olefin polymerization process using double catalyst

专利摘要:
Methods of controlling a weight ratio of a higher molecular weight component and a lower molecular weight component of an olefin polymer are disclosed. This weight ratio can be increased as the polymerization reaction temperature and / or residence time of the catalyst system are increased.
公开号:BR112015006379B1
申请号:R112015006379-9
申请日:2013-09-16
公开日:2021-03-02
发明作者:Qing Yang；Tony R. Crain；Jerry T. Lanier；Jeff S. Fodor
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
[0001] There are several methods that can be employed to adjust or control the relative amounts of the higher molecular weight component and the lower molecular weight component of a polymer produced using a dual catalyst system. For example, the composition of the catalyst and / or the composition of the reagent can be changed to vary the relative amounts of the highest molecular weight component and the lowest molecular weight component that are produced. However, additional methods are needed to adjust or control polymeric components that do not require changes in the composition of the catalyst or the composition of the reagent. Therefore, it is to this end that the present description is directed. SUMMARY OF THE INVENTION
[0002] This summary is provided to present a selection of concepts in a simplified way, which are described below in the detailed description. This summary is not intended to identify the necessary or essential characteristics of the claimed subject. Nor is this summary intended to be used to limit the scope of the claimed subject.
[0003] Various processes and methods related to the control of olefin polymerizations using double catalyst are disclosed in this document. In one embodiment, a polymerization process may comprise: (1) contacting a dual catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the olefin polymer comprises a higher molecular weight component and a lower molecular weight component, where the double catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and where the conditions of polymerization comprises a reaction temperature and residence time a dual catalyst system; and (2) the control of a weight ratio of the component of higher molecular weight to the component of lower molecular weight, adjusting the reaction temperature and / or the residence time of the dual catalyst system.
[0004] A method of controlling the weight ratio of the higher molecular weight component to the lower molecular weight component of an olefin polymer is provided in this document and in this embodiment, which the method may comprise: (i) contact with a system double catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the olefin polymer, where the dual catalyst system comprises a first metallocene catalyst component and a second component of metallocene catalyst, and in which the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (ii) adjust the reaction temperature and / or residence time of the dual catalyst system to control the weight ratio of the highest molecular weight component to the lowest molecular weight component.
[0005] A process for producing an olefin polymer with a target weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight is also provided in this document and in this embodiment, which the process may comprise: (a) contact with 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 and a second metallocene catalyst component, and wherein the polymerization conditions comprise a reaction temperature and residence time a dual catalyst system; and (b) controls the reaction temperature and / or residence time of the double reactor catalyst system to produce the olefin polymer with a target weight ratio from the highest molecular weight component to the lowest molecular weight component.
[0006] Another polymerization process is disclosed in this document, and in this embodiment, the process may comprise: (l) contact with a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the olefin polymer comprises a higher molecular weight component and a lower molecular weight component, wherein the double catalyst system comprises a first transition metal compound, a second composed of transition metal and a support activator, and in which the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (m) controls a weight ratio of the higher molecular weight component to the lower molecular weight component, adjusting the reaction temperature and / or the residence time of the dual catalyst system.
[0007] Another method of controlling the weight ratio of the highest molecular weight component to the lowest molecular weight component of an olefin polymer is disclosed in this document, and in this embodiment, the method may comprise: (i) contact with a system double catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the olefin polymer, wherein the double catalyst system comprises a first transition metal compound, a second composed of transition metal and a support activator, and in which the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (ii) adjust the reaction temperature and / or residence time of the dual catalyst system to control the weight ratio of the highest molecular weight component to the lowest molecular weight component.
[0008] Another process for producing an olefin polymer with a target weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight is disclosed in this document and in this modality, which the process may comprise: (a) contact with 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 transition metal compound, a second transition metal compound and a support activator, and in which the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (b) controls the reaction temperature and / or residence time of the double reactor catalyst system to produce the olefin polymer with a target weight ratio from the highest molecular weight component to the lowest molecular weight component.
[0009] In these methods and processes, the weight ratio of the highest molecular weight component to the lowest molecular weight component can increase the reaction temperature and / or the weight ratio of the highest molecular weight component to the lower molecular weight component may increase as the residence time of the catalyst system increases.
[0010] Both the above summary and the detailed description below are only exemplary and explanatory. In this sense, the above summary and the following detailed description should not be considered restrictive. In addition, features or variations may be provided in addition to those set forth herein. For example, certain modalities can be directed to various combinations and sub-combinations of resources described in the detailed description. BRIEF DESCRIPTION OF THE FIGURES
[0011] FIG. 1 presents a graph of the molecular weight distribution as a function of the temperature of the polymerization reaction to obtain Examples 1-5.
[0012] FIG. 2 presents a graph of the molecular weight distribution as a function of the reaction time of the catalyst system to obtain Examples 6-8. DEFINITIONS
[0013] To define more clearly the terms used in this document, the following definitions are provided. Unless otherwise stated, the following definitions apply to this disclosure. If a term is used in the disclosure, but is not specifically defined in this document, the IUPAC Compendium of Chemical Terminology definition, 2nd Ed (1997), can be applied as long as that definition does not conflict with any other type of disclosure or definition applied in this document, or make any claim to which the definition is applied indefinite or ineligible. Insofar as any definition or use provided by any document incorporated in this document by reference conflicts with the definition or use provided in this document, the definition or use provided in this document controls.
[0014] Regarding transitional terms or phrases of the claims, the transitional term "characterized by the fact of understanding", which is synonymous with "include", "contain", "have", or "characterized by", is inclusive and open, and it does not exclude additional elements, elements not recited or steps of the method. The transitional phrase "consist of" excludes any element, method or ingredient not specified in the claim. The transitional phrase "which essentially consists of" limits the scope of the claim to specific materials or steps and those that do not materially affect the basic or new characteristics of the claim. A claim "characterized by consisting essentially of" occupies a middle ground between closed claims that are written in a format "characterized by consisting of" and fully open claims that are drawn up in a format "characterized by the fact of understanding". Unless otherwise stated, describing a compound or composition as "characterized by essentially consisting of" should not be interpreted as "characterized by the fact of understanding", but is intended to describe the aforementioned component that includes materials that do not significantly alter the composition or method in which the term is applied. For example, raw material that consists essentially of material A may include impurities typically present in a commercially produced or commercially available sample of the recited compound or composition. When a claim includes different characteristics and / or classes of characteristics (for example, a method step, characteristics of the raw material and / or characteristics of the product, among other possibilities), the transitional terms characterized by the fact that it comprises, essentially consists of, consist of, apply only to the characteristic class for which it is used, and it is possible to have different transitional terms or phrases used by different classes within a claim. For example, a method may comprise several recited steps (and other non-recited steps), but they use a system preparation made up of specific components; as an alternative, which essentially consists of specific components; or alternatively, comprising specific components and other components not recited.
[0015] Although compositions and methods are often described in terms of "characterized by comprising", various components or steps, compositions and methods can also be "characterized by consisting essentially of" or "characterized by consisting of" various components or steps, unless otherwise stated.
[0016] The terms, "a / a" and "the / a" are intended to include alternatives in the plural, for example, at least one. For example, the disclosure of "an activator," "an olefin comonomer", etc., is intended to encompass, or mixtures or combinations of more than one, activator, olefin comonomer, etc., unless otherwise specified. form.
[0017] For any particular compound or group disclosed in this document, any name or structure (general or specific) presented is intended to cover all conformational isomers, regioisomers, stereoisomers and mixtures that may arise from a particular set of substituents , unless otherwise specified. The name or structure (general or specific) also encompasses all enantiomers, diastereomers and other optical isomers (if any) whether in racemic or enantiomeric form, as well as mixtures of stereoisomers, as would be recognized by one skilled in the art, a 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 seg-butyl group, an iso-butyl group and a t-butyl group.
[0018] Also, unless otherwise specified, any group containing carbon or a compound 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 group containing carbon or compound can have 1 to 20 carbon atoms, 1 to 18 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms , from 2 to 20 carbon atoms, from 2 to 12 carbon atoms, from 2 to 8 carbon atoms, or from 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, and / or stereochemistry, or the presence of the absence of an underlying branched structure or main structure. Any specific group that contains carbon is limited according to the chemical and structural requirements for that specific group, as understood by a common skill.
[0019] Other numerical scales are disclosed in this document. When claimants disclose or claim a range of any kind, claimants' intention is to individually disclose or claim every possible number that a range could reasonably cover, including range endpoints, as well as any sub-ranges and combinations of sub-ranges. ranges covered therein, unless otherwise specified. As a representative example, applicants disclose a weight ratio of the highest molecular weight component to the lowest molecular weight component can be in the range of approximately 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 approximately 1:10 to about 10: 1, the applicant intends to recite that the weight ratio can be equal to approximately 1:10, about 1: 9, about 1: 8, about 1: 7, about 1: 6, about 1: 5, about 1: 4, about 1: 3, about 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 the range of about 1: 2 to about 2: 1 ), and this also includes any combination of intervals between about 1:10 and 10: 1. Likewise, all other ranges disclosed in this document must be interpreted in a manner similar to these examples.
[0020] Claimants reserve the right to reserve or exclude any individual member of any group, including sub-bands or combinations of sub-bands within a group, which can be claimed according to the band or in any similar manner, if for any reason the claimants choose to claim less than a complete disclosure measure, for example, to explain a reference that claimants may not be aware of at the time of filing this application. In addition, claimants reserve the right to reserve or exclude any individual substituents, analogs, compounds, binders, structures or groups thereof, or any member of a claimed group, if for any reason the claimants choose to claim less than a complete measure for disclosure, for example, to explain a reference that claimants may not be aware of when filing this application.
[0021] The term "substituted" when used to describe a group or chain of carbon atoms, for example, when referring to a substituted analog of a given group or chain, is intended to describe either group or chain where any fraction of non-hydrogen formally replaces a hydrogen in that group or chain and is intended to be not limited. A group or chain can also be referred to in this document as "unsubstituted" or by equivalent terms, such as "unsubstituted," which refers to the original group or chain. "Substituted" is intended to be non-limited and may include hydrocarbon substituents as specified and as understood by one skilled in the art.
[0022] The term "hydrocarbons", whenever used in this specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers can be used to indicate the presence of particular groups in the hydrocarbon (for example, halogenated hydrocarbons indicate the presence of one or more halogen atoms, replacing an equivalent number of hydrogen atoms in hydrocarbon).
[0023] The term "alkanes" whenever used in this specification and claims refers to a saturated hydrocarbon compound. Other identifiers can be used to indicate the presence of particular groups in the alkane (for example, halogenated alkanes indicate the presence of one or more halogen atoms, replacing an equivalent number of hydrogen atoms in the alkane). The term "alkyl group" is used in this document in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from an alkane. An "alkyl group" and an "alkane" can be straight or branched, unless otherwise specified. Primary, secondary and tertiary alkyl groups can be derived by removing a hydrogen atom from a primary, secondary and tertiary carbon atom, respectively, from an alkane. The n-alkyl group can be derived by removing a hydrogen atom from a terminal carbon atom of a linear alkane. The groups RCH2 (R # H), R2CH (R # H) and R3C (R # H) are primary, secondary and tertiary alkyl groups, respectively. The carbon atom by which the indicated fraction is attached to the carbon atom is a secondary, tertiary and quaternary carbon atom, respectively.
[0024] The term "polymer" is used in this document generically to include olefin homopolymers, copolymers, 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. In this sense, the "polymer" encompasses copolymers, terpolymers, etc., derived from any olefin monomer and comonomer (s) disclosed in this document. Likewise, an ethylene polymer would include homopolymer ethylene, 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 ethylene and 1-hexene monomer and comonomer, respectively, the resulting polymer can be categorized as ethylene / 1-hexene copolymer. The term "polymer" should also include all polymers of molecular weight, and is even lower molecular weight polymers or oligomers. For the term "polymer", applicants intend to cover 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).
[0025] Likewise, the scope of the term "polymerization" includes homopolymerization of copolymerization, terpolymerization, etc., as well as processes that can also be referred to as process oligomerization. Therefore, a copolymerization process would involve contacting an olefin monomer (for example, ethylene) and an olefin comonomer (for example, 1-hexene) to produce an olefin copolymer.
[0026] The terms "catalyst composition," "catalyst mixture", "catalyst system," and the type, do not depend on the actual product or composition resulting from contact or reaction of the initial components of the claimed composition / mixture / system catalyst , the nature of the catalytic active site, or the destination of the co-catalyst, the transition metal compound (s) or metallocene compound (s), of 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, encompass the initial composition components, as well as any product (s) may be the result of contact with these starting components initial, and this is including the two heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition," "catalyst mixture", "catalyst system" and the like, can be used interchangeably throughout this disclosure.
[0027] The terms "contact product", "contact" and the like, are used in this document 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 combining or mixing. In addition, unless otherwise specified, upon contact with any component, it may occur in the presence or absence of any other component of the compositions described herein. Combining additional materials or components can be done by any suitable method. In addition, the term "contact product" includes mixtures, combinations, solutions, suspensions, reaction products and the like, or combinations thereof. Although it can "contact product" and often include reaction products, it is not necessary for the respective components to react with one 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.
[0028] Although any materials and methods similar or equivalent to those described in this document can be used in the practice and testing of this invention, typical materials and methods are described in this document.
[0029] All publications and patents mentioned in this document in its entirety, by reference, for the purpose of describing and disclosing, for example, the constructions and methodologies that are described in the publications, which can be used in connection with invention described herein. The publications discussed throughout the text are provided solely for publication before the filing date of this application. Nothing in this document is to be construed as an admission that inventors are not entitled to anticipate such disclosure by virtue of the prior invention. DETAILED DESCRIPTION OF THE INVENTION
[0030] Disclosure in this document are processes and methods aimed at controlling the weight of the component with the highest molecular weight to the component with the lowest molecular weight of an olefin polymer. Dual catalyst systems can often be employed and normally, one catalyst component of the dual catalyst system can mainly produce the highest molecular weight component and the other catalyst component can mainly produce the smallest molecular weight component. 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.
[0031] In one embodiment, a polymerization process is disclosed. In this embodiment, the polymerization process can comprise: (1) contact with a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, in that the olefin polymer comprises a higher molecular weight component and a lower molecular weight component, wherein the double catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and in which the polymerization conditions a reaction temperature and residence time comprise a dual catalyst system; and (2) controls a weight ratio of the higher molecular weight component to the lower molecular weight component, adjusting the reaction temperature and / or the residence time of the dual catalyst system.
