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc., as well as processes that can also be referred to as oligomerization processes. Therefore, a copolymerization process may involve contacting an olefin monomer (for example, ethylene) and an olefin comonomer (for example, 1-hexene) to produce an olefin copolymer.
[19] 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 (for example, 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 can be the result of contact with these initial starting components, and this is inclusive of heterogeneous or homogeneous catalyst systems or compositions. The terms "catalyst composition," "catalyst mixture", "catalyst system" and the like, can be used interchangeably throughout this disclosure.
[20] The terms "contact the product," "contact" and the like, are used here to describe compositions in which components are contacted together in any order, in any way and for any period of time. For example, components can be contacted by tapping or mixing. In addition, unless otherwise specified, contact of any component may occur in the presence or absence of any other component of the compositions described herein. The combination of additional materials or components can be done by any suitable method. In addition, the term "contact product" includes mixtures, beats, solutions, pastes, reaction products, and the like, or combinations thereof. Although "contact product" may include, and often does include, reaction products, the respective components are not required to react with another. 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.
[21] While any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, typical methods and materials are described herein.
[22] All publications and patents mentioned here 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 can be used in connection with the invention described here. The publications discussed throughout the text are provided for your disclosure only prior to the filing date of the present application. Nothing contained herein should be construed as an admission that the invention does not have the right to predate such disclosure by virtue of a previous invention. DETAILED DESCRIPTION OF THE INVENTION
[23] Targeted methods and processes for controlling double catalyst olefin polymerizations in a polymerization reactor system by adding an alcohol compound are disclosed here. In these methods and processes, the amount of the alcohol compound added to the reactor system can be used to adjust a melt index parameter (for example, MI, HLMI, etc.) of the olefin polymer, and in addition or alternatively, it can be used to adjust a molecular weight parameter (for example, Mw, Mz, etc.) of the olefin polymer. The polymerization reaction can be carried out in a reactor system that can contain one reactor, or alternatively, two or more reactors in series or in parallel.
[24] 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: [1] contacting a double catalyst system with an olefin monomer and an optional olefin comonomer in the polymerization reactor system under polymerization conditions to produce an olefin polymer, in which the double catalyst comprises a first metallocene catalyst component, a second metallocene catalyst component, an activator, and a cocatalyst; and [11] introducing an amount of an alcohol compound into the polymerization reactor system to (I) reduce to a melt index parameter (e.g., MI, HLMI) of the olefin polymer; (II) increasing a molecular weight parameter (for example, Mw, Mz, etc.) of the olefin polymer; or (III) reduce to a melt index parameter and increase a molecular weight parameter of the olefin polymer.
[25] Thus, the addition of the alcohol compound (for example, by increasing the amount of the alcohol compound) may decrease a melt index parameter of the olefin polymer. Illustrative and non-limiting examples of melt index parameters are MI (g / 10 min, ASTM D1238, 190 ° C, and 2.16 kg in weight) and HLMI (g / 10 min, ASTM D1238, 190 ° C and 21 , 6 kg in weight). In addition or alternatively, the addition of the alcohol compound (for example, by increasing the amount of the alcohol compound) may increase a molecular weight parameter of the olefin polymer. Illustrative and non-limiting examples of molecular weight parameters are Mw and Mz (in g / mol, determined using gel permeation chromatography (GPC) or other suitable analytical procedure).
[26] In another embodiment, a process for producing an olefin polymer with a target melt index parameter (eg, MI, HLMI, etc.), a target molecular weight parameter (eg, Mw, Mz, etc. .), or a target melt index parameter and a target molecular weight parameter, is disclosed. In this embodiment, the process may comprise: (a) contacting a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions, in which the double catalyst system comprises a first metallocene catalyst component, a second metallocene catalyst component, an activator, and a cocatalyst; and (b) controlling an amount of an alcohol compound introduced into the polymerization reactor system to produce the olefin polymer with the target melt index parameter (e.g., MI, HLMI, etc.), the molecular weight parameter target (e.g., Mw, Mz, etc.), or the target melt index parameter and the target molecular weight parameter.
[27] Thus, the addition of the alcohol compound (for example, by increasing the amount of the alcohol compound) can be used to produce an olefin polymer with a target melt index parameter, or a target molecular weight parameter, or both.
[28] In these methods and processes, the alcohol compound can be introduced (for example, added, injected, etc.) into the polymerization reactor system by any suitable means, for example, alone, or with a carrier (for example, a carrier gas, a liquid carrier, etc.). The alcohol compound can be introduced into the polymerization reactor system at any suitable location within the reactor system. In one embodiment, the alcohol compound can be added directly to a polymerization reactor within the polymerization reactor system, while in another embodiment, the alcohol compound can be introduced into the polymerization reaction system at a feed or inlet location. different from directly in a polymerization reactor, for example, in a recycling stream. In some embodiments, the alcohol compound can be added to the reactor alone, while in other embodiments, the alcohol compound can be added to the reactor with a carrier or solvent, non-limiting examples of which may include, but are not limited to, 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 certain embodiments, the alcohol compound can be added to the reactor with an olefin monomer / comonomer, such as 1-butene, 1-hexene, or 1-octene, and the like. In particular embodiments contemplated here, the alcohol compound can be added to the polymerization reactor system with the dual catalyst system. Additional power options for a polymerization reactor system are described in US Patent 7,615,596, the disclosure of which is incorporated herein by reference in its entirety.
[29] Generally, the characteristics of the methods and processes disclosed here (for example, the double catalyst system, the first metallocene catalyst component, the second metallocene component, the activator, the cocatalyst, the olefin monomer, the comonomer of olefin, the polymerization conditions, the polymerization reactor system, the alcohol compound, the amount of the alcohol compound, the melt index parameter, the molecular weight parameter, among others) are independently described here, and these characteristics can be combined in any combination to further describe the methods and processes disclosed.
[30] In certain methods and processes disclosed here, a double catalyst system can be contacted with an olefin monomer and optionally an olefin comonomer in the polymerization reactor system, and an alcohol compound can be added to the reactor system. As would be recognized by a person skilled in the art, additional components can be introduced into the polymerization reactor system in addition to these recited components, and those non-recited components are included here. For example, when operating a polymerization reactor system - depending, of course, on the type of polymerization reactor, the desired olefin polymer, etc., among other factors - solvents, thinners, fluidizing gases, recycling flows, etc. ., can also be added or introduced into the polymerization reactor and polymerization reactor system.
[31] 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 the range of about 1: 100 to about 100: 1, about 1:50 about 50: 1, about 1:25 to about 25: 1, about 1:10 to about 10: 1, or about 1: 5 to about 5: 1. Accordingly, ranges suitable for the weight ratio of the first metallocene catalyst component to the second metallocene catalyst component may include, among others, from about 1:15 to about 15: 1, from about 1:10 to about 10: 1, about 1: 8 to about 8: 1, about 1: 5 to about 5: 1, about 1: 4 to about 4: 1, about 1: 3 to about 3: 1, about 1: 2 to about 2: 1, about 1: 1.8 to about 1.8: 1, 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.
[32] Consistent with modalities disclosed here, the weight ratio of the first metallocene catalyst component to the second metallocene catalyst component can be kept substantially constant (for example, within +/- 5%), for example, for the production of a particular polymer grade. In these circumstances, the addition of the alcohol compound can be used to control, adjust, refine, etc., the production and properties of that particular polymer grade, without the need to vary the catalyst composition.
[33] Optionally, if additional control parameters for the dual catalyst polymerization process are desired other than the use of an alcohol compound, the methods and processes disclosed here may further comprise a step of adjusting the weight ratio of the first component of metallocene catalyst for the second metallocene catalyst component.
[34] In some embodiments, the polymerization conditions can be kept substantially constant (for example, within +/- 5%.), For example, for the production of a particular polymer grade. Representative polymerization conditions include absolute temperature, gauge pressure, residence time,% solids, and the like. As above, in these circumstances, the addition of the alcohol compound can be used to control, adjust, improve, etc., the production and properties of that particular polymer grade.
[35] Optionally, if additional control parameters for the dual catalyst polymerization process are desired other than the use of alcohol compounds, the methods and processes disclosed here may further comprise a step of adjusting at least one polymerization condition (for example , temperature, pressure, residence time, etc.).
[36] Unexpectedly, in these methods and processes, the melt index parameters such as MI and HLMI of the olefin polymer may decrease as the amount of alcohol compound added to the polymerization reactor system is increased. Also unexpectedly, the molecular weight parameters like Mw and Mz of the olefin polymer can increase as the amount of the alcohol compound added to the polymerization reactor system is increased. The alcohol compound can be added to the polymerization reactor system (for example, in a polymerization reactor) alone, with a conveyor, with the double catalyst system, etc. The amount of alcohol compound added to the reactor system is not particularly limited, while the amount of alcohol compound added to the reactor system is sufficient to impact at least one of MI, HLMI, Mw, and Mz of the olefin polymer. as described here, and does not negatively impact the catalytic activity or polymer production rate significantly (for example 20% + reduction in catalytic activity, polymer production rate, or both). While not limited to them, the amount of the alcohol compound added can normally be in a range of molar ratio of hydroxyl groups (-OH) of the alcohol compound to the total moles of the first metallocene catalyst component and the second catalyst component about 10: 1 to about 1000: 1 metallocene. This molar ratio is based on the respective amounts of the hydroxyl groups of the alcohol compound, the first component of metallocene catalyst, and the second component of metallocene catalyst fed into the reactor system (for example, in a polymerization reactor). As a non-limiting example of a 50: 1 molar ratio, in a continuous polymerization reactor system, the total amount of the first and second metallocene catalyst components fed into the reactors per time interval can be "Y" moles / hour ; thus, the amount of alcohol compound fed to the reactors would be equal to "50Y" moles / hour (moles of hydroxyl groups) for a 50: 1 molar ratio.
[37] In some embodiments, this molar ratio (moles of hydroxyl groups of the alcohol compound to total moles of metallocene components) can be in the range of about 10: 1 to about 1000: 1, from about 10: 1 to about 750: 1, from about 10: 1 to about 500: 1, from about 20: 1 to about 1000: 1, from about 20: 1 to about 750: 1, from about 20: 1 to about 500: 1, from about 20: 1 to about 250: 1, from about 20: 1 to about 200: 1, or from about 20: 1 to about 100: 1. In particular embodiments considered here, the molar ratio can be in the range of about 25: 1 to about 1000: 1, from about to about 25: 1 to about 500: 1, from about 25: 1 to about 100: 1, about 50: 1 to about 1000: 1, about 100: 1 to about 1000: 1, or about 50: 1 to about 500: 1.
[38] Unexpectedly, in these disclosed methods and processes, the Mz / Mw ratio of the olefin polymer may decrease as the amount of alcohol compound added to the polymerization reactor system is increased. However, also unexpectedly, the addition of the alcohol compound may substantially have no effect on Mn of the olefin polymer. In this regard, "substantially" no effect (substantially no change in Mn) means that Mn after adding the alcohol compound is within +/- 20% of the Mn before adding the alcohol compound. In some embodiments, Mn can be within +/- 10% or, alternatively, +/- 5%.
[39] In addition, in some embodiments, the step of introducing alcohol compounds into the polymerization reactor system, unexpectedly, may substantially have no effect (within +/- 20%; in some embodiments, within +/- 10% or, alternatively, +/- 5%) on the activity of the double catalyst system (or, for example, may have substantially no effect on the rate of production of the olefin polymer). As one skilled in the art would readily understand, an excess of the alcohol compound, compared to certain components of the dual catalyst system, can dramatically reduce the catalytic activity and the rate of polymer production and, eventually, can "kill" the reaction. Thus, the maximum practical amount of the alcohol compound added to the polymerization reactor system is limited.
[40] In one embodiment, the alcohol compound can be added to the polymerization reactor system continuously. For example, the alcohol compound can be added to the reactor whenever the olefin monomer or metallocene catalyst components, or both, are added to the reactor. Alternatively, the alcohol compound can be added periodically, on a basis as needed, or pulsed into the reactor. The intermittent addition to 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.
[41] The addition of alcohol compound can be used to produce olefin polymers having various melt flow rates and molecular weight properties. For example, the 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 Ranges contemplated for the MI of olefin polymers produced by the methods and processes disclosed herein may include, but are not limited to, from 0 to about 25 g / 10 min, from 0 to about 5 g / 10 min, from about 1 g / 10 min, from 0 to about 0.5 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 20 g / 10 min, from about 0.01 to about 2 g / 10 min, from about 0.01 to about 1 g / 10 min, from about 0.05 to about 15 g / 10 min, from about 0.05 to about 5 g / 10 min, from about 0.05 to about 1 g / 10 min, from about 0, 05 to about 0.5 g / 10 min, about 0.1 to about 2 g / 10 min, about 0.1 to about 1 g / 10 min, or about 0.1 to about 0.8 g / 10 min.
[42] The HLMI of the olefin polymer produced can be, for example, less than about 200, less than about 100, less than about 50, or less than about 25 g / 10 min. HLMI contemplated ranges of olefin polymers produced by the methods and processes disclosed herein may include, but are not limited to, 0 to about 100 g / 10 min, 0 to about 50 g / 10 min, 0 to about 25 g / 10 min, from 0 to about 20 g / 10 min, from about 0.005 to about 100 g / 10 min, from about 0.005 to about 50 g / 10 min, from about 0.005 to about 25 g / 10 min, from about 0.01 to about 100 g / 10 min, from about 0.01 to about 75 g / 10 min, from about 0.01 to about 10 g / 10 min, from about 0.1 to about 50 g / 10 min, from about 0.1 to about 20 g / 10 min, from about 0.1 to about 15 g / 10 min, from about 0, 1 to about 10 g / 10 min, from about 0.5 to about 100 g / 10 min, from about 0.5 to about 25 g / 10 min, or from about 1 to about 15 g / 10 min.
[43] In some embodiments, the average molecular weight by weight (Mw) of the olefin polymer produced by the methods and processes disclosed here can be in the range of about 70,000 to about 600,000 g / mol, from about 100,000 to about from 600,000 g / mol, or from about 100,000 to about 500,000 g / mol. In other embodiments, Mw can be in the range of about 100,000 to about 400,000 g / mol, from about 150,000 to about 475,000 g / mol, from about 200,000 to about 500,000 g / mol, from 200,000 to about from 400,000 g / mol, from about 225,000 to about 400,000 g / mol, or from about 250,000 to about 450,000 g / mol. Appropriate ranges for the numerical average molecular weight (Mn) of the olefin polymer may include, but are not limited to, from about 5,000 to about 50,000 g / mol, from about 5,000 to about 40,000 g / mol, from about 5,000 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, from about 7,000 to about 30,000 g / mol, from about 8,000 to about 25,000 g / mol, from about 9,000 to about 25,000 g / mol, or from about 9,000 to about 22,000 g / mol. In addition, suitable ranges for the average molecular weight z (Mz) of the olefin polymer can include, but are not limited to, from about 700,000 to about 3,000,000 g / mol, from about 800,000 to about 3,000,000 g / mol mol, from about 1,000,000 to about 3,000,000 g / mol, from about 700,000 to about 2,500,000 g / mol, from about 800,000 to about 2,500,000 g / mol, from about 1,000,000 to about from 2,500,000 g / mol, from about 800,000 to about 2,000,000 g / mol, or from about 1,000,000 to about 2,000,000 g / mol.