[0032] In another embodiment, a method for controlling the weight ratio of the higher molecular weight component to the lower molecular weight component of an olefin polymer is disclosed. In this embodiment, the method can comprise: (i) contact with a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the olefin polymer, in which the double catalyst system comprises a first metallocene catalyst component and a second metallocene catalyst component, and wherein the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (ii) adjust the reaction temperature and / or residence time of the dual catalyst system to control the weight ratio of the highest molecular weight component to the lowest molecular weight component.
[0033] In another embodiment, a process for producing an olefin polymer with a target weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight is disclosed. In this embodiment, the process may comprise: (a) contact with 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 and a second metallocene catalyst component, and wherein the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (b) controls the reaction temperature and / or residence time of the double reactor catalyst system to produce the olefin polymer with a target weight ratio from the highest molecular weight component to the lowest molecular weight component.
[0034] Generally, the characteristics of the processes and methods disclosed in this document (for example, the double catalyst system, the first component of the metallocene catalyst, the second component of the metallocene, the olefin monomer, the olefin comonomer, the conditions of polymerization, the reaction temperature, the residence time (also referred to as reaction time), the polymerization reactor system, the weight ratio of the highest molecular weight component to the lowest molecular weight component, among others) are described herein, and these resources may be combined in any combination to describe the methods and processes disclosed.
[0035] The weight ratio of the first component of the metallocene catalyst to the second component of the metallocene catalyst in the double catalyst system is generally not limited to any given variation in the weight ratio. However, in some embodiments, the weight ratio of the first component of the metallocene catalyst to the second component of the metallocene catalyst can be in a range from 1: 100 to about 100: 1, from about 1:50 to about from 50: 1, from about 1:25 to about 25: 1, from about 1:10 to about 10: 1, or from about 1: 5 to about 5: 1. Accordingly, suitable ranges for the weight ratio of the first component of the metallocene catalyst to the second component of the metallocene catalyst may include, but are not limited to, about 1:15 to about 15: 1, from about 1:10 to about 10: 1, from about 1: 8 to about 8: 1, from about 1: 5 to about 5: 1, from about 1: 4 to about 4: 1, from about 1: 3 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 1.1: 1, or from about 1: 1.05 to about 1.05: 1 and the like.
[0036] Consistent with modalities disclosed in this document, the weight ratio of the first component of the metallocene catalyst to the second component of the metallocene catalyst can be kept substantially constant (for example, within +/- 5%), for example, for production of a series of special polymer. In such circumstances, the temperature of the polymerization reaction and permanence of the catalyst can be used to control, adjust, fine-tine, etc., the production and properties of that degree of the particular polymer. In addition, other parameters of the polymerization process can also be varied, if necessary.
[0037] Optionally, if additional control parameters for the polymerization process of the double catalyst are desired in addition to the process parameters, such as temperature and residence reaction time, the methods and processes disclosed in this document may still comprise a step to adjust the weight ratio of the first component of the metallocene catalyst to the second component of the metallocene catalyst.
[0038] Another polymerization process consistent with the modalities disclosed in this document may comprise: (1) contact with a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions for produce an olefin polymer, wherein the olefin polymer comprises a higher molecular weight component and a lower molecular weight component, wherein the dual catalyst system comprises a first transition metal compound, a second metal compound transition and a support activator, and in which the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (2) controls a weight ratio of the higher molecular weight component to the lower molecular weight component, adjusting the reaction temperature and / or the residence time of the dual catalyst system.
[0039] Another method of controlling the weight ratio of the higher molecular weight component to the lower molecular weight component of an olefin polymer consistent with the modalities disclosed in this document may comprise: (i) contact with a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the olefin polymer, wherein the double catalyst system comprises a first transition metal compound, a second metal compound transition and a support activator, and in which the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (ii) adjust the reaction temperature and / or residence time of the dual catalyst system to control the weight ratio of the highest molecular weight component to the lowest molecular weight component.
[0040] Another process for producing an olefin polymer with a target weight ratio of the highest molecular weight component to the lowest molecular weight component consistent with the modalities disclosed in this document may comprise: (a) contact with a dual 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 transition metal compound, a second transition metal compound and an activator- support, and in which the polymerization conditions comprise a reaction temperature and residence time a double catalyst system; and (b) controls the reaction temperature and / or residence time of the double reactor catalyst system to produce the olefin polymer with a target weight ratio from the highest molecular weight component to the lowest molecular weight component.
[0041] Generally, the characteristics of the processes and methods disclosed in this document (for example, the dual catalyst system, the first metal transition component, the second metal transition component, the support activator, the olefin monomer, the olefin comonomer, the polymerization conditions, the reaction temperature, the residence time (also referred to as reaction time), the polymerization reactor system, the weight ratio of the highest molecular weight component to the lower molecular weight, among others) are independent described here, and these resources can be combined in any combination to describe the methods and processes disclosed.
[0042] The weight ratio of the first transition metal compound to the second compound in the transition metal double catalyst system is generally not limited to any given variation in the weight ratio. However, in some embodiments, the weight ratio of the first transition metal component to the second transition metal component can be in a range from 1: 100 to about 100: 1, from about 1:50 to about 50: 1, from about 1:25 to about 25: 1, from about 1:10 to about 10: 1, or from about 1: 5 to about 5: 1. Accordingly, suitable ranges for the weight ratio of the first transition metal component to the second transition metal component may include, but are not limited to, about 1:15 to about 15: 1, about 1 : 10 to about 10: 1, from about 1: 8 to about 8: 1, from about 1: 5 to about 5: 1, from about 1: 4 to about 4: 1, from about 1 : 3 to about 3: 1, from about 1: 2 to about 2: 1, from about 1: 1.8 to about 1.8: 1, from about 1: 1.5 to about 1.5 : 1, from about 1: 1.3 to about 1.3: 1, from about 1: 1.25 to about 1.25: 1, from about 1: 1.2 to about 1.2 : 1, from about 1: 1.15 to about 1.15: 1, from about 1: 1.1 to 1.1: 1, or from about 1: 1.05 to about 1.05: 1 and the like.
[0043] Consistent with the modalities disclosed in this document, the weight ratio of the first compound to the transition metal to the second transition metal compound can be kept substantially constant (for example, within +/- 5%), by example, for the production of a series of special polymer. In such circumstances, the temperature of the polymerization reaction and permanence of the catalyst can be used to control, adjust, fine-tine, etc., the production and properties of that degree of the particular polymer. In addition, other parameters of the polymerization process can also be varied, if necessary.
[0044] Optionally, if additional control parameters for the polymerization process of the double catalyst are desired in addition to the process parameters, such as temperature and residence reaction time, the methods and processes disclosed in this document may still comprise a step to adjust the weight ratio of the first transition metal component to the second transition metal component.
[0045] In each of the methods and processes disclosed in this document, the weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight may increase as the reaction temperature increases and / or the weight ratio of the component with the largest Molecular weight for the lower molecular weight component can increase as the residence time of the dual catalyst system (or reaction time) increases.
[0046] In addition, in these processes and methods, the reaction temperature can be adjusted or controlled (for example, increased, decreased), or the residence time of the catalyst system can be adjusted or controlled (for example, increased, decreased ), or both the reaction temperature and the residence time (or reaction time) can be adjusted or controlled (for example, increased, decreased).
[0047] Unexpectedly, in these processes and methods, the weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight may increase as the reaction temperature is increased. The reaction temperature, or the polymerization temperature, can be any appropriate temperature, depending on the type of polymerization reactor (s) used in the reactor system, the desired olefin polymer and the like, among other variables. Generally, however, the reaction temperature can be in the range of about 25 ° C to about 280 ° C, for example, from about 50 ° C to about 280 ° C, from about 60 ° C to about 200 ° C, from about 60 ° C to about 150 ° C or from 60 ° C to about 125 ° C. In certain embodiments, the reaction temperature can be in the range of about 60 ° C to about 120 ° C; Alternatively, from about 60 ° C to about 110 ° C; Alternatively, from about 70 ° C to about 120 ° C; Alternatively, from about 70 ° C to about 110 ° C; Alternatively, from about 80 ° C to about 120 ° C; Alternatively, from about 80 ° C to about 110 ° C; Alternatively, from about 80 ° C to about 105 ° C; or, alternatively, from about 85 ° C to about 115 ° C.
[0048] Also unexpectedly, the weight ratio of the highest molecular weight component to the lowest molecular weight component can increase as the residence time of the catalyst system (or reaction time) is increased. The residence time can be any suitable residence time, depending on the type of polymerization reactor (s) employed in the reactor system, the number of polymerization reactors, the desired olefin polymer, the rate of production of the polymers and the like, among other variables. Generally, however, the residence time can be in the range of about 5 min to about 5 hours, for example, from about 5 min to about 4 hours, from about 10 min to about 4 hours, from about 15 min to about 4 hours or from about 15 min to about 3 hours. In certain modalities, the residence time can be in an interval of about 10 min to about 3 hours; Alternatively, from about 10 min to about 2 hours; Alternatively, from about 10 min to about 90 min; Alternatively, from about 10 min to about 75 min; Alternatively, from about 15 min to about 2 hours; Alternatively, from about 15 min to about 90 min; Alternatively, from about 15 min to about 1 hour; or alternatively, from about 20 min to about 1 hour.
[0049] In these processes and methods, the weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight is generally not limited to any given variation in the weight ratio. However, in some embodiments, the weight ratio of the highest molecular weight component to the lowest molecular weight component can range from 1: 100 to about 100: 1, from about 1:50 to about 50: 1, from about 1:25 to about 25: 1, from about 1:10 to about 10: 1, or from about 1: 5 to about 5: 1. In that sense, appropriate ranges for the weight of the highest molecular weight component for the lowest molecular weight component may include, but are not limited to, about 1:15 to about 15: 1, from about 1:10 to about from 10: 1, from about 1: 8 to about 8: 1, from about 1: 5 to about 5: 1, from about 1: 4 to about 4: 1, from about 1: 3 to about from 3: 1, from about 1: 2 to about 2: 1, from about 1: 1.8 to about 1.8: 1, from about 1: 1.5 to about 1.5: 1 , from about 1: 1.3 to about 1.3: 1, from about 1: 1.25 to about 1.25: 1, from about 1: 1.2 to about 1.2: 1, from about 1: 1.15 to about 1.15: 1, from about 1: 1.1 to about 1.1: 1, or from about 1: 1.05 to about 1.05: 1 and the like .
[0050] For the production of a certain grade of an olefin polymer, with certain desired polymer properties, a target weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight can be established. Thus, when the degree of special polymer is produced, variables can be adjusted to achieve the target weight ratio. Accordingly, in some modalities, the processes and methods provided in this document may optionally also comprise the steps of determining (or measuring) the weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight and adjusting the temperature reaction time and / or residence time of the catalyst system based on the difference between the measured weight and the target weight ratio. As a representative example, if the ratio of the measured weight is different from the target weight ratio for the production of a certain degree of the olefin polymer, then the reaction temperature and / or the residence time can be adjusted (increased or decreased) as needed) to make the ratio of the measured weight equivalent to the target weight.
[0051] In certain modalities, for example, where the polymerization reactor system contains a slurry reactor (one or more than one), the% of the solid reactors can be in a range of about 25 to about 70 in Weight. %, or from about 30 to about 65 by weight. %. For example, the% of solid reactors can be in the range of about 30 to 60 by weight. %; alternatively, from about 30 to about 55 by weight. %; alternatively, from about 35 to 65 by weight. %; alternatively, from about 35 to about 60 by weight. %; alternatively, from about 35 to about 55 by weight. %; alternatively, from about 40 to about 60 by weight. %; alternatively, from about 40 to about 55 by weight. %; or alternatively, from about 40 to about 50 by weight. %.
[0052] Consistent with the modalities disclosed in this document, the polymerization conditions that can be adjusted and / or controlled in the processes and methods described here can be the polymerization reaction temperature and / or the residence time (or reaction time) of the double catalyst system. However, other polymerization conditions or process variables can be adjusted and / or controlled during the operation of a polymerization reactor system, and such conditions or variables may include, but are not limited to, reactor pressure, the rate of flow from the catalyst system to the reactor, monomer (and comonomer, if used) flow rate in the reactor, olefin polymer exit rate, recycling rate, hydrogen flow rate (if used), cooling state of the reactor, slurry density, circulating pump power, and the like.
[0053] In some embodiments, discussed in more detail here below, the olefin polymer may comprise an ethylene copolymer, for example, an ethylene / α-olefin copolymer, such as an ethylene / 1-hexene copolymer. In these embodiments, the density of the ethylene copolymer can be controlled by adjusting the weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight and, in addition, adjusting the molar ratio of ethylene to the olefin comonomer (for example, the molar ratio of ethylene to 1-hexene, producing a copolymer of ethylene / 1-hexene).
[0054] In one embodiment, no hydrogen is added to the polymerization reactor system. As one skilled in the art would recognize, hydrogen can be generated in situ by the first and / or second component of the metallocene catalyst (or the first and / or second transition metal) during the olefin polymerization process of the double catalyst. In the present modality, there is no "hydrogen added" to the reactor system.
[0055] Although not mandatory, however, hydrogen can be added to the polymerization reactor system in certain modalities. Optionally, for example, the methods and processes presented here can also constitute a one-step hydrogen addition step to the polymerization reactor system to adjust a molecular weight parameter (for example, the average weight molecular weight (Mw ), the average molecular weight number (Mn), Mw / Mn, etc.) of the olefin polymer, and / or adjust the melt index (MI) of the olefin polymer, if desired. Generally, the hydrogen addition step can decrease the Mw (and / or Mn), and / or increase the polymer's MI. Furthermore, in addition to the impact of the temperature reaction time and permanence on the weight ratio of the component with the highest molecular weight to the component with the lowest molecular weight of the polymer, the hydrogen addition step, in some modalities, can increase the weight of the component with the highest molecular weight for the component with the lowest molecular weight.
[0056] In the modalities where hydrogen is added to the polymerization reactor system, the addition of hydrogen can be carried out substantially constant (for example, within +/- 20%), for example, for the production of a series of special polymer . For example, the proportion of hydrogen to the olefin monomer in the polymerization process can be controlled, often by the ratio of the 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 during polymerization performed by a specific copolymer bill. However, in other modalities, the monomer, comonomer (or comonomers), and / or hydrogen can be periodically pulsed into the reactor, for example, in a similar way to that employed in US Patent No. 5,739,220 and Publication US Patent No. 2004/0059070, the disclosures to which the addendum is incorporated by reference in its entirety. CATALYST SYSTEMS
[0057] In some embodiments, the dual catalyst system may include a first metallocene catalyst component and a second metallocene catalyst component. The first metallocene catalyst component and the second metallocene catalyst component can independently 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 independently of the system which may comprise a transition metal Group III, IV, V or VI, or a combination of two or more transition metals. The first component of the metallocene catalyst and the second component of the metallocene catalyst 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. In this sense, the first component of the metallocene catalyst and the second component of the independent metallocene catalyst can comprise titanium, or zirconium or hafnium, alone or in combination.
[0058] In one embodiment, the first component of the metallocene catalyst can produce the lowest molecular weight component of the olefin polymer, and the second component of the metallocene catalyst can produce the highest molecular weight component of the olefin polymer. These component terms are relative, are used in reference to each other, and are not limited to the actual molecular weights of the respective components. While not limited thereto, the first component of the metallocene catalyst may comprise a metallocene compound without a bridge (for example, with zirconium or hafnium) such as those described in US Patent No. 7,619,047, the disclosure of which is incorporated into the addendum by reference in its entirety.
[0059] In another embodiment, the first component of the metallocene catalyst can produce the lower molecular weight component of the olefin polymer, and the first component of the metallocene catalyst can include zirconium, or alternatively, hafnium. Representative and non-limiting examples of metallocene compounds that can be used as the first metallocene compound may include, but are not limited to, the following (Ph = phenyl):