[44] In some embodiments, the Mw / Mn ratio of the olefin polymer produced by the methods and processes disclosed here can be in the range of about 5 to about 50, about 5 to about 40, about 5 about 35, about 8 to about 30, about 10 to about 40, about 10 to about 35, about 12 to about 35, about 15 to about 35, about 12 to about 40, about 15 to about 30, about 18 to about 30, about 7 to about 45, about 8 to about 40, about 9 to about 35, about 10 to about 30, or about 12 to about 28. Likewise, in some embodiments, the Mz / Mw ratio of the olefin polymer can be a range of about 3 to about 7, about 3 to about 6, about 3 to about 5.5, about 3.5 to about 7, about 3.5 to about 6, about 3, 5 to about 5.5, about 3.5 to about 5, about 3.8 to about 6.5, about 3.8 to about 6, about 3.8 toabout 5.5, about 3.8 to about 5.3, about 3.8 to about 5, or about 3.8 to about 4.8.
[45] 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 metallocene catalyst component, the second metallocene catalyst component, or both catalyst components, during the double catalyst olefin polymerization process. In this mode, there is no “hydrogen added” to the reactor system.
[46] Although not required, however, hydrogen can be added to the polymerization reactor system in certain embodiments. Optionally, for example, the methods and processes provided here may further comprise a step of adding hydrogen to the polymerization reactor system to adjust a molecular weight parameter (for example, Mw, Mz, etc.) of the olefin polymer, and to adjust the melt index parameter (MI, HLMI, etc.) of the olefin polymer, or to adjust the molecular weight parameter and melt index parameter of the olefin polymer, if desired. Generally, the hydrogen addition step can decrease Mw, decrease Mz, increase MI or increase HLMI, or any combination thereof, of the polymer. In addition, the addition of hydrogen can also decrease the Mn of the polymer.
[47] In modalities where hydrogen is added to the polymerization reactor system, the addition of hydrogen can be kept substantially constant (for example, within +/- 20%.), For example, to produce a degree of particular polymer. For example, the ratio of hydrogen to the olefin monomer in the polymerization process can be controlled, often by the ratio of hydrogen feed to the olefin monomer entering the reactor. In addition, the addition of a comonomer (or comonomers) can be, and generally is, substantially constant throughout the course of the polymerization for a particular degree of copolymer. However, in other embodiments, it is contemplated that the monomer, comonomer (or comonomers), or hydrogen, or combinations thereof, may be periodically pulsed to the reactor, for example, in a similar manner to that employed in US Patent 5,739,220 and US Patent Publication 2004/0059070, the disclosures of which are incorporated herein by reference in their entirety.
[48] The 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 here. 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 the range of about 1: 100 to about 100: 1, about 1:50 about 50: 1, about 1:25 to about 25: 1, about 1:10 to about 10: 1, or about 1: 5 to about 5: 1. Accordingly, ranges suitable for the 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, about 1: 8 to about 8: 1, about 1: 5 to about 5: 1, about 1: 4 to about 4: 1, about 1: 3 to about 3: 1, about 1: 2 to about 2: 1, about 1: 1.8 to about 1.8: 1, 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.
[49] In the disclosed methods and processes, the MI (or HLMI, or both) of the olefin polymer may decrease, the Mw (or Mz, or both) of the olefin polymer may increase, or the melt index parameter may decrease and the molecular weight parameter may increase, as the amount of alcohol 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, the introduction of the alcohol compound into the polymerization reactor system can increase the weight ratio of the higher molecular weight component to the lowest molecular weight component.
[50] In addition, the addition of the alcohol compound to the polymerization reactor system may have substantially no effect on the peak molecular weight (Mp) of the lower molecular weight component of the olefin polymer. In addition or alternatively, in certain embodiments, the addition of the alcohol compound to the polymerization reactor system may 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 adding the alcohol compound is within +/- 20% of the peak molecular weight before the addition of the alcohol compound. In some embodiments, the peak molecular weights can be within +/- 10% or, alternatively, +/- 5%.
[51] For the production of a particular grade of an olefin polymer, with certain desired polymer properties, a target MI (or HLMI, or both) of the olefin polymer can be established. Thus, when the degree of the particular polymer is produced, the variables can be adjusted in order to achieve the target MI (or HLMI, or both). Accordingly, in some embodiments, the processes and methods provided here optionally may further comprise the steps of determining (or measuring) the MI (or HLMI, or both) of the olefin polymer, and then adjusting the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between the measured MI (or HLMI, or both) and the target MI (or HLMI, or both). As a representative example, if the measured MI (or HLMI, or both) is greater than the target MI (or HLMI, or both) for the production of a particular grade of olefin polymer, then the alcohol compound can be added in an appropriate amount to prepare the measured MI (or HLMI, both) equivalent to the target MI (or HLMI, or both). For example, the feed rate of the alcohol compound can be increased to reduce the MI (or HLMI, or both) of the olefin polymer.
[52] Likewise, for the production of a particular grade of an olefin polymer, with certain desired polymer properties, a target Mw (or Mz, or both) of the olefin polymer can be established. Thus, when the degree of the particular polymer is produced, the variables can be adjusted in order to achieve the target Mw (or Mz, or both). Accordingly, in some embodiments, the processes and methods provided here optionally may further comprise the steps of determining (or measuring) the Mw (or Mz, or both) of the olefin polymer, and then adjusting the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between the measured Mw (or Mz, or both) and the target Mw (or Mz, or both). As a representative example, if the measured Mw (or Mz, or both) is less than the target Mw (or Mz, or both) for the production of a particular grade of olefin polymer, then the alcohol compound can be added in an appropriate amount to prepare the measured Mw (or Mz, or both) equivalent to the target Mw (or Mz, or both). For example, the feed rate of the alcohol compound can be increased to reduce the Mw (or Mz, or both) of the olefin polymer.
[53] Consistent with modalities disclosed here, optionally, as needed, various polymerization conditions or process variables can be adjusted or controlled during the operation of a polymerization reactor system, and these conditions or variables can include, among others, temperature reaction time, reactor pressure, dwell time, catalyst system flow rate in the reactor, monomer (and comonomer, if used) flow rate in the reactor, olefin polymer exit rate, recycling rate, hydrogen flow (if used), reactor cooling status, slurry density, pump circulation force, and the like.
[54] In each of the methods and processes disclosed here, the melt index parameter (for example, MI, HLMI) of the olefin polymer may decrease, the molecular weight parameter (for example, Mw, Mz) of the olefin polymer it may increase, or the melt index parameter may decrease and the molecular weight parameter may increase, as the amount of alcohol compound added to the polymerization reactor system increases. ALCOHOL COMPOUNDS
[55] Alcohol compounds suitable for use here may include, for example, monools (monoalcohols), diols, triols, or polyols, as well as combinations thereof. In addition, suitable alcohol compounds can be straight or branched, and can be a primary alcohol, a secondary alcohol, or a tertiary alcohol. Typically, the alcohol compound can comprise a hydrocarbon alcohol, although this is not a requirement. For example, the alcohol compound can comprise an alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol, an arylalkyl alcohol, and the like, as well as combinations thereof.
[56] The number of carbon atoms in the alcohol compound is not particularly limited, although in some embodiments, the alcohol compound may comprise a C1 to C32 alcohol; alternatively, a C1 to C18 alcohol; alternatively, a C1 to C12 alcohol; alternatively, a C1 to C8 alcohol; alternatively, a C1 to C4 alcohol; alternatively, a C2 to C12 alcohol; or alternatively, a C2 to C6 alcohol. Representative and non-limiting examples of suitable alcohol compounds (for example, mono-ol compounds) can include the following: methanol, ethanol, propanol (for example, isopropanol, n-propanol), butanol (for example, n-butanol, isobutanol ), pentanol, hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol, phenol, benzyl alcohol, etc., as well as combinations thereof. In one embodiment, the alcohol compound can comprise methanol, ethanol, propanol (for example, isopropanol, n-propanol), butanol (for example, n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol, decanol, hexadecanol and related, or a combination thereof. In another embodiment, the alcohol compound can comprise cyclohexanol, phenol, benzyl alcohol, and the like, or a combination thereof. In yet another embodiment, the alcohol compound may comprise methanol, ethanol, propanol (for example, isopropanol, n-propanol), butanol (for example, n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol, and the like, or a combination of them. In yet another embodiment, the alcohol compound can comprise methanol, ethanol, propanol (for example, isopropanol, n-propanol), butanol (for example, n-butanol, isobutanol) and the like, or a combination thereof, or alternatively, ethanol, propanol (for example, isopropanol, n-propanol), butanol (for example, n-butanol, isobutanol), and the like, or a combination thereof.
[57] In certain embodiments, the alcohol compound may comprise a diol, illustrative examples of which may include, but are not limited to, methanediol, ethylene glycol, propylene glycol, butanediol (for example, 1,4-butanediol), pentanediol, octanediol, bisphenol A, and the like, as well as any combination thereof. In this sense, the alcohol compound can comprise ethylene glycol, propylene glycol, or both, in some modalities; alternatively, methanediol; alternatively, ethylene glycol; alternatively, propylene glycol; alternatively, butanediol (for example, 1,4-butanediol); alternatively, pentanediol; alternatively, octanodiol; or alternatively, bisphenol A.
[58] In other embodiments, the alcohol compound may comprise a triol, a polyol, or combinations thereof, illustrative examples of which may include, but are not limited to, glycerol, benzenotriol, erythritol, xylitol, mannitol, and the like, as well as combinations of the same. In this sense, the alcohol compound can comprise glycerol in some modalities; alternatively, benzenotriol; alternatively, erythritol; alternatively, xylitol; or alternatively, mannitol.
[59] The alcohol compound, in accordance with an embodiment disclosed herein, may have a boiling point of at least 60 ° C, such as, for example, a boiling point of at least 65 ° C, a boiling point of at least 70 ° C, or a boiling point of at least 85 ° C. Alcohol compounds having boiling points of at least 100 ° C, or at least 150 ° C, can be used as well. In yet another embodiment, the alcohol compound can have a boiling point in the range of 60 ° C to 400 ° C; alternatively, a boiling point in the range of 60 ° C to 350 ° C; alternatively, a boiling point in the range of 70 ° C to 300 ° C; alternatively, a boiling point in the range of 80 ° C and 275 ° C; alternatively, a boiling point in the range of 80 ° C to 250 ° C; alternatively, a boiling point in the range of 100 ° C to 350 ° C; alternatively, a boiling point in the range of 125 ° C to 350 ° C; alternatively, a boiling point in the range of 125 ° C to 300 ° C; or, alternatively, a boiling point in the range of 150 ° C and 275 ° C.
[60] The alcohol compound can be miscible with or soluble in a hydrocarbon solvent. For example, the alcohol compound may be miscible with or soluble in a hydrocarbon solvent comprising (or consisting essentially of, or consisting of) a C3 to C10 hydrocarbon; alternatively, a C3 to C10 aliphatic hydrocarbon; alternatively, a C3 to C8 aliphatic hydrocarbon; or, alternatively, an aliphatic C4 to C8 hydrocarbon. The aliphatic hydrocarbon can be cyclic or acyclic, and can be linear or branched, unless otherwise specified. Illustrative aliphatic hydrocarbon solvent may include, but is not limited to, propane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, heptane, octane, cyclohexane, cycloheptane, methylcyclohexane, methylcylheptane, and the like, including mixtures or combinations of the same.
[61] In addition, the alcohol compound may be miscible with or soluble in a hydrocarbon solvent comprising (or consisting essentially of, or consisting of) a C6 to C10 aromatic hydrocarbon or, alternatively, a C6 to C8 aromatic hydrocarbon. Illustrative aromatic hydrocarbon solvents may include, but are not limited to, benzene, toluene, xylene, ethylbenzene, and the like, including mixtures or combinations thereof.
[62] In one embodiment, the alcohol compound can be miscible with or soluble in propane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, heptane, octane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, benzene, toluene, xylene, ethylbenzene, or a mixture thereof. In another embodiment, the alcohol compound may be miscible with or soluble in propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or a mixture thereof. In yet another embodiment, the alcohol compound can be miscible with or soluble in propane; alternatively, isobutane; alternatively, n-butane; alternatively, n-pentane; alternatively, isopentane; alternatively, neopentane; alternatively, n-hexane; alternatively, heptane; alternatively, octane; alternatively, cyclohexane; alternatively, cycloheptane; alternatively, methylcyclohexane; alternatively, methylcycloheptane; alternatively, benzene; alternatively, toluene; alternatively, xylene; or alternatively, ethylbenzene.
[63] Depositors also contemplate that the alcohol compound can be miscible with or soluble in a mixed aliphatic hydrocarbon solvent ISOPAR®, such as, for example, ISOPAR® C, ISOPAR® E, ISOPAR® G, ISOPAR® H, ISOPAR ® L, ISOPAR® M, or a mixture of them.
[64] The alcohol compound, in certain embodiments, can be a liquid (under atmospheric pressure) at a temperature in the range of 50 ° C to 400 ° C; alternatively, in a range of 50 ° C to 200 ° C; alternatively, in a range of 50 ° C to 150 ° C; alternatively, in a range of 50 ° C to 125 ° C; alternatively, in a range of 75 ° C to 250 ° C; alternatively, in a range of 75 ° C to 175 ° C; alternatively, in a range of 75 ° C to 125 ° C; alternatively, alternatively, SYSTEMS in a range of 60 in a range of 60 ° C to 150 CATALYST ° C to oC. 250 oC; or
[65] In some embodiments, the dual catalyst system may comprise a first metallocene catalyst component and a second metallocene catalyst component, while in other embodiments, the dual catalyst system may comprise a first metallocene catalyst component, a second metallocene catalyst component, an activator, and a cocatalyst. The first metallocene catalyst component and the second metallocene catalyst component independently may comprise, for example, a transition metal (one or more than one) of Groups IIIB-VIIIB of the Periodic Table of the Elements. In one embodiment, the first metallocene catalyst component and the second metallocene catalyst component can independently 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 may independently 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 can independently comprise titanium, or zirconium, or hafnium, alone or in combination.
[66] 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 to them, the first metallocene catalyst component can comprise a metallocene without a bridge; alternatively, a hafnium or zirconium based metallocene compound, or a dinuclear metallocene compound based on zirconium / hafnium or hafnium, zirconium without bridge; alternatively, a hafnium or zirconium-based metallocene compound without bridging containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl and one indenyl group; alternatively, a bridged zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl and one indenyl group. Illustrative and non-limiting examples of bridged metallocene compounds (for example, with zirconium or hafnium) that can be used in catalyst systems consistent with the modalities of the present invention are described in US Patents 7,199,073, 7,226,886, 7,312. 283, and 7,619,047, whose disclosures are incorporated here as a reference in their entirety.
[67] 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 used as the first metallocene compound can include, among others, the following (Ph = phenyl):


[68] In addition, the first metallocene catalyst component may comprise a bridged dinuclear metallocene as described in US Patents 7,919,639 and 8,080,681; whose disclosures are incorporated here as a reference in their entirety. The first metallocene catalyst component may comprise a dinuclear metallocene compound based on zirconium / hafnium or hafnium, zirconium without bridging. For example, the first metallocene catalyst component may comprise a bridged zirconium-based homodinuclear metallocene compound, or a bridged hafnium-based homodinuclear metallocene compound, or a zirconium / hafnium-based heterodinuclear metallocene compound , zirconium without bridging (ie, a dinuclear compound with two hafniums, or two zirconia, or one zirconium and one hafnium). Representative non-limiting dinuclear compounds may include the following:

and the like, as well as combinations thereof.
[69] While not limited to these, the second metallocene catalyst component may comprise a bridged metallocene compound, for example, with titanium, zirconium, or hafnium, such as a bridged zirconium-based metallocene compound with a fluorenyl group, and no aryl groups in the bridged group, or a zirconium-based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and no aryl groups in the bridge group. Such bridged metallocenes, in some embodiments, may contain an alkenyl substituent (for example, a terminal alkenyl) in the bridge group, in a cyclopentadienyl-type group (for example, a cyclopentadienyl group, a fluorenyl group, etc.), or bridge group and the cyclopentadienyl group. In another embodiment, the second metallocene catalyst component may comprise a zirconium or hafnium-based metallocene compound with a fluorenyl group, and an aryl group in the bridge group; alternatively, a metallocene compound based on zirconium or bridged hafnium with a cyclopentadienyl group and a fluorenyl group, and an aryl group in the bridge group; alternatively, a zirconium-based metallocene compound with a fluorenyl group, and an aryl group in the bridge group; or alternatively, a hafnium-based metallocene compound bridged with a fluorenyl group, and an aryl group in the bridge group. In these and other embodiments, the aryl group in the bridge group can be a phenyl group. Optionally, these bridged metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl) in the bridge group, in a cyclopentadienyl group, or in the bridge groups and the cyclopentadienyl group. Illustrative and non-limiting examples of bridged metallocene compounds (for example, with zirconium or hafnium) that can be used in catalyst systems consistent with the modalities of the present invention are described in US Patents 7,026,494, 7,041,617, 7,226. 886, 7,312,283, 7,517,939, and 7,619,047; whose disclosures are incorporated here as a reference in their entirety.
[70] 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, hafnium, or both. Representative and non-limiting examples of metallocene compounds that can be used as the second metallocene compound may include, but are not limited to, the following (Ph = phenyl, Me = methyl, and t-Bu = tert-butyl):