and the like, as well as their combinations.
[0060] In addition, the first component of the metallocene catalyst can comprise a bridged dinuclear metallocene such as those described in US Patent Nos. 7,919,639 and 8,080,681, the disclosures of which are incorporated in this document by reference, in their entirety. Representative and non-limiting dinuclear compounds may include the following:


and the like, as well as their combinations.
[0061] While not limited thereto, the second component of the metallocene catalyst may comprise a bridged metallocene (for example, with titanium, zirconium or hafnium) as described in US Patent Nos. 7,226,886 and 7,619,047, the disclosures of which are incorporated herein by reference, in their entirety.
[0062] In another embodiment, the second component of the metallocene catalyst can produce the higher molecular weight component of the olefin polymer, and the second component of the metallocene catalyst can include zirconium and / or hafnium. Representative and non-limiting examples of the metallocene compounds that can be used as the second metallocene compound can include, but are not limited to, the following (Ph = phenyl, Me = methyl and t-Bu = tert-butyl):

[0063] In other embodiments, the double catalyst system may comprise a first transition metal compound, a second transition metal compound and a support activator. In such embodiments, the methods and processes disclosed in this document are not limited to any specific catalyst system based on transition metals; thus, any catalyst system based on the transition metal (one or more than one) suitable for the polymerization of an optional olefin monomer (and comonomer (s)) of the olefin can be employed with a support activator. The first transition metal compound and the second transition metal compound independently can 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 transition metal compound and the second transition metal compound independently of the system which may comprise a transition metal Group III, IV, V or VI or a combination of two or more transition metals. The first transition metal compound and the second transition metal compound independently may comprise chromium, titanium, zirconium, hafnium, vanadium or a combination thereof, or may comprise chromium, titanium, zirconium, hafnium or a combination thereof, in other modalities. In this sense, the first transition metal compound and the second transition metal compound can independently comprise chromium, or titanium or zirconium, hafnium, alone or in combination. In one embodiment, the first transition metal compound can produce the lowest molecular weight component of the olefin polymer, and the second transition metal compound can produce the highest molecular weight component of the olefin polymer.
[0064] Several systems based on the transition metal from the catalyst known to one skilled in the art are useful in the polymerization of olefins. These include, but are not limited to, Ziegler-Natta based catalyst systems (e.g., Ziegler based catalyst systems), chromium based catalyst systems, metallocene based catalyst systems, Phillips catalyst systems, Ballard catalyst systems, coordination compound catalyst systems, post-metallocene catalyst systems and the like, including combinations thereof. The methods and processes disclosed in this document are not limited to the aforementioned catalyst systems, but applicants nevertheless contemplate the specific modalities directed to the use of these catalyst systems in the olefin polymerizations of the dual catalyst system described herein. For example, the dual catalyst system may comprise a catalyst system based on Ziegler-Natta, a catalyst system based on chromium and / or a catalyst system based on metallocene; alternatively, a catalyst system based on the Ziegler-Natta; alternatively, a chromium-based catalyst system; or, alternatively, a metallocene-based catalyst system. Examples of representative and non-limiting systems based on the transition metal catalyst system from those disclosed in US Patent Nos. 3,887,494, 3,119,569, 4,053,436, 4,981,831, 4,364,842, 4,444,965, 4,364,855, 4,504,638, 4,364,854, 4,444,964, 4,444,962, 3,976,632, 4,248,735, 4,297,460, 4,397,766, 2,825,534, 4,4, 5,4, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5 5,037,911, 5,219,817, 5,221,654, 4,081,407, 4,296,001, 4,392,990, 4,405,501, 4,151,122, 4,247,421, 4,460,756, 4,182,815, 4,735,931, 4,820,785, 4,988,657, 5,436,305, 5,647,247, 5, 5, 5, 5, 5, 7, 5, 5, 5, 7, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 7 5,275,992, 3,900,457, 4,939,217, 5,210,352, 5,436,305, 5,401,817, 5,631,335, 5,571,880, 5,191,132, 5,480,848, 5,399,636, 5,565,592, 5,347,026, 5,594,078, 5,498,581, 5,496,781, 5,563,284, 5,554,795, 5,420,320, 5,451,649, 5,541,272, 5,705,478, 5,631,203, 5,654,454, 5,705,579, 5,668,230, 6,300,271, 6,831,141, 6,653,416, 6,613,712, 7,294,599, 6,355,594, 6,395,666, 6,833,338, 7,417,097, 6,548,442, and 7,312,283, each of which is incorporated into the addendum by reference in its entirety.
[0065] In some embodiments, the double catalyst system may contain an activator. For example, the dual catalyst system can comprise a support activator, an aluminoxane compound, an organoborane or organoborate compound, an ionizing ionic compound and the like or any combination thereof. The catalyst system can contain one or more of an activator.
[0066] In one embodiment, the double catalyst system may comprise an aluminoxane compound, an organoborane or organoborate compound, an ionizing ionic compound and the like or a combination thereof. Examples of such activators are disclosed in, for example, US Patent Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938,5,919,983, and 8,114,946, the disclosures of which are incorporated herein by reference, in their entirety. In another embodiment, the double catalyst system may comprise an aluminoxane compound. In another embodiment, the double catalyst system can comprise an organoborane or an organoborate compound. In another embodiment, the double catalyst system may contain an ionizing ionic compound.
[0067] 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-removing anion. Examples of such materials are disclosed in, for example, US Patent Nos. 7,294,599 and 7,601,665, the disclosures of which are incorporated herein by reference, in their entirety.
[0068] The solid oxide used to produce the support activator can include oxygen and one or more elements from Groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 from the periodic table, or comprising oxygen and one or more elements of the lanthanides or actinide elements (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 include 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.
[0069] Accordingly, suitable examples of solid oxide materials that can be used to form the support activator may 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 respective mixed oxides and their combinations. This includes co-gel or co-precipitates from materials other than solid oxide. The solid oxide can encompass oxide materials such as alumina, respective "mixed oxides", such as silica-alumina and combinations and mixtures thereof. Mixed oxides such as silica-alumina can be single or multiple phases of chemistry with more than one metal combined with oxygen to form the solid oxide. Examples of mixed oxides that can be used to form an activator support, alone or in combination, may include, but are not limited to, silica-alumina, silica-Titanium, zirconia-silica, titania-alumina, alumina-zirconia, zinc -aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia and the like. The solid oxide used here can also cover oxide materials such as silica coated alumina, as described in US Patent No. 7,884,163, the disclosure of which is incorporated by reference in its entirety by reference.
[0070] Likewise, in one embodiment, the solid oxide can include silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or any combination thereof. In another embodiment, the solid oxide may include silica, alumina, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or any combination thereof. In another embodiment, the solid oxide may include silica-alumina, silica-coated alumina, titania-silica, silica-zirconia, alumina-boria or any combination of these. In another embodiment, the solid oxide may comprise silica; alternatively, alumina; alternatively, silica-alumina; or, alternatively, silica-coated alumina.
[0071] Silica-alumina, which can be used normally can have an alumina content of about 5 to about 95% by weight. In one embodiment, the alumina content of silica-alumina can be from about 5 to about 50%, or about 8% to about 30%, alumina by weight. In another embodiment, silica-alumina compounds with high alumina content can be employed, in which the alumina content of these silica-alumina compounds can normally vary from about 60% to about 90%, or about 65% for about 80%, alumina by weight. According to 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, pore volume and particle size, as would be recognized by those skilled in the art.
[0072] The electron removal 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 removal anion electron). According to one embodiment, the electron removal component can be an electron removal 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 removal anions may include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, counterions, trifluoromethanesulfonate, fluoroirate, fluorotitanate, fluorotitanate, phosphorate similar, including mixtures and combinations thereof. In addition, other ionic or non-ionic compounds that serve as sources for these electron removal anions can also be employed. It is anticipated that the electron removal anion may be, or may comprise, fluoride, chloride, bromide, phosphate, trifluoromethanesulfonate, bisulfate, or sulfate and the like or any combination of these, in some embodiments herein. In other embodiments, the electron-removing anion can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, counterions, trifluoromethanesulfonate, fluorozirconate, fluorotitanate and the like, or combinations thereof.
[0073] 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 zirconia-silica, chlorinated zirconia-silica, brominated silica zirconia, sulfated zirconia-silica, fluoridated titanium-silica, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-coated silica alumina and the like, as well as any mixture or combination thereof. In another embodiment, the dual catalyst system may comprise a support-activator, and the support-activator may comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated zirconia-silica, fluorinated silica-coated alumina, sulfated silica-coated alumina and the like, as well as any mixture or combination thereof.
[0074] Commonly used polymerization co-catalysts may include, but are not limited to, alkyl metal or organometal co-catalysts, with the metal encompassing boron, aluminum and the like. The dual catalyst systems presented herein can comprise a co-catalyst, or a combination of co-catalysts. For example, boron alkyl and / or alkyl aluminum compounds can often be used as co-catalysts in such catalyst systems. Representative boron compounds can include, but are not limited to, tri-n-butyl borane, tripropylborane, triethylborane and the like, and this includes combinations of two or more of these materials. While not limited to them, representative aluminum compounds (for example, organoaluminium compounds) may include, trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n- octyl aluminum, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum chloride and the like, as well as any combination of these. OLEFINE MONOMERS AND OLEFINE POLYMERS
[0075] Olefin monomers contemplated in this document typically include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. Homopolymerization processes using a simple olefin, such as ethylene, propylene, butene, hexene, octene and the like, are included, as well as copolymerization, terpolymerization, etc., reactions using an olefin monomer with at least one different olefinic compound. As previously disclosed, polymerization processes are intended to encompass oligomerization processes.
[0076] As an example, any resulting ethylene copolymer, 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.
[0077] Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can 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, the four normal octenes (e.g., 1-octene), the four normal nonenos, the five normal decenes, and so on, 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 in this document. Styrene can also be used as a monomer or as a comonomer. In one embodiment, the olefin monomer can be 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.
[0078] 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 C3-C20 α-olefin etc.) According to one embodiment, the olefin monomer in the polymerization process can be ethylene. In this embodiment, examples of suitable olefin comonomers may include, 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 their combinations. According to one 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, a comonomer can comprise 1-butene, 1-hexene, 1-octene or combinations thereof.
[0079] In general, the amount of comonomer introduced into a polymerization reactor to produce the 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 comonomer based on the total weight of the monomer and comonomer. In yet another embodiment, the amount of comonomer introduced into a polymerization reactor can be from about 0.1 to about 35 weight percent 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% of the weight percent comonomer based on the total weight of the monomer and comonomer.
[0080] While not intended to be bound by this theory, where branched, substituted, or functionalized olefins are used as reagents, it is believed that a steric impediment can prevent and / or delay the polymerization reaction. Thus, branched and / or cyclic part (s) of the olefin removed somewhat from the carbon-carbon double bond would not be expected to hinder the reaction in the way that the same olefin substituent located closest to the carbon-carbon double bond could.
[0081] According to one embodiment, at least one monomer / reagent can be ethylene, thus, the polymerization reaction can be a homopolymerization involving only ethylene or a copolymerization with a different acyclic, cyclic, terminal, internal, linear, branched olefin. , substituted or unsubstituted. In addition, the methods disclosed in this document are intended for olefin to also encompass diolefin compounds which include, but are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, and the like.
[0082] Olefin polymers encompassed herein may include any polymer (or oligomer) produced from any olefin monomer (and optional comonomer (s)) described herein. For example, the olefin polymer may comprise an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer (for example, 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 polymeric components may be present in the olefin polymer, in addition to the higher molecular weight component and the lower molecular weight component. Thus, 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. POLYMERIZATION REACTOR SYSTEMS
[0083] The disclosed methods are intended for any olefin polymerization process using various types of polymerization reactors, polymerization reactor systems and polymerization reaction conditions. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing (including oligomerization) of olefin monomers and comonomers (one or more of a comonomer) 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, gaseous reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor and the like, or combinations thereof. The polymerization conditions for the various types of the reactor are well known to those skilled in the art. Gaseous phase can comprise fluidized bed reactors or horizontal stage reactors. Slurry reactors can comprise vertical or horizontal circuits. High pressure reactors can contain autoclave or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes can use intermittent or continuous product discharge. Polymerization reactor processes and systems may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, and / or diluent.
[0084] A polymerization reactor system may comprise a single reactor or multiple reactors (2 reactors, more than 2 reactors, etc.) of the same or of a 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. Production of polymers in multiple reactors can include several steps in at least two separate polymerization reactors, interconnected by a transfer device making it possible to transfer the polymers resulting from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may differ from the operational conditions in other reactor (s). Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent continuous polymerization reactors. Multiple reactor systems can include any combination including, without limitation, multiple cycle reactors, multiple gas phase reactors, a combination of gas phase and cycle reactors, multiple high pressure reactors or a combination of high pressure reactors with reactors cycle and / or gas. The multiple reactors can be operated in series, in parallel, or both.
[0085] According to one embodiment, the polymerization reactor system may comprise at least slurry reactor in the circuit comprising vertical or horizontal circuits. Monomer, diluent, catalyst and comonomer can be continuously fed through a cycle 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 a suspension comprising polymer particles and the diluent from that reactor. Effluent from the reactor can be abruptly evaporated to remove liquids that comprise the polymer diluent, monomer and / or solid comonomer. Various technologies can be used for this separation step including, but not limited to, instant evaporation which can include any combination of heat addition and pressure reduction; separation by cyclonic action in a cyclone or hydrocyclone; or separation by centrifugation.
[0086] A typical sludge polymerization process (also known as particle-shaped process) is disclosed, for example, in US Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235 , 6,262,191 and 6,833,415, each of which is incorporated herein by reference in its entirety.
[0087] Suitable diluents used in sludge polymerization include, among others, 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 circuit polymerization reactions can occur under mass conditions, where no diluents are used. One example is the polymerization of propylene monomer, as disclosed in U.S. Patent No. 5,455,314, which is incorporated herein by reference in its entirety.
[0088] According to another embodiment, the polymerization reactor system may comprise at least one gas phase reactor (for example, a fluidized bed reactor). Such reactor systems can employ a continuous recycling stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. 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 fresh or new monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for a multi-stage gas phase olefin polymerization, in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones, while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. A type of gas phase reactor is disclosed in Patent Nos. U.S. 5,352,749, 4,588,790 and 5,436,304, each of which are incorporated herein by reference in their entirety.
[0089] According to yet another modality, the 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 zone of the reactor. The initiators, catalysts and / or catalyst components can be entrained in a gaseous flow and introduced into another zone of the reactor. Gas streams can be mixed for polymerization. Heat and pressure can be used appropriately to obtain optimal polymerization reaction conditions.
[0090] According to yet another embodiment, the polymerization reactor system may comprise a solution polymerization reactor, in which the monomer / monomer is contacted with the catalyst composition by appropriate 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. Agitation can be used to obtain better temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
[0091] The polymerization reactor system may further comprise any combination of at least one feedstock, feed system, at least one feed from the catalyst system or catalyst components, and / or at least one polymer recovery system . Suitable reactor systems may further comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, reactor refrigeration, 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.
[0092] Polymerization conditions that can be controlled for efficiency and to provide the properties of the desired polymer can include temperature, pressure and the concentrations of various reagents. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. A suitable polymerization temperature can be any temperature below the depolymerization temperature, according to the Gibbs Free Energy Equation. This typically ranges from about 60 ° C to about 280 ° C, for example, or from 60 ° C to about 110 ° C, depending on the type of polymerization reactor. In some reactor systems, the polymerization temperature can generally be within a range of about 70 ° C to about 90 ° C, or from about 75 ° C to about 85 ° C.
[0093] Appropriate pressures will also vary according to the reactor and the type of polymerization. The pressure for liquid phase polymerizations in a loop reactor can typically be less than 1000 psig. The pressure for gas phase polymerization can be in the range of 200 to 500 psig. High pressure polymerization in tubular or autoclave reactors can generally be carried out 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
[0094] Modalities of the invention are further illustrated by the following examples, which should not be considered in any way to impose limitations on the scope of this invention described in this document. Various other aspects, modalities, modifications, and respective equivalents that, after reading the description here, can be suggested to one of those skilled in the art without departing from the meaning of the present invention or the scope of the added claims.
[0095] Molecular Weight and Molecular Weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent company) equipped with an IR4 detector (PolymerChar, Spain) and three Styragel HMW-6E GPC columns (Waters, MA ) running at 145 ° C flow rate of the mobile phase 1, 2,4-trichlorobenzene (TCB) containing 0.5 g / L 2,6-di-t-butyl-4-methylphenol (BHT) was fixed at 1 ml / min and the concentrations of polymer solutions were generally maintained 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 h with occasional and gentle stirring 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, and MARLEX BHB5003, as a broad standard. The full table of the broad standard was predetermined in a separate experiment with SEC-MALS. EXAMPLES 1-5 Impact of the polymerization reaction temperature on the molecular weight distribution and on the ratio between the higher molecular weight component and the lower molecular weight component of the polymer.
[0096] The polymerization experiments of examples 1-5 were carried out in a one-gallon (3.8-L) stainless steel reactor with 2 L of isobutane. No hydrogen and comonomers were used in these examples. 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. MET-A and MET-B metallocenes had the following structures:

[0097] Approximately 1.5 mg of MET-A and 1.5 mg of MET-B (a weight ratio of 1: 1) were used in examples 1-5 and the metallocene solutions MET-A and MET-B were pre-mixed before being loaded into the reactor.
[0098] The polymerization experiments were carried out as follows. First, 1 mmol of triisobutylaluminum (TIBA), 300 mg of sulfated alumina and the premixed metallocene solution containing META and MET-B were added in that order through a loading port while slowly isobutane vapor was vented. The loading door was closed and 2L of isobutane was added. The reactor contents were stirred and heated to the desired polymerization reaction temperature, and this temperature was maintained for the duration of 45 min of the polymerization experiment using an automatic temperature control system. Ethylene was fed on demand to maintain 14% mol of ethylene (based on isobutane). After the polymerization experiment was completed, the reactor was cooled and ventilated and the polymer produced was removed from the reactor and dried.
[0099] Table I summarizes the reaction temperature, amount of polymer produced and the weight ratio between the higher molecular weight component and the lower molecular weight component of the polymer, for examples 1-5. The ratio of the higher molecular weight component to the lower molecular weight component of the polymer is illustrated graphically in FIG. 1 for the polymers of examples 1-5. The weight ratios in table I were obtained by fitting the respective molecular weight distribution curves with a Gaussian distribution. FIG. 1 demonstrates the impact of the polymerization reaction temperature on the molecular weight distribution (amount of polymer versus the log of molecular weight). As shown in FIG. 1, and unexpectedly, as the reaction temperature increased from 85 ° C to 100 ° C, the weight ratio between the higher molecular weight component and the lower molecular weight component increased (for example, relatively more high molecular weight material was produced). In addition, the impact of temperature appeared to change the relative heights of the lower molecular weight and the higher molecular peaks, as shown in FIG. 1, but it did not appear to significantly change the entire molecular weight distribution to a higher (right) or lower (left) molecular weight. Table I. Examples 1-5.
EXAMPLES 6-8 Impact of the reaction time of the catalyst system on the molecular weight distribution and on the ratio between the higher molecular weight component and the lower molecular weight component of the polymer.
[0100] The polymerization experiments of examples 6-8 were performed in substantially the same manner as those of examples 1-5, with the following differences. In examples 6-8, approximately 2 mg each of MET-A and MET-B (a weight ratio of 1: 1), 0.8 mmol of TIBA and 200 mg of sulfated alumina were used. The polymerization reaction temperature was 92 oC, and the ethylene concentration was 14 mol% (based on isobutane).
[0101] The reaction times to obtain examples 6-8 ranged from 25 min to 60 min, as shown in table II, which also lists the amount of polymer produced and the weight ratio between the largest molecular weight component and the lower molecular weight component of the polymer, for examples 6-8. The ratio of the higher molecular weight component to the lower molecular weight component of the polymer is illustrated graphically in FIG. 2 for the polymers of examples 6-8. The weight ratios in table II were obtained by fitting the distribution curves of the respective molecular weight with a Gaussian distribution. Fig. 2 demonstrates the impact of the reaction time on the molecular weight distribution (amount of polymer versus the log of molecular weight). As shown in FIG. 2, and unexpectedly, as the reaction time increased from 25 to 60 min., The weight ratio between the higher molecular weight component and the lower molecular weight component increased (for example, relatively more high molecular weight material was produced) . In addition, the impact of the reaction time appeared to change the relative heights of the lower molecular weight and the higher molecular peaks, as shown in FIG. 2, but it did not appear to significantly change the entire molecular weight distribution to a higher (right) or lower (left) molecular weight. Table II EXAMPLES 6-8