and the like, as well as combinations thereof.
[71] In some embodiments, the dual catalyst system may comprise an activator. For example, the dual catalyst system can comprise a first metallocene catalyst component, a second metallocene catalyst component, and an activator, such as a support activator, an aluminoxane compound, an organoboro or organoborate compound, a compound ionizing ion, and the like, or any combination thereof. The catalyst system can contain one or more of an activator.
[72] In one embodiment, the dual catalyst system may comprise an aluminoxane compound, an organoboro or organoborate compound, an ionizing ionic 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; whose disclosures are incorporated here as a reference in their entirety. In another embodiment, the dual catalyst system can comprise an aluminoxane compound. In yet another embodiment, the double catalyst system can comprise an oraganoboro or organoborate compound. In yet another embodiment, the dual catalyst system can comprise an ionizing ionic compound.
[73] 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, US Patents 7,294,599 and 7,601,665; whose disclosures are incorporated here as a reference in their entirety.
[74] The solid oxide used to produce the support activator can 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, solid oxide can comprise oxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr.
[75] In this regard, suitable examples of solid oxide materials that can be used to form the activator-supports can include, but are not limited to, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3 , Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including mixed oxides thereof, and combinations thereof. This includes cogels or coprecipitate from different solid oxide materials. The solid oxide may 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 of a 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 a support activator, alone or in combination, may include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina -barium, silica-boron, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide used here 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.
[76] Accordingly, in one embodiment, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boron, zinc oxide, any oxides mixtures thereof, or any combination thereof. In another embodiment, the solid oxide may comprise silica, alumina, titania, zirconia, magnesia, boron, zinc oxide, any mixed oxides thereof, or any combination thereof. In yet another aspect, the solid oxide may comprise silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boron or any combination thereof. In yet another embodiment, the solid oxide may comprise silica; alternatively, alumina; alternatively, silica-alumina; or alternatively, silica-coated alumina.
[77] The silica-alumina that can be used normally can have an alumina content of about 5 to about 95% by weight. In one embodiment, the silica-alumina alumina content 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, in which the alumina content of these silica-alumina materials can normally vary 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 may comprise alumina without silica, and according to another embodiment, the solid oxide component may comprise silica without alumina. In addition, 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.
[78] The electron withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide after treatment (compared to the solid oxide that is not treated with at least one electron withdrawing anion. ). According to one embodiment, the electron-withdrawing component may be an electron-withdrawing anion derived from a salt, acid, or other compound, such as a volatile organic compound, which serves as a source or precursor to 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, fluorozirconate, fluorotitanate, phosphonate mixtures and compounds themselves. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions can also be employed. It is envisaged that the electron withdrawing anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate and the like, or any combination thereof, in some embodiments provided here. In other embodiments, the electron-withdrawing anions may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, triflate, fluozirconate, fluorotitanate, and the like, or any combination thereof.
[79] 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, alumina coated with fluorinated silica, alumina coated with sulfated silica, alumina coated with silica phosphate, and the like, or mixtures or combinations thereof. In another embodiment, the dual catalyst system can comprise a support activator, and the support activator can comprise a fluorinated solid oxide, a sulfated solid oxide, or a combination thereof. In yet 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 silica-zirconia, fluorinated silica-coated alumina. , alumina coated with sulfated silica and the like, as well as any mixture or combination thereof.
[80] As described here, the alcohol compound can be added to the polymerization reactor system (for example, in a polymerization reactor) alone, with a conveyor, with the double catalyst system, etc., and the amount of the alcohol compound added to the reactor system is not particularly limited, while the amount of alcohol compound added to the reactor system is sufficient to impact at least one of MI, HLMI, Mw and Mz of the olefin polymer as described here, and does not negatively impact the catalytic activity or polymer production rate significantly (for example, 20% + reduced catalytic activity, polymer production rate, or both). However, while not limited to them, the amount of alcohol compound added can normally be in a range of moles of hydroxyl groups (-OH) of the alcohol compound to the weight (in grams) of the activator (for example, an activator- support comprising a solid oxide treated with an electron withdrawing anion) from about 1: 10,000 to about 1:10. This range of weight ratios is based on the respective amounts of the hydroxyl groups of the alcohol compound and the activator weight (for example, activator-support) fed into the reactor system (for example, in a polymerization reactor). As a non-limiting example of a 1: 1000 ratio, in a continuous polymerization reactor system, the total amount of an activator, such as a support activator, fed into the reactors per time interval can be "W" g / hour ; thus, the amount of alcohol compound fed into the reactors would be equal to "0.001W" moles / hour (moles of hydroxyl groups) for a ratio of 1: 1000.
[81] In some embodiments, this ratio (moles of hydroxyl groups of the alcohol compound to the weight of the activator, such as a support activator) can be in the range of about 1: 10,000 to about 1:10, of about from 1: 5,000 to about 1:10, from about 1: 2,500 to about 1:10, from about 1: 10,000 to about 1:50, from about 1: 5,000 to about 1:50, from about 1: 5,000 to about 1: 100, from about 1: 5,000 to about 1: 250, or from about 1: 5,000 to about 1: 500. In particular embodiments considered here, the ratio can be in the range of about 1: 7,000 to about 1: 100, from about to about 1: 2,500 to about 1: 250, from about 1: 1,500 to about from 1: 250, from about 1: 1,500 to about 1: 500, from about 1: 2,000 to about 1: 1,000, or from about 1: 1,500 to about 1: 1,000.
[82] Commonly used polymerization cocatalysts that can be used in the dual catalyst system may include, but are not limited to, metal alkyl, or organometal, cocatalysts, with the metal, for example, aluminum. The dual catalyst systems provided herein may comprise a cocatalyst, or a combination of cocatalysts. While not limited to them, representative aluminum compounds (eg, organoaluminium compounds) can include trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylaluminium , diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminium chloride, and the like, as well as any combination thereof. Thus, a dual catalyst system provided herein can comprise a first metallocene catalyst component, a second metallocene catalyst component, an activator, and a cocatalyst. In one embodiment, the cocatalyst may comprise an organoaluminium compound, such as triethyl aluminum or triisobutylaluminium, while the activator may comprise a fluorinated solid oxide or a sulfated solid oxide, representative examples of which may include fluorinated alumina, sulfated alumina, fluorinated silica-fluorinated alumina, sulfated silica-alumina, fluorinated silica-zirconia, alumina coated with fluorinated silica, alumina coated with sulfated silica, as well as any combination thereof.
[83] The amount of alcohol compound added to the reactor system, based on the amount of cocatalyst, is not particularly limited, while the amount of alcohol compound added to the reactor system is sufficient to impact at least one MI , HLMI, Mw, and Mz of the olefin polymer as described here, and does not negatively impact the catalytic activity or polymer production rate significantly (e.g. 20% + reduction in catalytic activity, polymer production rate, or both ). As one skilled in the art would readily understand, an excess of the alcohol compound, compared to the cocatalyst component of the dual catalyst system, can drastically reduce catalytic activity and the rate of polymer production and, eventually, can "kill" the reaction. Therefore, while not limited to them, the amount of the added alcohol compound can normally be in a range of moles of hydroxyl groups (-OH) from the alcohol compound to the moles of the cocatalyst (for example, an organoaluminium compound) of about 0.05: 1 to about 0.9: 1. This molar ratio is based on the respective amounts of the hydroxyl groups of the alcohol compound and the cocatalyst fed into the reactor system (for example, in a polymerization reactor). As a non-limiting example of a 0.5: 1 molar ratio, in a continuous polymerization reactor system, the amount of the cocatalyst component (for example, an organoaluminium compound) fed into the time interval reactors can be "Z "moles / hour; thus, the amount of alcohol compound fed into the reactors would be equal to "0.5Z" moles / hour (moles of hydroxyl groups) for a molar ratio of 0.5: 1.
[84] In some embodiments, the molar ratio (moles of hydroxyl groups of the alcohol compound to moles of cocatalyst, such as organoaluminium compounds) can be in the range of about 0.05: 1 to about 0.85: 1 , from about 0.1: 1 to about 0.9: 1, from about 0.1: 1 to about 0.85: 1, from about 0.05: 1 to about 0.8: 1, from about 0.1: 1 to about 0.8: 1, from about 0.05: 1 to about 0.75: 1, from about 0.1: 1 to about 0.75 : 1, from about 0.15: 1 to about 0.85: 1, or from about 0.15: 1 to about 0.75: 1. In particular embodiments considered here, the molar ratio can be in the range of about 0.2: 1 to about 0.9: 1, from about to about 0.2: 1 to about 0.8: 1 , from about 0.2: 1 to about 0.7: 1, from about 0.2: 1 to about 0.6: 1, from about 0.1: 1 to about 0.6: 1, or from about 0.25: 1 to about 0.75: 1. OLEFINE MONOMERS AND OLEFINE POLYMERS
[85] Olefin monomers contemplated here typically include olefin compounds having 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 reactions, terpolymerization, etc., using an olefin monomer with at least one different olefinic compound. For example, the resulting copolymers, ethylene terpolymers, etc., can generally 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.
[86] Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins may be used. For example, typical unsaturated compounds that can be polymerized to produce olefin polymers can include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene , 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, four normal octenes (for example, 1-octene), four normal nonenos, five normal decenos, 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 here. Styrene can also be used as a monomer or as 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.
[87] 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 (for example, a C2-C20 α-olefin, a α-olefin C3-C20, 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, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene , 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, or combinations thereof. According to another embodiment, the comonomer may comprise an α-olefin (for example, 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.
[88] Generally, the amount of comonomer introduced into a polymerization reactor system to produce a copolymer can be from about 0.01 to about 50 weight percent of the comonomer based on the total weight of the monomer and comonomer. According to another embodiment, the amount of comonomer introduced into a polymerization reactor can be from about 0.01 to about 40 weight percent 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 0.01 to about 35 weight percent 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 about 0.5 to about 20 weight percent of the comonomer based on the total weight of the monomer and comonomer.
[89] Although not intended to be bound by this theory, where branched, substituted, or functionalized olefins are used as reagents, it is believed that a steric deterrent can prevent and / or delay the polymerization reaction. Thus, branched and / or cyclic portions of the olefin removed from the carbon-carbon double bond would not be expected to prevent the reaction in the way that the same substituents as the same olefin substituents located closest to the carbon-carbon double bond would.
[90] According to one embodiment, at least one monomer / reagent can be ethylene, so the polymerization reaction can be a homopolymerization involving only ethylene, or a copolymerization with an acyclic, cyclic, terminal, internal, linear, branched, olefin. replaced or unsubstituted. In addition, the methods disclosed herein are intended for olefin to also include diolefin compounds which include, but are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and the like.
[91] Olefin polymers included here can include any polymer (or oligomer) produced from any olefin monomer (and optional comonomers) described here. For example, the olefin polymer may comprise an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer (eg, 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. In addition, 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 may have a unimodal molecular weight distribution. POLYMERIZATION REACTOR SYSTEMS
[92] 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 monomers and comonomers (one or more than one comonomer) of olefin to produce homopolymers, copolymers, terpolymers, and the like. The various types of polymerization reactors include those that can be referred to as a batch reactor, slurry reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations of themselves. Suitable polymerization conditions are used for the various types of reactor. 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 can also include direct partial or complete recycling of unreacted monomer, unreacted comonomer, or diluent.
[93] A polymerization reactor system may 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 may 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 phases in at least two separate polymerization reactors, interconnected by a transfer system, making it possible to transfer the polymers resulting from the first polymerization reactor in the second reactor. The desired polymerization conditions in one of the reactors may differ from the operational conditions of the other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization. Various reactor systems can include any combination, including but not limited to, several loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of phase reactors with handle or high pressure gas. The various reactors can be operated in series, in parallel, or both.
[94] According to one 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 fed continuously to a loop reactor where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of a monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent. The effluent from the reactor can be evaporated to remove the solid polymer from the liquids comprising the diluent, monomer, comonomer, etc. Various technologies can be used for this separation step including, but not limited to, vaporization which can include any combination of heat addition and pressure reduction, separation by cyclonic action on a cyclone or hydrocyclone, or separation by centrifugation.
[95] A typical pulp polymerization process (also known as the particle shape 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 its entirety.
[96] Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some loop polymerization reactions can occur under bulk conditions where no thinner is used. An example is polymerization of the propylene monomer as disclosed in US Patents 5,455,314, which is incorporated by reference in its entirety.
[97] According to another embodiment, the polymerization reactor system may comprise at least one gas phase reactor (for example, a fluidized bed reactor). These systems can employ a continuous recycling stream that contains one or more monomers continuously recycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product can be removed from the reactor and new or fresh monomer can be added to replace the polymerized monomer. These gas phase reactors can comprise a process for multi-stage polymerization of olefin gas phase, in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a polymer containing catalyst formed in a first catalyst zone. polymerization to a second polymerization zone. A 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.
[98] 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 several zones where fresh monomer, initiators, or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a reactor zone. Starters, catalysts, catalyst components, etc. they can be dragged in a gaseous flow and introduced into another zone of the reactor. Gaseous streams can be mixed for polymerization. Heat and pressure can be used properly to obtain optimal polymerization reaction conditions.
[99] 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 proper stirring or other means. A carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer / comonomer can be brought in the vapor phase 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 polymer solution in a reaction medium. Stirring can be used to obtain the best temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat from polymerization.
[100] The polymerization reactor system may further comprise any combination of at least one feedstock feeder system, at least one feeder system for catalyst or catalyst components, and at least one polymer recovery system. Suitable reactor systems may also comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, refrigeration reactor, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis, and process control. Depending on the desired properties of the olefin polymer, hydrogen can be added to the polymerization reactor as needed (for example, continuously, pulsed, etc.) and, as discussed above.
[101] The polymerization conditions that are controlled for efficiency and to provide the desired polymer properties can include temperature, pressure, and the concentrations of various reagents. The polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature, according to the Gibbs free energy equation. This typically includes about 60 ° C to about 280 ° C, for example, or 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.
[102] Appropriate pressures will also vary according to the reactor and type of polymerization. The pressure for liquid phase polymerization in a loop reactor can typically be 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. Operating above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages. EXAMPLES
[103] Modalities of the invention are further illustrated by the following examples, which should not be considered in order to impose limitations on the scope of that invention described here. Various other aspects, modalities, modifications, and equivalents thereof, which, after reading the description here, may suggest to a person skilled in the art without departing from the spirit of the present invention or the scope of the appended claims.
[104] 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.
[105] 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 at 1 mL / min, and the polymer solution concentrations were in the range of 1.0-1.5 mg / mL, depending on the molecular weight. Sample preparation was carried out at 150 ° C for nominally 4 hr with occasional and gentle agitation, before the solutions were transferred to sample vials for injection. The integral calibration method was used to deduce the molecular weights and molecular weight distributions using polyethylene resin Chevron Phillips Chemicals Company’s HDPE, MARLEX BHB5003, as a broad standard. The integral standard table was predetermined in a separate experiment with SEC-MALS. Mn is the average molecular weight, Mw is the average molecular weight by weight, Mz is the average molecular weight z, and Mp is the peak molecular weight.
[106] Sulfated alumina activator-supports were prepared as follows. Bohemite was obtained from W.R. Grace and Company, under the name "Alumina A" and having a surface area of about 300 m2 / g and a pore volume of about 1.3 ml / g. This material was obtained as a powder having an average particle size of about 100 microns. This material was impregnated 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 calcinate the resulting powder mixture, the material was fluidized in a dry air flow at about 550 ° C for about 6 hours. After that, the sulfated alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere. EXAMPLES 1-4 Impact of the addition of isopropyl alcohol on the melt index and molecular weight parameters of an ethylene / 1-hexene copolymer.
[107] The polymerization experiments of Examples 1-4 were carried out in a one-gallon (3.8-L) stainless steel reactor 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:

[108] Approximately 2 mg of MET-A and 2 mg of MET-B (a 1: 1 weight ratio) were used in Examples 1-4, and the metallocene solutions MET-A and MET-B were premixed before being loaded into the reactor.
[109] The polymerization experiments were carried out as follows. First, 0.6 mmol of triisobutylaluminum (TIBA), 300 mg of sulfated alumina, and the premixed metallocene solution containing MET-A and MET-B were added in that order through a loading port while slowly venting steam of isobutane. The loading door 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 and isopropyl alcohol were 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 for the specified weight ratio to maintain the target pressure of 420 psig of pressure for the duration of 45 minutes of each polymerization experiment. The reactor was maintained at the desired reaction temperature throughout the experiment by an automated heating-cooling system.
[110] Table I summarizes the amount of isopropyl alcohol added, the amount of polymer produced, and the melt flow and molecular weight parameters for the polymers of Examples 1-4. As shown in Table I, and unexpectedly, the addition of isopropyl alcohol decreased MI and HLMI, and increased Mw and Mz of the polymer. In addition, the addition of isopropyl alcohol decreased the polymer's Mz / Mw ratio. Furthermore, and quite surprising, the addition of isopropyl alcohol did not significantly impact the amount of polymer produced (or the catalytic activity).
[111] The impact of the addition of isopropyl alcohol on the molecular weight distributions (amount of polymer versus the logarithm of molecular weight) of the polymers of Examples 1-4 is illustrated graphically in the figure. As shown in the figure, and unexpectedly, the addition of isopropyl alcohol increased the weight ratio of the highest molecular weight component (HMW) to the lowest molecular weight component (LMW); relatively more higher molecular weight material was produced. In addition, the peak molecular weight of the lowest molecular weight component and the peak molecular weight of the highest molecular weight component were not substantially affected by the addition of isopropyl alcohol.


[112] The invention is described above with reference to various aspects and modalities, and specific examples. Many variations will appear to those skilled in the art in the light of the detailed description above. All of these 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 (embodiments are described as "comprising" but, alternatively, may "consist essentially of" or "consist of"):
[113] Mode 1. Method for controlling the polymerization reaction in a polymerization reactor system, the method comprising: (i) contacting a double catalyst system with an olefin monomer and an optional olefin comonomer in the reactor system polymerization under polymerization conditions to produce an olefin polymer, wherein the dual catalyst system comprises a first metallocene catalyst component, a second metallocene catalyst component, an activator, and a cocatalyst; and (ii) introducing an amount of an alcohol compound into the polymerization reactor system to reduce a melt index parameter (for example, MI, HLMI, etc.) to increase a molecular weight parameter (for example, Mw, Mz, etc.), or to reduce a melt index parameter and increase a molecular weight parameter of the olefin polymer.
[114] Mode 2. A process for producing an olefin polymer with a target melt index parameter (eg MI, HLMI, etc.), a target molecular weight parameter (eg Mw, Mz, etc. ), or a target melt index parameter and a target molecular weight parameter, the process comprising: (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, a second metallocene catalyst component, an activator, and a cocatalyst; and (b) controlling an amount of an alcohol compound introduced into the polymerization reactor system to produce the olefin polymer with the target melt index parameter (e.g., MI, HLMI, etc.), the molecular weight parameter target (e.g., Mw, Mz, etc.), or the target melt index parameter and the target molecular weight parameter.
[115] Mode 3. The method or process defined in mode 1 or 2, wherein the alcohol compound comprises any alcohol compound disclosed herein, for example, a monool, a diol, a triol, a polyol, etc. , as well as combinations thereof.
[116] Mode 4. The method or process defined in any of modalities 1-3, wherein the alcohol compound comprises a hydrocarbon alcohol, for example, an alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol, an arylalkyl alcohol, etc., as well as combinations thereof.
[117] Mode 5. The method or process defined in any of modalities 1-4, wherein the alcohol compound comprises a C1 to C32 alcohol, for example, a C1 to C18 alcohol, a C1 to C8 alcohol, a C1 to C4 alcohol, etc.
[118] Modality 6. The method or process defined in any of modalities 1-3, wherein the alcohol compound comprises any mono-ol disclosed herein, for example, methanol, ethanol, propanol (for example, isopropanol, n- propanol), butanol (e.g. n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol, phenol, benzyl alcohol, etc., as well as combinations thereof.
[119] Mode 7. The method or process defined in any of the modalities 1-3, wherein the alcohol compound comprises any diol disclosed herein, for example, methanediol, ethylene glycol, propylene glycol, butanediol (for example, 1, 4-butanediol), pentanediol, octanediol, bisphenol A, etc., as well as combinations thereof.
[120] Mode 8. The method or process defined in any of the modalities 1-3, wherein the alcohol compound comprises any triol disclosed herein, for example, glycerol, benzenotriol, etc., as well as combinations thereof.
[121] Mode 9. The method or process defined in any of the modalities 1-3, wherein the alcohol compound comprises any polyol disclosed herein, for example, erythritol, xylitol, mannitol etc., as well as combinations thereof.
[122] Mode 10. The method or process defined in any of modalities 1-9, wherein the alcohol compound has a boiling point in any range disclosed here, for example, at least 60 ° C, at least 100 ° C, in a range of 60 ° C to 400 ° C, in a range of 100 ° C to 350 ° C, etc.
[123] Mode 11. The method or process defined in any of modalities 1-10, wherein the alcohol compound is a liquid at a temperature in any range disclosed here, for example, from 50 ° C to 200 ° C, from 50 ° C to 150 ° C, from 75 ° C to 250 ° C, from 75 ° C to 175 ° C, etc.
[124] Mode 12. The method or process defined in any of modalities 1-12, wherein the alcohol compound is miscible with or soluble in any C3 to C10 hydrocarbon solvent disclosed here, for example, propane, cyclohexane, isobutane , n-butane, n-pentane, isopentane, neopentane, n-hexane, benzene, etc., as well as mixtures thereof.
[125] Mode 13. The method or process defined in any of modalities 1-12, wherein the catalyst system comprises any (one or more) first metallocene catalyst component, any (one or more) second catalyst component metallocene, any (one or more) activators and any (one or more) cocatalysts disclosed here.
[126] Mode 14. The method or process defined in any of modalities 1-13, wherein the activator comprises an aluminoxane compound.
[127] Mode 15. The method or process defined in any one of the modalities 1-13, in which the activator comprises an organoboro or organoborate compound.
[128] Mode 16. The method or process defined in any of modalities 1-13, in which the activator comprises an ionizing ionic compound.
[129] Mode 17. The method or process defined in any of modalities 1-13, wherein the activator comprises a support activator comprising a solid oxide treated with an electron withdrawing anion, for example, a support activator comprising any solid oxide treated with any electron-withdrawing anion disclosed here.
[130] Mode 18. The method or process defined in mode 17, in which the support activator comprises a fluorinated solid oxide, a sulfated solid oxide, or a combination thereof.
[131] Modality 19. The method or process defined in modality 17, in which the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, barium, 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, fluorozirconate, fluorotitanate, phospho-tungstate, or combinations thereof.
[132] Mode 20. The method or process defined in mode 17, in which 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, alumina coated with fluorinated silica, alumina coated with sulfated silica, alumina coated with phosphate silica, or any combination of the same.
[133] Mode 21. The method or process defined in mode 17, in which the support activator comprises fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, alumina coated with fluorinated silica, alumina coated with sulfated silica, or any combination thereof.
[134] Mode 22. The method or process defined in any of modalities 1-21, in which the amount of the alcohol compound introduced into the polymerization reactor system is in any range of molar ratios disclosed here, based on the moles of groups hydroxyl (-OH) of the alcohol compound for the total moles of the first metallocene catalyst component and the second metallocene catalyst component, for example, from about 10: 1 to about 1000: 1, from about 20: 1 to about 500: 1, from about 25: 1 to about 100: 1, etc.
[135] Mode 23. The method or process defined in any of modalities 1-22, in which the amount of alcohol compound introduced into the polymerization reactor system is in any range of reasons described here, based on the moles of groups hydroxyl (-OH) of the alcohol compound for the weight of the activator in grams, for example, from about 1: 10,000 to about 1:10, from about 1: 5,000 to about 1: 100, from about 1 : 1,500 to about 1: 500, etc.
[136] Modality 24. The method or process defined in any of modalities 1-23, wherein the cocatalyst comprises any organoaluminium compound disclosed here.
[137] Modality 25. The method or process defined in modality 24, in which the organoaluminium compound comprises trimethylalumin, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n- octyl aluminum, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum chloride, or any combination thereof.
[138] Modality 26. The method or process defined in modality 24 or 25, in which the organoaluminium compound comprises triethylaluminium.
[139] Modality 27. The method or process defined in modality 24 or 25, in which the organoaluminium compound comprises triisobutylaluminium.
[140] Mode 28. The method or process defined in any of the modes 24-27, in which the activator comprises a fluorinated solid oxide, a sulfated solid oxide, or a combination thereof.
[141] Mode 29. The method or process defined in any of the modes 24-28, in which the activator comprises fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, silica-coated alumina fluorinated, alumina coated with sulfated silica, or any combination thereof.
[142] Mode 30. The method or process defined in any of modalities 1-29, in which the amount of the alcohol compound introduced into the polymerization reactor system is in any range of molar ratios disclosed here, based on the moles of groups hydroxyl (-OH) of the alcohol compound for the total moles of the cocatalyst, for example, from about 0.05: 1 to about 0.9: 1, from about 0.1: 1 to about 0.8 : 1, from about 0.2: 1 to about 0.7: 1, etc.
[143] Mode 31. The method or process defined in any of modalities 1-30, in which 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.
[144] Mode 32. The method or process defined in any of modalities 1-31, in which the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof .
[145] Modality 33. The method or process defined in any of modalities 1-32, in which the polymerization reactor system comprises a loop paste reactor.
[146] Mode 34. The method or process defined in any of modalities 1-33, in which the polymerization reactor system comprises a single reactor.
[147] Mode 35. The method or process defined in any of modalities 1-33, in which the polymerization reactor system comprises 2 reactors.
[148] Mode 36. The method or process defined in any of modalities 1-33, in which the polymerization reactor system comprises more than 2 reactors.
[149] Modality 37. The method or process defined in any of modalities 1-36, wherein the olefin monomer comprises a C2-C20 olefin.
[150] Mode 38. The method or process defined in any one of modalities 1-37, wherein the olefin monomer and optional olefin comonomer independently comprise a C2-C20 alpha-olefin.
[151] Mode 39. The method or process defined in any one of modalities 1-38, wherein the olefin monomer comprises ethylene.
[152] Mode 40. The method or process defined in any of modalities 1-39, in which the catalyst system is contacted with ethylene and a C3-C10 alpha-olefin comonomer.
[153] Mode 41. The method or process defined in any of modalities 1-40, in which the catalyst system is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a mixture of the same.
[154] Mode 42. The method or process defined in either mode 1-41, wherein the olefin polymer in step (ii) or step (b) (or both) has a multimodal molecular weight distribution.
[155] Mode 43. The method or process defined in either mode 1-41, in which the olefin polymer in step (ii) or step (b) (or both) has a bimodal molecular weight distribution.
[156] Mode 44. The method or process defined in either mode 1-41, wherein the olefin polymer in step (ii) or step (b) (or both) has a unimodal molecular weight distribution.
[157] Mode 45. The method or process defined in any of modalities 1-44, wherein the melt index (MI) of the olefin polymer in step (ii) or step (b) (or both) is in any range disclosed here, for example, from 0 to about 25 g / 10 min, from 0 to about 1 g / 10 min, from 0 to about 0.5 g / 10 min, etc.
[158] Mode 46. The method or process defined in any of modalities 1-45, wherein the high-charge melt index (HLMI) of the olefin polymer in step (ii) or step (b) (or both) is in any range disclosed here, for example, from 0 to about 100 g / 10 min, from about 0.1 to about 50 g / 10 min, from about 0.5 to about 25 g / 10 min , etc.
[159] Mode 47. The method or process defined in any of modalities 1-46, in which the numerical average molecular weight (Mn) of the olefin polymer in step (ii) or step (b) (or both) is in any range disclosed here, for example, from about 5,000 to about 40,000 g / mol, from about 6,000 to about 25,000 g / mol, from about 9,000 to about 22,000 g / mol, etc.
[160] Mode 48. The method or process defined in any of modalities 1-47, wherein the average molecular weight (Mw) of the olefin polymer in step (ii) or step (b) (or both) is in any range disclosed here, for example, from about 100,000 to about 600,000 g / mol, from about 200,000 to about 500,000 g / mol, or from about 225,000 to about 400,000 g / mol.
[161] Mode 49. The method or process defined in any one of modalities 1-48, in which the molecular weight of the medium z (Mz) of the olefin polymer in step (ii) or step (b) (or both) is in any range disclosed here, for example, from about 700,000 to about 3,000,000 g / mol, from about 800,000 to about 2,500,000 g / mol, or from about 1,000,000 to about 2,000,000 g / mol.
[162] Mode 50. The method or process defined in any of modalities 1-49, in which the Mw / Mn ratio of the olefin polymer in step (ii) or step (b) (or both) is in any disclosed range here, for example, from about 10 to about 40, from about 12 to about 35, from about 15 to about 35, from about 15 to about 30, etc.
[163] Mode 51. The method or process defined in any of modalities 1-50, in which the Mz / Mw ratio of the olefin polymer in step (ii) or step (b) (or both) is in any disclosed range here, for example, from about 3 to about 7, from about 3.5 to about 7, from about 3.5 to about 6, from about 3.8 to about 5.5, etc. .
[164] Mode 52. The method or process defined in any of modalities 1-51, wherein the olefin polymer is an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, or an ethylene copolymer / 1-octene.
[165] Mode 53. The method or process defined in any of modalities 1-52, wherein the olefin polymer is an ethylene / 1-hexene copolymer.
[166] Mode 54. The method or process defined in any of modalities 1-53, wherein the first metallocene catalyst component and the second metallocene catalyst component independently comprise chromium, vanadium, titanium, zirconium, hafnium, or a combination of them.
[167] Mode 55. The method or process defined in any of modalities 1-54, wherein the first metallocene catalyst component and the second metallocene catalyst component independently comprise titanium, zirconium, hafnium, or a combination thereof .
[168] Modality 56. The method or process defined in any of modalities 1-55, wherein the first metallocene catalyst component comprises any first metallocene catalyst component disclosed herein, for example, a bridged metallocene compound, a dinuclear metallocene compound without a bridge, etc.
[169] Modality 57. The method or process defined in any of modalities 1-56, wherein the first metallocene catalyst component comprises zirconium.
[170] Modality 58. The method or process defined in any of modalities 1-57, wherein the second metallocene catalyst component comprises any second metallocene catalyst component disclosed herein, for example, a bridged metallocene compound, etc.
[171] Mode 59. The method or process defined in any of modalities 1-58, wherein the second metallocene catalyst component comprises zirconium, hafnium, or both.
[172] Mode 60. The method or process defined in any of modalities 1-59, wherein a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component is substantially constant, for example, for a degree of particular polymer.
[173] Mode 61. The method or process defined in any of modalities 1-59, further comprising a step of adjusting a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component.
[174] Mode 62. The method or process defined in any of modalities 1-61, and that the polymerization conditions comprise a polymerization reaction temperature in a range of 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).
[175] Mode 63. The method or process defined in any of modalities 1-62, in which the polymerization conditions are substantially constant, for example, for a particular degree of polymer.
[176] Mode 64. The method or process defined in any one of modalities 1-62, further comprising a step of adjusting at least one polymerization condition, for example, temperature, pressure, residence time, etc.
[177] Mode 65. The method or process defined in any of modalities 1-64, in which no hydrogen is added to the polymerization reactor system.
[178] Mode 66. The method or process defined in any of modalities 1-64, in which hydrogen is added to the polymerization reactor system, and the addition of hydrogen is substantially constant, for example, for a particular degree of polymer .
[179] Mode 67. The method or process defined in any of modalities 1-64, further comprising a step of adding hydrogen to the polymerization reactor system to adjust the Mw or Mz (or Mw and Mz) of the polymer.
[180] Mode 68. The method or process defined in any of modalities 1-64, further comprising a step of adding hydrogen to the polymerization reactor system to adjust the polymer's MI or HLMI (or MI and HLMI).
[181] Mode 69. The method or process defined in any of the modalities 66-68, in which the step of adding hydrogen decreases Mw, decreases Mz, increases MI, or increases the polymer's HLMI, as well as any combination of the same.
[182] Mode 70. The method or process defined in any of modalities 1-69, further comprising the steps of determining (or measuring) the MI, and adjusting the amount of the alcohol compound introduced into the polymerization reactor system based on in the difference between the measured IM and the target IM.
[183] Mode 71. The method or process defined in any of modalities 1-70, further comprising the steps of determining (or measuring) the HLMI, and adjusting the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between the measured HLMI and the target HLMI.
[184] Mode 72. The method or process defined in any of modalities 1-71, further comprising the steps of determining (or measuring) the Mw, and adjusting the amount of the alcohol compound introduced into the polymerization reactor system based on in the difference between the measured Mw and the target Mw.
[185] Mode 73. The method or process defined in any of modalities 1-72, further comprising the steps of determining (or measuring) the Mz, and adjusting the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between the measured Mz and the target Mz.
[186] Mode 74. The method or process defined in any of modalities 1-73, wherein the olefin polymer comprises a higher molecular weight component and a lower molecular weight component.
[187] Mode 75. The method or process defined in mode 74, in which the introduction of the alcohol compound into the polymerization reactor system increases the weight ratio of the highest molecular weight component to the lowest molecular weight component.
[188] Mode 76. The method or process defined in mode 74 or 75, wherein the introduction of the alcohol compound into the polymerization reactor system has substantially no effect on the peak molecular weight of the lowest molecular weight component.
[189] Mode 77. The method or process defined in any of the 74-76 modes, in which the introduction of the alcohol compound into the polymerization reactor system has substantially no effect on the peak molecular weight of the most molecular weight component high.
[190] Mode 78. The method or process defined in any of the 74-77 modes, in which the first metallocene catalyst component produces the lowest molecular weight component.
[191] Mode 79. The method or process defined in any of the 74-78 modes, in which the second metallocene catalyst component produces the highest molecular weight component.
[192] Mode 80. The method or process defined in any of modalities 1-79, in which the alcohol compound is introduced into the polymerization reactor system continuously.
[193] Mode 81. The method or process defined in any of modalities 1-79, in which the alcohol compound is introduced into the polymerization reactor system periodically.
[194] Mode 82. The method or process defined in any of modalities 1-81, 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.
[195] Mode 83. The method or process defined in any of modalities 1-82, in which the introduction of the alcohol compound into the polymerization reactor system has substantially no effect on the catalytic activity of the double catalyst system (or substantially no effect on the rate of olefin polymer production).
[196] Mode 84. The method or process defined in any of modalities 1-83, in which the olefin polymer MI may decrease as the amount of alcohol compound added to the polymerization reactor system increases.
[197] Mode 85. The method or process defined in any of modalities 1-84, in which the olefin polymer HLMI decreases as the amount of alcohol compound added to the polymerization reactor system increases.
[198] Mode 86. The method or process defined in any of modalities 1-85, in which the Mw of the olefin polymer increases as the amount of the alcohol compound added to the polymerization reactor system increases.
[199] Mode 87. The method or process defined in any of modalities 1-86, in which the Mz of the olefin polymer increases as the amount of alcohol compound added to the polymerization reactor system increases.
[200] Mode 88. The method or process defined in any of modalities 1-87, in which the Mz / Mw ratio of the olefin polymer decreases as the amount of alcohol compound added to the polymerization reactor system increases.
[201] Mode 89. The method or process defined any of modalities 1-88, wherein the compound introduction of alcohol into the polymerization reactor system has substantially no effect on the Mn of the olefin polymer.