[0102] The invention has been described above with reference to numerous specific embodiments and examples. Many variations will be suggested 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 attached claims. Other embodiments of the invention may include, but are not limited to, the following:
[0103] Modality Polymerization process, the process characterized by the fact that it comprises: (1) bringing into contact a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions for produce an olefin polymer, where the olefin polymer is composed of a major molecular weight component and a minor molecular weight component, wherein the double catalyst system comprises a first metallocene catalyst component and a second catalyst component metallocene, and in which the polymerization conditions comprise a reaction temperature and a residence time of a dual catalyst system; and (2) controlling a weight ratio between the higher molecular weight component and the lower molecular weight component by adjusting the reaction temperature and / or the residence time of the dual catalyst system.
[0104] Modality 2. Method of controlling a weight ratio of a component of higher molecular weight and a component of lower molecular weight of an olefin polymer, the method characterized by the fact that it comprises: (i) putting in contact a double system of catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the olefin polymer, where the double catalyst system comprises a first metallocene catalyst component and a second component of metallocene catalyst, and in which the polymerization conditions comprise a reaction temperature and a residence time of a dual catalyst system; and (ii) adjusting the reaction temperature and / or residence time of the dual catalyst system to control the weight ratio between the highest molecular weight component and the lowest molecular weight component.
[0105] Modality 3. Process for producing an olefin polymer with a target weight ratio between a component of higher molecular weight and a component of lower molecular weight, the process characterized by the fact that it comprises: (a) bringing into contact a system double catalyst 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 and a second metallocene catalyst component, and wherein the polymerization conditions comprise a reaction temperature and a residence time of a dual catalyst system; and (b) controlling the reaction temperature and / or residence time of the double catalyst reactor system to produce the olefin polymer with the target weight ratio between the highest molecular weight component and the lowest molecular weight component.
[0106] Mode 4. Method or process as defined in any of the modalities 1-3, characterized by the fact that it understands that the double catalyst system comprises any activator disclosed in this document.
[0107] Modality 5. Method or process defined as in any of modalities 1-4, characterized by the fact that it understands that the double catalyst system comprises an activator support, an aluminoxane compound, an organoborate or organoboro compound, a ionizing ionic compound, or any combination of these.
[0108] Modality 6. Method or process defined as in any of modalities 1-5, characterized by the fact that it understands that the double catalyst system comprises an aluminoxane compound, an organoborate or organoboro compound, an ionizing ionic compound, or any combination of these.
[0109] Mode 7. Method or process as defined in any of modalities 1-6, characterized by the fact that it understands that the double catalyst system comprises an aluminoxane compound.
[0110] Modality 8. Method or process as defined in any of modalities 1-6, characterized by the fact that it understands that the double catalyst system comprises an organoborate or organoboro compound.
[0111] Mode 9. Method or process as defined in any of modalities 1-6, characterized by the fact that it understands that the double catalyst system comprises an ionizing ionic compound.
[0112] Mode 10. Method or process as defined in any of modalities 1-5, characterized by the fact that it understands that the double catalyst system comprises an activator support comprising a solid oxide treated with an electron-withdrawing anion, for example , comprising any solid oxide and any electron-withdrawing anion disclosed in this document.
[0113] Mode 11. Method or process as defined in any of modalities 1-5, characterized by the fact that it comprises that the double catalyst system comprises an activator support comprising fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, silica -Fluoridated alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated zirconia-silica, chlorinated zirconia-silica, brominated silica-zirconia, sulfated zirconia-fluoridated silica-titania, fluoridated silica-titanium, sulfated silica-coated alumina, phosphate-silica-coated alumina and the like, as well as any mixture or combination thereof.
[0114] Modality 12. Method or process as defined in any one of modalities 1-5, characterized by the fact that it understands that the double catalyst system comprises an activator support comprising fluoridated alumina, sulfated alumina, fluorinated silica-alumina, silica- sulfated alumina, fluoridated zirconia-silica, fluoridated silica-coated alumina, sulfated silica-coated alumina or any combination thereof.
[0115] Mode 13. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the double catalyst system comprises any co-catalyst disclosed in this document, for example, an alkyl metal, organoalumin etc.
[0116] Modality 14. Method or process as defined in any of the preceding claims, characterized by the fact that the double catalyst system comprises an organoaluminium compound that includes trimethylaluminum, triethylalumin, tri-n-propylaluminum, tri-n- butylaluminum, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminium chloride or any combination thereof.
[0117] Modality 15. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight increases as the reaction temperature increases .
[0118] Mode 16. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the reaction temperature is in any range of reaction temperatures disclosed in this document.
[0119] Mode 17. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the reaction temperature is in the range of about 60 ° C to about 110 ° C, or about 80 ° C to about 105 ° C.
[0120] Modality 18. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight increases as the residence time increases (or reaction time) of the dual catalyst system.
[0121] Mode 19. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the residence time of the double catalyst system is in any residence time interval disclosed in this document.
[0122] Mode 20. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the resistance time of the double catalyst system is in a range of about 10 min to about 2 hours, or about 15 min to about 90 min.
[0123] Mode 21. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight is in any range of weight ratios disclosed in this document.
[0124] Mode 22. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight is in a range of about 1 : 100 to about 100: 1, from about 1:10 to about 10: 1, or from about 1: 5 to about 5: 1.
[0125] Mode 23. Method or process as defined in any of the preceding claims, characterized by the fact that it understands that the reactor solids% are in any range of solids% disclosed in this document.
[0126] Mode 24. Method or process as defined in any of the preceding claims, characterized by the fact that it comprises that the solid% reactor is in a range of about 30 to about 65% by weight.
[0127] Mode 25. Method or process as defined in any of the preceding claims, characterized by the fact that it comprises that the solid% reactor is in a range of about 30 to about 55% by weight.
[0128] Modality 26. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the polymerization reactor system comprises a batch reactor, a slurry reactor, a gas phase reactor, a reactor solution, a high pressure reactor, a tubular reactor, an autoclave reactor or a combination of these.
[0129] Modality 27. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor or a combination of these.
[0130] Modality 28. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the polymerization reactor system comprises a slurry reactor.
[0131] Mode 29. Method or process as defined in any of modalities 1-28, characterized by the fact that it understands that the polymerization reactor system comprises a single reactor.
[0132] Mode 30. Method or process as defined in any of modalities 1-28, characterized by the fact that it understands that the polymerization reactor system comprises 2 reactors.
[0133] Mode 31. Method or process as defined in any of modalities 1-28, characterized by the fact that it understands that the polymerization reactor system comprises more than 2 reactors.
[0134] Mode 32. Method or process as defined in any one of modalities 1-31, characterized by the fact that it understands that the olefin polymer has a multimodal molecular weight distribution.
[0135] Modality 33. Method or process as defined in any of modalities 1-31, characterized by the fact that it understands that the olefin polymer has a bimodal molecular weight distribution.
[0136] Modality 34. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the olefin monomer comprises a C2-C20 olefin.
[0137] Modality 35. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the olefin monomer and the optional olefin comonomer comprise a C2-C20 alpha-olefin.
[0138] Mode 36. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the olefin monomer comprises ethylene.
[0139] Mode 37. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the olefin monomer comprises ethylene and the optional olefin comonomer comprises a C3-C10 alpha-olefin.
[0140] Mode 38. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the olefin monomer comprises ethylene and the optional olefin comonomer comprises 1-butene, 1-hexene, 1-octene or one mixture of them.
[0141] Mode 39. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the olefin polymer comprises any olefin polymer disclosed in this document.
[0142] Mode 40. Method or process as defined in any of the previous modalities, characterized by the fact that the olefin polymer comprises an ethylene homopolymer, an ethylene / 1-hexene copolymer, an ethylene / 1- copolymer octene or a combination thereof.
[0143] Mode 41. Method or process as defined in any of the previous modalities, characterized by the fact that the olefin polymer comprises an ethylene copolymer, and the density of the ethylene copolymer is controlled by adjusting a molar ratio between ethylene and the olefin comonomer, and adjusting the ratio of the weight of the higher molecular weight component to the lower molecular weight component.
[0144] Mode 42. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the first metallocene catalyst component and the second metallocene catalyst component independently comprise chromium, vanadium, titanium, zirconium, hafnium or a combination of these.
[0145] Mode 43. Method or process as defined in any of the previous modalities, characterized by the fact that it understands that the first component of metallocene catalyst and the second component of metallocene catalyst independently comprise titanium, zirconium, hafnium or a combination of these .
[0146] Mode 44. Method or process as defined in any of the preceding modalities, characterized by the fact that it understands that the weight ratio between the first metallocene catalyst component and the second metallocene catalyst component is in any range of weight ratios disclosed in this document.
[0147] Mode 45. Method or process as defined in any of the preceding modalities, characterized by the fact that it understands that the weight ratio between the metallocene catalyst component and the second metallocene catalyst component is in a range of about 1: 100 to about 100: 1, about 1:10 to about 10: 1, about 1: 5 to about 5: 1, or about 1: 2 to 2: 1.
[0148] Modality 46. Method or process as defined in any of the preceding modalities, characterized by the fact that it comprises the first metallocene catalyst component, produces the lowest molecular weight component.
[0149] Mode 47. Method or process as defined in any of the preceding modalities, characterized by the fact that it understands that the first metallocene catalyst component comprises any metallocene catalyst component disclosed in this document.
[0150] Mode 48. Method or process as defined in any of the preceding modalities, characterized by the fact that it comprises the first metallocene catalyst component comprises zirconium.
[0151] Mode 49. Method or process as defined in any of the preceding modalities, characterized by the fact that it comprises the second metallocene catalyst component produces the component with the highest molecular weight.
[0152] Modality 50. Method or process as defined in any of the preceding modalities, characterized by the fact that it understands that the second metallocene catalyst component comprises any second metallocene catalyst component disclosed in this document.
[0153] Modality 51. Method or process as defined in any of the preceding modalities, characterized by the fact that it comprises the second metallocene catalyst component, comprising zirconium and / or hafnium.
[0154] Mode 52. Method or process as defined in any of modalities 1-51, characterized by the fact that it understands that a weight ratio between the first metallocene catalyst component and the second metallocene catalyst component is substantially constant, for example , for a special polymer grade.
[0155] Mode 53. Method or process as defined in any one of claims 1-51, characterized in that it further comprises the step of adjusting the weight ratio between the first metallocene catalyst component and the second metallocene catalyst component.
[0156] Mode 54. Method or process as defined in any of modalities 1-53, characterized by the fact that it understands that no hydrogen is added to the polymerization reactor system.
[0157] Mode 55. Method or process as defined in any of modalities 1-53, characterized by the fact that it understands that hydrogen is added to the polymerization reactor system, and the addition of hydrogen is substantially constant, for example, for a particular degree of polymer.
[0158] Mode 56. Method or process as defined in any of modalities 1-53, characterized by the fact that it also comprises a step of adding hydrogen to the polymerization reactor system to adjust a molecular weight parameter (for example, Mw, Mn, Mw / Mn, etc.) of the polymer.
[0159] Mode 57. Method or process as defined in any of modalities 1-53, characterized by the fact that it also comprises a step of adding hydrogen to the polymerization reactor system to adjust the average weight of the molecular weight (Mw ) and / or melt index (MI) of the polymer.
[0160] Mode 58. Method or process as defined in any of the modes 55-57, characterized by the fact that it understands that the hydrogen addition step decreases the Mw and / or increases the melt index of the polymer.
[0161] Mode 59. Method or process as defined in any of the modes 55-58, characterized by the fact that it understands that the hydrogen addition step increases the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight.
[0162] Modality 60. Method or process as defined in any of the previous modalities, characterized by the fact that it also comprises the steps of determining (or measuring) the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight and adjusting the reaction temperature and / or resistance time of the dual catalyst system based on the difference between the measured weight and the target weight ratio.
[0163] Mode 61. Polymerization process, the process characterized by the fact that it comprises: (1) bringing into contact a double catalyst system with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under conditions of polymerization to produce an olefin polymer, where the olefin polymer is composed of a major molecular weight component and a minor molecular weight component, wherein the double catalyst system comprises a first transition metal compound, a second compound of transition metal and an activator support and in which the polymerization conditions comprise a reaction temperature and a residence time of a dual catalyst system; and (2) controlling a weight ratio between the higher molecular weight component and the lower molecular weight component by adjusting the reaction temperature and / or the residence time of the dual catalyst system.
[0164] Mode 62. Method of controlling a weight ratio of a component of higher molecular weight and a component of lower molecular weight of an olefin polymer, the method characterized by the fact that it comprises: (i) bringing into contact a double system of catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the olefin polymer, where the double catalyst system comprises a first transition metal compound, a second compound of transition metal and an activator support and in which the polymerization conditions comprise a reaction temperature and a residence time of a dual catalyst system; and (ii) adjusting the reaction temperature and / or residence time of the dual catalyst system to control the weight ratio between the highest molecular weight component and the lowest molecular weight component.
[0165] Mode 63. Process for producing an olefin polymer with a target weight ratio between a component of higher molecular weight and a component of lower molecular weight, the process characterized by the fact that it comprises: (a) bringing into contact a system double catalyst 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 transition metal compound, a second transition metal compound and a support-activator and in which the polymerization conditions comprise a reaction temperature and a residence time of a dual catalyst system; and (b) controlling the reaction temperature and / or residence time of the double catalyst reactor system to produce the olefin polymer with the target weight ratio between the highest molecular weight component and the lowest molecular weight component.
[0166] Mode 64. Method or process as defined in any of the modalities 61-63, characterized by the fact that it understands that the double catalyst system includes any support-activator disclosed in this document.
[0167] Mode 65. Method or process as defined in any of the modalities 61-64, characterized by the fact that it understands that the double catalyst system comprises an activator support comprising a solid oxide treated with an electron-withdrawing anion, for example , comprising any solid oxide and any electron-withdrawing anion disclosed in this document.
[0168] Mode 66. Method or process as defined in any of the modalities 61-65, characterized by the fact that it understands that the double catalyst system comprises an activator support comprising fluoridated alumina, chlorinated alumina, brominated alumina, sulfated alumina, silica -Fluoridated alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated zirconia-silica, chlorinated zirconia-silica, brominated silica-zirconia, sulfated zirconia-fluorinated silica-titania, fluoridated silica-titania, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-silica-coated alumina and the like, as well as any mixture or combination thereof.
[0169] Mode 67. Method or process as defined in any of the modalities 61-65, characterized by the fact that it understands that the double catalyst system comprises an activator support comprising fluoridated alumina, sulfated alumina, fluorinated silica-alumina, silica- sulfated alumina, fluoridated zirconia-silica, fluoridated silica-coated alumina, sulfated silica-coated alumina or any combination thereof.
[0170] Mode 68. Method or process as defined in any of the modalities 61-67, characterized by the fact that it understands that the double catalyst system comprises any co-catalyst disclosed in this document, for example, an alkyl metal, organoalumin etc.
[0171] Mode 69. Method or process as defined in any of the modalities 61-68, characterized by the fact that it understands that the double catalyst system comprises an organoaluminium compound that includes trimethylaluminum, triethylalumin, tri-n-propylaluminum, triple n-butylalumin, triisobutylaluminum, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminium chloride or any combination thereof.
[0172] Mode 70. Method or process as defined in any of the modalities 61-69, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight increases as the temperature increases reaction.
[0173] Mode 71. Method or process as defined in any of the modalities 61-70, characterized by the fact that it understands that the reaction temperature is in any range of reaction temperatures disclosed in this document.
[0174] Mode 72. Method or process as defined in any of the modalities 61-71, characterized by the fact that it understands that the reaction temperature is in a range of about 60 ° C to about 110 ° C, or about from 80 ° C to about 105 ° C.
[0175] Mode 73. Method or process as defined in any of the modalities 61-72, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight increases as time increases residence time (or reaction time) of the dual catalyst system.
[0176] Mode 74. Method or process as defined in any of the modalities 61-73, characterized by the fact that it understands that the residence time of the double catalyst system is in any residence time interval disclosed in this document.
[0177] Mode 75. Method or process as defined in any of the modalities 61-74, characterized by the fact that it understands that the resistance time of the double catalyst system is in a range of about 10 min to about 2 hours, or from about 15 min to about 90 min.
[0178] Mode 76. Method or process as defined in any of the modalities 61-75, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight is in any range of reasons weight disclosed in this document.
[0179] Mode 77. Method or process as defined in any of the modalities 61-76, characterized by the fact that it understands that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight is in an interval of about from 1: 100 to about 100: 1, from about 1:10 to about 10: 1, or from about 1: 5 to about 5: 1.
[0180] Mode 78. Method or process as defined in any of the modalities 61-77, characterized by the fact that it understands that the solid% of reactor is in any range of solids% disclosed in this document.
[0181] Mode 79. Method or process as defined in any of the modalities 61-78, characterized by the fact that it understands that the solid% of reactor is in a range of about 30 to about 65% by weight.
[0182] Mode 80. Method or process as defined in any of the modalities 61-79, characterized by the fact that it understands that the solid% of reactor is in a range of about 30 to about 55% by weight.
[0183] Mode 81. Method or process as defined in any of the modalities 61-80, characterized by the fact that it understands that 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 of these.
[0184] Mode 82. Method or process as defined in any of the modalities 61-81, characterized by the fact that it understands that the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor or a combination of these.
[0185] Mode 83. Method or process as defined in any of the modalities 61-82, characterized by the fact that it understands that the polymerization reactor system comprises a slurry reactor.
[0186] Mode 84. Method or process as defined in any of the modalities 61-83, characterized by the fact that it understands that the polymerization reactor system comprises a single reactor.
[0187] Mode 85. Method or process as defined in any of the modalities 61-83, characterized by the fact that it understands that the polymerization reactor system comprises 2 reactors.
[0188] Mode 86. Method or process as defined in any of the modalities 61-83, characterized by the fact that it understands that the polymerization reactor system comprises more than 2 reactors.
[0189] Mode 87. Method or process as defined in any of the modalities 61-86, characterized by the fact that it understands that the olefin polymer has a multimodal molecular weight distribution.
[0190] Mode 88. Method or process as defined in any of the modalities 61-86, characterized by the fact that it understands that the olefin polymer has a bimodal molecular weight distribution.
[0191] Mode 89. Method or process as defined in any of the modalities 61-88, characterized by the fact that it understands that the olefin monomer comprises a C2-C20 olefin. Mode 90. Method or process as defined in any of the modalities 61-89, characterized by the fact that it understands that the olefin monomer and the optional olefin comonomer comprise a C2-C20 alpha-olefin.
[0192] Mode 91. Method or process as defined in any of the modalities 61-90, characterized by the fact that it understands that the olefin monomer comprises ethylene.
[0193] Mode 92. Method or process as defined in any of the modalities 61-91, characterized by the fact that it understands that the olefin monomer comprises ethylene and the optional olefin comonomer comprises a C3-C10 alpha-olefin.
[0194] Mode 93. Method or process as defined in any of the modalities 61-92, characterized by the fact that the olefin monomer comprises ethylene and the optional olefin comonomer comprises 1-butene, 1-hexene, 1-octene or a mixture of them.
[0195] Mode 94. Method or process as defined in any of the modalities 61-93, characterized by the fact that it understands that the olefin polymer comprises any olefin polymer disclosed in this document.
[0196] Mode 95. Method or process as defined in any of the modes 61-94, characterized by the fact that the olefin polymer comprises an ethylene homopolymer, an ethylene / 1-hexene copolymer, an ethylene / 1- octene or a combination thereof.
[0197] Mode 96. Method or process as defined in any of the modalities 61-95, characterized by the fact that the olefin polymer comprises an ethylene copolymer, and the density of the ethylene copolymer is controlled by adjusting a molar ratio between ethylene and the olefin comonomer, and adjusting the ratio of the weight of the higher molecular weight component to the lower molecular weight component.
[0198] Mode 97. Method or process as defined in any of the modalities 61-96, characterized by the fact that it understands that the first transition metal compound and the second transition metal compound independently comprise any transition metal disclosed in this document , for example, chromium, vanadium, titanium, zirconium, hafnium or a combination of these.
[0199] Mode 98. Method or process as defined in any of the modalities 61-97, characterized by the fact that it understands that the first transition metal compound and the second transition metal compound independently comprise any transition metal disclosed in this document , for example, chromium, titanium, zirconium, hafnium or a combination of these.
[0200] Mode 99. Method or process as defined in any of the modalities 61-98, characterized by the fact that it understands that the double catalyst system comprises any transition metal based catalyst system disclosed in this document, for example, that a catalyst system based on Ziegler-Natta, a chrome based catalyst system, a metallocene based catalyst system, a Phillips catalyst system, a Ballard catalyst system, a coordinating compound catalyst system, a post-metallocene catalyst or combinations thereof.
[0201] Mode 100. Method or process as defined in any of the modalities 61-99, characterized by the fact that it understands that the double catalyst system comprises a catalyst system based on Ziegler-Natta, a catalyst system based on chromium and / or a metallocene-based catalyst system.
[0202] Mode 101. Method or process as defined in any of the modalities 61-100, characterized by the fact that it understands that the double catalyst system comprises a catalyst system based on Ziegler-Natta.
[0203] Mode 102. Method or process as defined in any of the modalities 61-100, characterized by the fact that it understands that the double catalyst system comprises a catalyst system based on chromium.
[0204] Mode 103. Method or process as defined in any of the modalities 61-100, characterized by the fact that it understands that the double catalyst system comprises a catalyst system based on metallocene.
[0205] Mode 104. Method or process as defined in any of the modalities 61-103, characterized by the fact that it understands that the weight ratio between the first transition metal component and the second transition metal component is in any range of reasons weight disclosed in this document.
[0206] Mode 105. Method or process as defined in any of the modalities 61-104, characterized by the fact that it understands that the weight ratio between the first transition metal component and the second transition metal component is in an interval of about from 1: 100 to about 100: 1, from about 1:10 to about 10: 1, from about 1: 5 to about 5: 1, or from about 1: 2 to 2: 1.
[0207] Mode 106. Method or process as defined in any of the modalities 61-105, characterized by the fact that it understands that the first transition metal compound produces the lowest molecular weight component.
[0208] Mode 107. Method or process as defined in any of the modalities 61-106, characterized by the fact that it understands that the second transition metal compound produces the largest molecular weight component.
[0209] Mode 108. Method or process as defined in any of the modalities 61-107, characterized by the fact that it understands that a weight ratio between the first transition metal compound and the second transition metal compound is substantially constant, for example, for a special polymer grade.
[0210] Mode 109. Method or process as defined in any of the modalities 61-107, characterized by the fact that it also comprises the step of adjusting the weight ratio between the first transition metal compound and the second transition metal compound .
[0211] Mode 110. Method or process as defined in any of the modalities 61-109, characterized by the fact that it understands that no hydrogen is added to the polymerization reactor system.
[0212] Mode 111. Method or process as defined in any of the modalities 61-109, characterized by the fact that it understands that hydrogen is added to the polymerization reactor system, and the addition of hydrogen is substantially constant, for example, for a degree of polymer in particular.
[0213] Mode 112. Method or process as defined in any of the modalities 61-109, characterized by the fact that it also comprises a step of adding hydrogen to the polymerization reactor system to adjust a molecular weight parameter (for example, Mw, Mn, Mw / Mn, etc.) of the polymer.
[0214] Mode 113. Method or process as defined in any of the modalities 61-109, characterized by the fact that it also comprises a step of adding hydrogen to the polymerization reactor system to adjust the average weight of the molecular weight (Mw ) and / or melt index (MI) of the polymer.
[0215] Mode 114. Method or process as defined in any of the modalities 111-113, characterized by the fact that it understands that the hydrogen addition step decreases the Mw and / or increases the melt index of the polymer.
[0216] Mode 115. Method or process as defined in any of the modalities 111-114, characterized by the fact that it understands that the hydrogen addition step increases the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight.
[0217] Mode 116. Method or process as defined in any of the modalities 61-115, characterized by the fact that it also comprises the steps of determining (or measuring) the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight and adjust the reaction temperature and / or resistance time of the dual catalyst system based on the difference between the measured weight and the target weight ratio.