权利要求:
Claims (20)
[0001]
1. Method for controlling a polymerization reaction in a polymerization reactor system, the method characterized by the fact that it comprises: (i) contacting a double catalyst system with an olefin monomer and an optional olefin comonomer in the reactor system from polymerization under polymerization conditions to produce an olefin polymer, wherein the dual catalyst system comprises a first metallocene catalyst component, a second metallocene catalyst component, an activator and a cocatalyst; and (ii) introducing an amount of an alcohol compound into the polymerization reactor system to (I) reduce a melt index parameter of the olefin polymer; (II) increasing a molecular weight parameter of the olefin polymer selected from Mw, Mz, or both; or (III) reducing a melt index parameter of the olefin polymer and increasing a molecular weight parameter of the olefin polymer selected from Mw, Mz, or both.
[0002]
2. Method according to claim 1, characterized in that the alcohol compound comprises methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol, phenol, benzyl alcohol or a combination of the same.
[0003]
3. Method according to claim 1, characterized in that the double catalyst system comprises: a first metallocene catalyst component comprising a zirconium-containing metallocene compound; a second metallocene catalyst component comprising a bridged metallocene compound containing zirconium or hafnium; an activator comprising an activator-support, an aluminoxane compound, an organoboro or organoborate compound, an ionizing ionic compound, or any combination thereof; and a cocatalyst comprising an organoaluminium compound.
[0004]
4. Method according to claim 3, characterized by the fact that: the activator comprises an activator-support comprising a fluorinated solid oxide, a sulfated solid oxide, or a combination thereof; the amount of alcohol compound introduced into the polymerization reactor system is in the range of 1: 10,000 to 1:10, based on the moles of hydroxyl groups (-OH) of the alcohol compound for the weight of the activator-support in grams added the polymerization reactor system; and the alcohol compound comprises a hydrocarbon C1 to C12 alcohol.
[0005]
5. Method according to claim 1, characterized by the fact that the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.
[0006]
6. Method according to claim 1, characterized by the fact that the polymerization reactor system comprises a single reactor.
[0007]
7. Method according to claim 1, characterized in that the olefin monomer comprises ethylene and the olefin comonomer comprises a C3-C10 alpha-olefin.
[0008]
8. Method, according to claim 1, characterized by the fact that it further comprises: determining an MI and adjusting the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between a determined MI and a target MI; determine an HLMI and adjust the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between a determined HLMI and a target HLMI; determine the Mw and adjust the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between the determined Mw and the target Mw; or determine Mz and adjust the amount of the alcohol compound introduced into the polymerization reactor system based on the difference between the determined Mz and the target Mz; or any combination thereof.
[0009]
9. Method according to claim 1, characterized by the fact that: a weight ratio of the first metallocene catalyst component to the second metallocene catalyst component is in the range of 1:10 to 10: 1; and 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 by the fact that: the cocatalyst comprises an organoaluminium compound; and the amount of the alcohol compound introduced in the polymerization reactor system is in a range of molar ratio of 0.1: 1 to 0.9: 1, based on the moles of hydroxyl groups (-OH) of the alcohol compound for the moles of organoaluminium compound added to the polymerization reactor system.
[0011]
11. Method, according to claim 1, characterized by the fact that the amount of the alcohol compound introduced in the polymerization reactor system is in a range of 10: 1 to 1000: 1 molar ratio, based on the mole ratio of hydroxyl groups (-OH) of the alcohol compound to the total moles of the first metallocene catalyst component and the second metallocene catalyst component added to the polymerization reactor system.
[0012]
12. 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 the molecular weight parameter, the melt index parameter, or both the molecular weight parameter and the melt index parameter; or both.
[0013]
13. Process for producing an olefin polymer with a target melt index parameter, a target molecular weight parameter, or a target melt index parameter and a target molecular weight parameter, the process characterized by the fact that it comprises: (a) contacting a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions, where the double catalyst system comprises a first metallocene catalyst component, a second metallocene catalyst component, an activator and a cocatalyst; and (b) controlling an amount of an alcohol compound introduced into the polymerization reactor system to produce the olefin polymer with the target melt index parameter, the target molecular weight parameter, or the target melt index parameter and the target molecular weight parameter; where: the fusion index parameter is MI, HLMI, or both; and the molecular weight parameter is Mw, Mz, or both.
[0014]
14. Process according to claim 13, characterized by the fact that the olefin polymer has: a melt index (MI) of less than 10 g / 10 min; a numerical average molecular weight (Mn) in the range of 5,000 to 40,000 g / mol; an average molecular weight by weight (Mw) in a range of 100,000 to 600,000 g / mol; or an Mw / Mn ratio in a range of 10 to 40; or any combination thereof.
[0015]
15. Process according to claim 14, characterized in that the alcohol compound comprises a C1 to C8 alkyl alcohol and the olefin polymer is an ethylene / α-olefin copolymer.
[0016]
16. Process according to claim 13, characterized by the fact that MI and HLMI of the olefin polymer decrease as the amount of alcohol compound added to the polymerization reactor system increases.
[0017]
17. Process according to claim 13, characterized in that the Mw and Mz of the olefin polymer increase as the amount of alcohol compound added to the polymerization reactor system increases.
[0018]
18. Process according to claim 13, 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 lower molecular weight component high for the lowest molecular weight component increases as the amount of alcohol compound added to the polymerization reactor system increases; a peak molecular weight of the lower molecular weight component is substantially unchanged as the amount of the alcohol compound added to the polymerization reactor system increases; or a peak molecular weight of the highest molecular weight component is substantially unchanged as the amount of the alcohol compound added to the polymerization reactor system increases; or any combination thereof.
[0019]
19. Process according to claim 13, characterized by the fact that: the polymerization reactor system comprises a loop paste reactor; the alcohol compound comprises isopropyl alcohol; and the olefin polymer is an ethylene / 1-hexene copolymer.
[0020]
20. Process according to claim 19, characterized in that the double catalyst system comprises: a first metallocene catalyst component comprising a zirconium-containing metallocene compound; 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.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112016002782B1|2020-12-29|methods for controlling double metallocene catalyst olefin polymerizations with an alcohol compound

---

BR112015018293B1|2021-06-01|METHODS TO CONTROL POLYMERIZATIONS OF DOUBLE CATALYST OLEFIN WITH AN ORGANOZINC COMPOUND

---

US9944736B2|2018-04-17|Processes for preparing metallocene-based catalyst systems

---

BR112015006379B1|2021-03-02|olefin polymerization process using double catalyst

---

US9884930B2|2018-02-06|Processes for preparing metallocene-based catalyst systems in cyclohexene

---

US10131725B2|2018-11-20|Production of high haze films using metallocene-based catalyst systems in cyclohexene

---

CN107922542B|2020-09-25|Method for controlling die swell in a dual catalyst olefin polymerization system

---

BR112017026207B1|2021-11-09|PROCESS FOR PRODUCTION OF CATALYST COMPOSITION, OLEFIN POLYMERIZATION PROCESS AND CATALYST COMPOSITION

同族专利:

---

公开号 | 公开日

---

EP3030593A1|2016-06-15|

---

US9303099B2|2016-04-05|

---

RU2016103487A|2017-09-12|

---

WO2015021040A1|2015-02-12|

---

EP3030593B1|2021-03-10|

---

CN104341544B|2018-06-08|

---

US20150045521A1|2015-02-12|

---

BR112016002782A2|2017-08-01|

---

US8957168B1|2015-02-17|

---

RU2655383C2|2018-05-28|

---

US20150133612A1|2015-05-14|

---

CN104341544A|2015-02-11|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3248179A|1962-02-26|1966-04-26|Phillips Petroleum Co|Method and apparatus for the production of solid polymers of olefins|

---

US3242099A|1964-03-27|1966-03-22|Union Carbide Corp|Olefin polymerization catalysts|

---

US4501885A|1981-10-14|1985-02-26|Phillips Petroleum Company|Diluent and inert gas recovery from a polymerization process|

---

US4588790A|1982-03-24|1986-05-13|Union Carbide Corporation|Method for fluidized bed polymerization|

---

US4808561A|1985-06-21|1989-02-28|Exxon Chemical Patents Inc.|Supported polymerization catalyst|

---

US4939217A|1987-04-03|1990-07-03|Phillips Petroleum Company|Process for producing polyolefins and polyolefin catalysts|

---

US4794096A|1987-04-03|1988-12-27|Fina Technology, Inc.|Hafnium metallocene catalyst for the polymerization of olefins|

---

US5565175A|1990-10-01|1996-10-15|Phillips Petroleum Company|Apparatus and method for producing ethylene polymer|

---

US5575979A|1991-03-04|1996-11-19|Phillips Petroleum Company|Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator|

---

US5436304A|1992-03-19|1995-07-25|Exxon Chemical Patents Inc.|Process for polymerizing monomers in fluidized beds|

---

US5352749A|1992-03-19|1994-10-04|Exxon Chemical Patents, Inc.|Process for polymerizing monomers in fluidized beds|

---

US5576259A|1993-10-14|1996-11-19|Tosoh Corporation|Process for producing α-olefin polymer|

---

US5455314A|1994-07-27|1995-10-03|Phillips Petroleum Company|Method for controlling removal of polymerization reaction effluent|

---

KR100388716B1|1994-09-08|2003-11-28|엑손모빌 오일 코포레이션|Catalytic Control of Resin with Wide or Dual Molecular Weight Distribution in a Single Reactor|

---

US5525678A|1994-09-22|1996-06-11|Mobil Oil Corporation|Process for controlling the MWD of a broad/bimodal resin produced in a single reactor|

---

IT1270125B|1994-10-05|1997-04-28|Spherilene Srl|PROCESS FOR THE POLYMERIZATION OF OLEFINE|

---

US5670589A|1995-02-08|1997-09-23|Phillips Petroleum Company|Organoaluminoxy product, catalyst systems, preparation, and use|

---

DE69611554T2|1995-02-20|2001-07-05|Tosoh Corp|Catalyst for the polymerization of olefins and process for the preparation of olefin polymers|

---

EP0889912B1|1996-03-27|2000-07-12|The Dow Chemical Company|Highly soluble olefin polymerization catalyst activator|

---

US5739220A|1997-02-06|1998-04-14|Fina Technology, Inc.|Method of olefin polymerization utilizing hydrogen pulsing, products made therefrom, and method of hydrogenation|

---

US6239235B1|1997-07-15|2001-05-29|Phillips Petroleum Company|High solids slurry polymerization|

---

KR100531628B1|1998-03-20|2005-11-29|엑손모빌 케미칼 패턴츠 인코포레이티드|Continuous slurry polymerization volatile removal|

---

US6300271B1|1998-05-18|2001-10-09|Phillips Petroleum Company|Compositions that can produce polymers|

---

US6262191B1|1999-03-09|2001-07-17|Phillips Petroleum Company|Diluent slip stream to give catalyst wetting agent|

---

US20040059070A1|2002-09-19|2004-03-25|Whitte William M.|Process and apparatus for controlling molecular weight distribution and short chain branching for olefin polymers|

---

JP2004115697A|2002-09-27|2004-04-15|Tonen Chem Corp|METHOD FOR MANUFACTURING alpha-OLEFIN COPOLYMER|

---

US6861487B2|2003-04-15|2005-03-01|Saudi Basic Industries Corporation|Catalyst precursor for the polymerization of olefins and polymerization process using the same|

---

US7238756B2|2003-10-15|2007-07-03|Univation Technologies, Llc|Polymerization process and control of polymer composition properties|

---

US7838605B2|2003-10-17|2010-11-23|Univation Technologies, Llc|Polymerization monitoring and control using improved leading indicators|

---

US7041617B2|2004-01-09|2006-05-09|Chevron Phillips Chemical Company, L.P.|Catalyst compositions and polyolefins for extrusion coating applications|

---

US7119153B2|2004-01-21|2006-10-10|Jensen Michael D|Dual metallocene catalyst for producing film resins with good machine direction elmendorf tear strength|

---

US7294599B2|2004-06-25|2007-11-13|Chevron Phillips Chemical Co.|Acidic activator-supports and catalysts for olefin polymerization|

---

US7199073B2|2004-11-10|2007-04-03|Chevron Phillips Chemical Company, Lp|Resins that yield low haze films and the process for their production|

---

US7323523B2|2004-12-07|2008-01-29|Nova Chemicals S.A.|Adjusting polymer characteristics through process control|

---

US7026494B1|2005-01-10|2006-04-11|Chevron Phillips Chemical Company, Lp|Polymerization catalysts for producing high melt index polymers without the use of hydrogen|

---

US7312283B2|2005-08-22|2007-12-25|Chevron Phillips Chemical Company Lp|Polymerization catalysts and process for producing bimodal polymers in a single reactor|

---

US7226886B2|2005-09-15|2007-06-05|Chevron Phillips Chemical Company, L.P.|Polymerization catalysts and process for producing bimodal polymers in a single reactor|

---

US7615596B2|2005-09-30|2009-11-10|Chevron Phillips Chemical Company Lp|Multiple component feed methods and systems|

---

US7517939B2|2006-02-02|2009-04-14|Chevron Phillips Chemical Company, Lp|Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching|

---

US7619047B2|2006-02-22|2009-11-17|Chevron Phillips Chemical Company, Lp|Dual metallocene catalysts for polymerization of bimodal polymers|

---

US7662894B2|2006-12-19|2010-02-16|Saudi Bosic Industries Corporation|Polymer supported metallocene catalyst composition for polymerizing olefins|

---

US8080681B2|2007-12-28|2011-12-20|Chevron Phillips Chemical Company Lp|Nano-linked metallocene catalyst compositions and their polymer products|

---

US7884163B2|2008-03-20|2011-02-08|Chevron Phillips Chemical Company Lp|Silica-coated alumina activator-supports for metallocene catalyst compositions|

---

US8114946B2|2008-12-18|2012-02-14|Chevron Phillips Chemical Company Lp|Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches|

---

US7919639B2|2009-06-23|2011-04-05|Chevron Phillips Chemical Company Lp|Nano-linked heteronuclear metallocene catalyst compositions and their polymer products|

---

US8440772B2|2011-04-28|2013-05-14|Chevron Phillips Chemical Company Lp|Methods for terminating olefin polymerizations|

---

US10273315B2|2012-06-20|2019-04-30|Chevron Phillips Chemical Company Lp|Methods for terminating olefin polymerizations|

---

US8680218B1|2013-01-30|2014-03-25|Chevron Phillips Chemical Company Lp|Methods for controlling dual catalyst olefin polymerizations with an organozinc compound|

---

US8957168B1|2013-08-09|2015-02-17|Chevron Phillips Chemical Company Lp|Methods for controlling dual catalyst olefin polymerizations with an alcohol compound|US8957168B1|2013-08-09|2015-02-17|Chevron Phillips Chemical Company Lp|Methods for controlling dual catalyst olefin polymerizations with an alcohol compound|

---

EP3420013A1|2016-10-27|2019-01-02|Kordsa Teknik Tekstil Anonim Sirketi|Exotherm stopper mixtures|

---

WO2018113942A1|2016-12-21|2018-06-28|Kordsa Teknik Tekstil Anonim Sirketi|Exotherm stopper compositions|

---

US10723819B2|2017-02-20|2020-07-28|Exxonmobil Chemical Patents, Inc.|Supported catalyst systems and processes for use thereof|

---

WO2018151903A1|2017-02-20|2018-08-23|Exxonmobil Chemical Patents Inc.|Supported catalyst systems and processes for use thereof|

---

CN111108130A|2017-08-04|2020-05-05|埃克森美孚化学专利公司|Has the advantages ofcontaining-CH2-SiMe3Hybrid catalysts of partially unbridged hafnocenes|

---

US10844150B2|2017-08-04|2020-11-24|Exxonmobil Chemical Patents Inc.|Mixed catalysts with 2,6-bispyridyl iron complexes and bridged hafnocenes|

---

US10703838B2|2017-10-31|2020-07-07|Exxonmobil Chemical Patents Inc.|Mixed catalyst systems with four metallocenes on a single support|

---

US10926250B2|2017-12-01|2021-02-23|Exxonmobil Chemical Patents Inc.|Catalyst systems and polymerization processes for using the same|

---

EP3717522A1|2017-12-01|2020-10-07|ExxonMobil Chemical Patents Inc.|Catalyst systems and polymerization processes for using the same|

---

US10865258B2|2018-01-31|2020-12-15|Exxonmobil Chemical Patents Inc.|Mixed catalyst systems containing bridged metallocenes with a pendant group 13 element, processes for making a polymer product using same, and products made from same|

---

US10851187B2|2018-01-31|2020-12-01|Exxonmobil Chemical Patents Inc.|Bridged metallocene catalysts with a pendant group 13 element, catalyst systems containing same, processes for making a polymer product using same, and products made from same|

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

---

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

---

2020-12-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US13/962,982|US8957168B1|2013-08-09|2013-08-09|Methods for controlling dual catalyst olefin polymerizations with an alcohol compound|

---

US13/962,982|2013-08-09|

---

PCT/US2014/049770|WO2015021040A1|2013-08-09|2014-08-05|Methods for controlling dual metallocene catalyst olefin polymerizations with an alcohol compound|

---