权利要求:
Claims (15)
[0001]
1. Polymerization process characterized by comprising: (1) contacting a double catalyst system with an olefin monomer and an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, in which the olefin polymer comprises a component of higher molecular weight and a component of lower molecular weight, wherein the double catalyst system comprises a first component of metallocene catalyst and a second component of metallocene catalyst, and in which the polymerization conditions comprise a reaction temperature and a residence time of the double catalyst system; and (2) controlling a weight ratio between the highest molecular weight component and the lowest molecular weight component by adjusting the reaction temperature and / or the residence time of the dual catalyst system, where the weight ratio between the component higher molecular weight and the lower molecular weight component increases as the reaction temperature increases.
[0002]
2. Process according to claim 1, characterized by the fact that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight increases as the residence time of the catalyst system increases.
[0003]
3. Process 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 of these.
[0004]
4. Process according to claim 1, characterized by the fact that the polymerization reactor system comprises a single reactor.
[0005]
5. Process according to claim 1, characterized in that the olefin monomer comprises ethylene and the olefin comonomer comprises a C3-C10 alpha-olefin.
[0006]
Process according to claim 1, characterized in that it further comprises the steps of: determining the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight; and adjusting the reaction temperature and / or resistance time of the dual catalyst system based on the difference between the determined weight ratio and a target weight ratio.
[0007]
Process according to claim 1, characterized in that the first metallocene catalyst component and the second metallocene catalyst component independently comprise titanium, zirconium, hafnium or a combination thereof.
[0008]
8. Process according to claim 1, characterized by the fact that the weight ratio between the first metallocene catalyst component and the second metallocene catalyst component is in the range of 1:10 to 10: 1.
[0009]
Process according to claim 1, characterized in that the weight ratio between the first metallocene catalyst component and the second metallocene catalyst component is substantially constant.
[0010]
10. Polymerization process characterized by comprising: (1) contacting a double catalyst system with an olefin monomer and an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, in which the The olefin polymer comprises a higher molecular weight component and a lower molecular weight component, in which the double catalyst system comprises a first transition metal compound, a second transition metal compound and a support activator, in which the Support activator comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated zirconia-chlorinated silica, chlorinated zirconia-silica , sulfated zirconia-silica, fluoridated silica-titania, fluoridated silica-coated alumina, sulfated silica-coated alumina, silica-coated alumina phosphate and any combination thereof, and wherein the polymerization conditions comprise a reaction temperature and a residence time of the dual catalyst system; and (2) controlling a weight ratio between the highest molecular weight component and the lowest molecular weight component by adjusting the reaction temperature, and / or the residence time of the dual catalyst system, where the weight ratio between the higher molecular weight component and the lower molecular weight component increases as the reaction temperature increases.
[0011]
11. Process according to claim 10, characterized in that the double catalyst system comprises a first transition metal compound, a second transition metal compound, a support activator and a co-catalyst.
[0012]
12. Process according to claim 1, characterized by the fact that: the double catalyst system comprises a first metallocene catalyst component, a second metallocene catalyst component, an activator and an optional co-catalyst, in which the activator comprises an activator-support, an aluminoxane compound, an organoborane or organoborate compound, an ionizing ionic compound or a combination thereof; the olefin monomer comprises ethylene and the olefin comonomer comprises 1-butene, 1-hexene, 1-octene or a mixture thereof; the first metallocene catalyst component and the second metallocene catalyst component independently comprise titanium, zirconium, hafnium or a combination thereof; and the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor or a combination thereof.
[0013]
13. Process according to claim 12, characterized by the fact that: the activator comprises an aluminoxane compound; the first metallocene catalyst component comprises a zirconium-based metallocene compound without a bridge; and the second metallocene catalyst component comprises a metallocene compound based on zirconium or bridged hafnium.
[0014]
Process according to claim 12, characterized in that the double catalyst system comprises: a first metallocene catalyst component comprising a zirconium-based metallocene compound without a bridge; a second metallocene catalyst component comprising a metallocene compound based on zirconium or bridged hafnium; a support activator comprising a solid oxide treated with an electron removal anion; and an organoaluminium compound.
[0015]
15. Process according to claim 1, characterized by the fact that the weight ratio between the component with the highest molecular weight and the component with the lowest molecular weight increases as the residence time of the catalyst system increases.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

DE1051004B|1953-01-27|1959-02-19|Phillips Petroleum Company, Bartlesville, OkIa. |Process for the production of high molecular weight olefin polymers or olefin copolymers|

---

US3226205A|1960-10-03|1965-12-28|Phillips Petroleum Co|Reactor impeller with feed inlet along shaft|

---

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

---

US3119569A|1962-03-28|1964-01-28|Baricordi Antonio|Grinding apparatus|

---

US3225023A|1962-11-30|1965-12-21|Phillips Petroleum Co|Process for controlling melt index|

---

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

---

US3622521A|1967-08-21|1971-11-23|Phillips Petroleum Co|Olefin polymerization with chromium and titanium-containing compounds|

---

US3625864A|1969-04-23|1971-12-07|Phillips Petroleum Co|Polymerization catalyst system additives|

---

US3900457A|1970-10-08|1975-08-19|Phillips Petroleum Co|Olefin polymerization catalyst|

---

US3887494A|1970-11-12|1975-06-03|Phillips Petroleum Co|Olefin polymerization catalyst|

---

US3976632A|1974-12-04|1976-08-24|Phillips Petroleum Company|Reactivation of organochromium olefin polymerization catalyst in presence of oxygen|

---

US4053436A|1975-08-26|1977-10-11|Phillips Petroleum Company|Spray dried titanium-containing catalyst for stress crack resistant polymer|

---

US4081407A|1976-03-18|1978-03-28|Phillips Petroleum Company|Catalyst support prepared by alcohol treatment of hydrogels|

---

US4151122A|1977-12-05|1979-04-24|Phillips Petroleum Company|Reduction and reoxidation of cogel or self-reduced catalyst|

---

US4182815A|1977-12-05|1980-01-08|Phillips Petroleum Company|Reduction and reoxidation of cogel or self-reduced catalyst|

---

US4247421A|1979-05-03|1981-01-27|Phillips Petroleum Company|Activation of supported chromium oxide catalysts|

---

US4297460A|1979-06-01|1981-10-27|Phillips Petroleum Co.|Treatment of silica|

---

US4248735A|1979-06-01|1981-02-03|Phillips Petroleum Company|Treatment of silica|

---

US4397766A|1979-12-14|1983-08-09|Phillips Petroleum Company|Solubilized chromium salt in particulate support|

---

US4296001A|1980-02-06|1981-10-20|Phillips Petroleum Company|Titanium impregnated silica-chromium catalysts|

---

US4301034A|1980-05-21|1981-11-17|Phillips Petroleum Company|Silica from single phase controlled hydrolysis of silicate ester|

---

US4339559A|1980-05-21|1982-07-13|Phillips Petroleum Company|Polymerization using silica from single phase controlled hydrolysis of silicate ester|

---

US4444964A|1980-12-31|1984-04-24|Phillips Petroleum Company|Polymerization process using phosphate supported chromium catalyst|

---

US4444965A|1980-12-31|1984-04-24|Phillips Petroleum Company|Olefin polymerization using chromium on an aluminum phosphate produced from a concentrated mass|

---

US4364854A|1980-12-31|1982-12-21|Phillips Petroleum Company|Acid gelling aluminum phosphate from concentrated mass and catalyst containing same|

---

US4364855A|1980-12-31|1982-12-21|Phillips Petroleum Company|Production of aluminum phosphate from concentrated mass|

---

US4364842A|1980-12-31|1982-12-21|Phillips Petroleum Company|Phosphate supported chromium catalyst|

---

US4444962A|1980-12-31|1984-04-24|Phillips Petroleum Company|Polymerization process using catalysts with acid gelled aluminum phosphate base|

---

US4504638A|1980-12-31|1985-03-12|Phillips Petroleum Company|Ethylene polymers made from phosphate supported chromium catalyst|

---

US4460756A|1981-04-02|1984-07-17|Phillips Petroleum Company|Olefin polymerization method|

---

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

---

US4392990A|1982-01-20|1983-07-12|Phillips Petroleum Company|Heating silica gel in inert atmosphere before activation|

---

US4405501A|1982-01-20|1983-09-20|Phillips Petroleum Company|Aging of chromium-containing gel at high pH|

---

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

---

US4530914A|1983-06-06|1985-07-23|Exxon Research & Engineering Co.|Process and catalyst for producing polyethylene having a broad molecular weight distribution|

---

US4806513A|1984-05-29|1989-02-21|Phillips Petroleum Company|Silicon and fluorine-treated alumina containing a chromium catalyst and method of producing same|

---

US4547557A|1984-07-09|1985-10-15|Phillips Petroleum Company|Silica-titania cogel from two-step hydrolysis|

---

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

---

US4820785A|1986-06-16|1989-04-11|Phillips Petroleum Company|In situ comonomer generation in olefin polymerization|

---

US4735931A|1986-06-16|1988-04-05|Phillips Petroleum Company|In situ comonomer generation in olefin polymerization|

---

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

---

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

---

US4855271A|1987-06-22|1989-08-08|Phillips Petroleum Company|Catalyst and polymerization of olefins|

---

US4981831A|1988-07-25|1991-01-01|Phillips Petroleum Company|Twice-aged porous inorganic oxides, catalysts, and polymerization processes|

---

US5705478A|1989-02-21|1998-01-06|Washington University|Covalently linked β subunits of the glycoprotein hormones as antagonists|

---

US4988657A|1989-10-06|1991-01-29|Phillips Petroleum Company|Process for olefin polymerization|

---

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

---

US5237025A|1990-10-09|1993-08-17|Phillips Petroleum Company|Process for making bimodal polyolefins using two independent particulate catalysts|

---

CA2043904C|1990-10-09|1997-10-07|Kent E. Mitchell|Olefin polymerization|

---

US5221654A|1991-01-02|1993-06-22|Phillips Petroleum Company|Fluorided aluminas, catalysts, and polymerization processes|

---

US5219817A|1991-01-02|1993-06-15|Phillips Petroleum Company|Fluorided aluminas, catalysts, and polymerization processes|

---

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|

---

US5571880A|1991-05-09|1996-11-05|Phillips Petroleum Company|Organometallic fluorenyl compounds and use thereof in an alpha-olefin polymerization process|

---

US5610247A|1991-07-23|1997-03-11|Phillips Petroleum Company|Unbridged metallocenes of 9-substituted fluorenyl compounds and use thereof|

---

US5210352A|1991-05-09|1993-05-11|Phillips Petroleum Company|Fluorene compounds|

---

US5451649A|1991-05-09|1995-09-19|Phillips Petroleum Company|Organometallic fluorenyl compounds, preparation, and use|

---

US5668230A|1991-07-23|1997-09-16|Phillips Petroleum Company|Olefin polymerization|

---

US5466766A|1991-05-09|1995-11-14|Phillips Petroleum Company|Metallocenes and processes therefor and therewith|

---

US5631335A|1991-05-09|1997-05-20|Phillips Petroleum Company|Process of polymerizing olefins using diphenylsilyl or dimethyl tin bridged 1-methyl fluorenyl metallocenes|

---

US5401817A|1991-05-09|1995-03-28|Phillips Petroleum Company|Olefin polymerization using silyl-bridged metallocenes|

---

US5191132A|1991-05-09|1993-03-02|Phillips Petroleum Company|Cyclopentadiene type compounds and method for making|

---

US5436305A|1991-05-09|1995-07-25|Phillips Petroleum Company|Organometallic fluorenyl compounds, preparation, and use|

---

US5627247A|1991-05-09|1997-05-06|Phillips Petroleum Company|Organometallic fluorenyl compounds and use thereof in olefin polymerization|

---

US5594078A|1991-07-23|1997-01-14|Phillips Petroleum Company|Process for producing broad molecular weight polyolefin|

---

US5244990A|1992-01-07|1993-09-14|Phillips Petroleum Company|Prepolymerized catalyst and use thereof|

---

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|

---

US5179178A|1992-05-15|1993-01-12|Phillips Petroleum Company|Olefin polymerization|

---

US5399636A|1993-06-11|1995-03-21|Phillips Petroleum Company|Metallocenes and processes therefor and therewith|

---

US5347026A|1993-06-11|1994-09-13|Phillips Petroleum Company|Fluorene compounds and methods for making|

---

US5354721A|1993-06-22|1994-10-11|Phillips Petroleum Company|Organo-aluminoxy product and use|

---

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

---

US5624877A|1994-02-25|1997-04-29|Phillips Petroleum Company|Process for producing polyolefins|

---

US5496781A|1994-05-16|1996-03-05|Phillips Petroleum Company|Metallocene catalyst systems, preparation, and use|

---

US5498581A|1994-06-01|1996-03-12|Phillips Petroleum Company|Method for making and using a supported metallocene catalyst system|

---

US5541272A|1994-06-03|1996-07-30|Phillips Petroleum Company|High activity ethylene selective metallocenes|

---

US5420320A|1994-06-08|1995-05-30|Phillips Petroleum Company|Method for preparing cyclopentadienyl-type ligands and metallocene compounds|

---

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|

---

US5563284A|1994-09-09|1996-10-08|Phillips Petroleum Company|Cyclopentadienyl-type ligands, metallocenes, 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|

---

US5631203A|1995-05-04|1997-05-20|Phillips Petroleum Company|Metallocene compounds and preparation thereof containing terminal alkynes|

---

US5654454A|1995-05-30|1997-08-05|Phillips Petroleum Company|Metallocene preparation and use|

---

US5869575A|1995-08-02|1999-02-09|The Dow Chemical Company|Ethylene interpolymerizations|

---

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

---

US5705579A|1996-07-17|1998-01-06|Phillips Petroleum Company|Olefin polymerization|

---

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|

---

US6355594B1|1999-09-27|2002-03-12|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6395666B1|1999-09-29|2002-05-28|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6613712B1|1999-11-24|2003-09-02|Phillips Petroleum Company|Organometal catalyst compositions with solid oxide supports treated with fluorine and boron|

---

US6548442B1|1999-12-03|2003-04-15|Phillips Petroleum Company|Organometal compound catalyst|

---

CA2395292C|1999-12-16|2009-05-26|Phillips Petroleum Company|Organometal compound catalyst|

---

BR9906022A|1999-12-30|2001-09-25|Opp Petroquimica S A|Process for the controlled production of polyethylene and its copolymers|

---

EP1419185B8|2001-07-17|2005-08-10|O &amp; D Trading Limited|Polymerisation control process|

---

EP1444272A1|2001-09-11|2004-08-11|Exxonmobil Chemical Patents Inc.|Method for preparing polyolefins|

---

EP1446428B1|2001-11-19|2006-10-11|Ineos Europe Limited|Polymerisation control process|

---

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|

---

KR101113341B1|2002-10-15|2012-09-27|엑손모빌 케미칼 패턴츠 인코포레이티드|Multiple catalyst system for olefin polymerization and polymers produced therefrom|

---

US7106437B2|2003-01-06|2006-09-12|Exxonmobil Chemical Patents Inc.|On-line measurement and control of polymer product properties by Raman spectroscopy|

---

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

---

JP5301151B2|2004-04-07|2013-09-25|ユニオンカーバイドケミカルズアンドプラスティックステクノロジーエルエルシー|Method for controlling olefin polymerization|

---

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

---

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

---

DE102005035477A1|2005-07-26|2007-02-01|Basell Polyolefine Gmbh|Preparation of olefin polymers, e.g. polyethylene, for producing pressure pipes for transport of gas and wastewater, by polymerization of alpha-olefin with hybrid catalyst to produce higher and lower molecular weight polymer components|

---

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

---

US7625982B2|2005-08-22|2009-12-01|Chevron Phillips Chemical Company Lp|Multimodal polyethylene compositions and pipe made from same|

---

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|

---

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

---

US7786227B2|2007-08-07|2010-08-31|Equistar Chemicals, Lp|Monomer concentration prediction and control in a polymerization process|

---

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|

---

US20130274427A1|2010-12-22|2013-10-17|BASELL POLOYOLEFINE GmbH|Process for controlling the relative activity of active centers of catalyst systems comprising at least one late transition metal catalyst component and at least one ziegler catalyst component|BR112017026907A2|2015-07-08|2018-08-14|Chevron Phillips Chemical Co Lp|ziegler-natta - metallocene dual catalyst systems with activator supports|

---

US9540457B1|2015-09-24|2017-01-10|Chevron Phillips Chemical Company Lp|Ziegler-natta—metallocene dual catalyst systems with activator-supports|

---

US9845367B2|2015-09-24|2017-12-19|Chevron Phillips Chemical Company Lp|Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina|

---

KR101711788B1|2016-03-09|2017-03-14|한화케미칼 주식회사|Hybride catalyst compositon, preparation method thereof, and manufactured polyolefin using the same|

---

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|

---

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

---

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|

---

EP3700947A1|2017-10-23|2020-09-02|ExxonMobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

WO2020046406A1|2018-08-30|2020-03-05|Exxonmobil Chemical Patents Inc.|Polymerization processes and polymers made therefrom|

---

US10899860B2|2018-08-30|2021-01-26|Exxonmobil Chemical Patents Inc.|Polymerization processes and polymers made therefrom|

---

US10927205B2|2018-08-30|2021-02-23|Exxonmobil Chemical Patents Inc.|Polymerization processes and polymers made therefrom|

---

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

---

WO2019094131A1|2017-11-13|2019-05-16|Exxonmobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

WO2019094132A1|2017-11-13|2019-05-16|Exxonmobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

US11130827B2|2017-11-14|2021-09-28|Exxonmobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

EP3717525A1|2017-11-28|2020-10-07|ExxonMobil Chemical Patents Inc.|Catalyst systems and polymerization processes for using the same|

---

EP3717527A1|2017-11-28|2020-10-07|ExxonMobil Chemical Patents Inc.|Polyethylene compositions and films made therefrom|

---

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:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/625,065|US8940842B2|2012-09-24|2012-09-24|Methods for controlling dual catalyst olefin polymerizations|

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US13/625,065|2012-09-24|

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PCT/US2013/059961|WO2014047010A1|2012-09-24|2013-09-16|Methods for controlling dual catalyst olefin polymerizations|

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