polymerization process of olefins, ethylene polymer, article comprising the same and catalyst compos

专利摘要:
CATALYST COMPOSITIONS FOR PRODUCTION OF HIGH Mz / Mw POLYOLEFINS. The present invention provides a polymerization process using a double loop-metallocene catalyst system. Polymers produced from the polymerization process are also supplied, and these polymers have a reverse comonomer distribution, a non-bimodal molecular weight distribution, a Mw / Mn ratio of about 3 to about 8, and a Mz ratio / Nw of about 3 to about 6.
公开号:BR112012026842B1
申请号:R112012026842-2
申请日:2011-04-15
公开日:2020-10-27
发明作者:Qing Yang；Max P. Mcdaniel；William B. Beaulieu；Joel L. Martin；Tony Crain
申请人:Chevron Phillips Chemical Company Lp.；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
[0001] The present invention generally relates to the field of olefin polymerization catalysis, metallocene catalyst compositions, methods for the polymerization and copolymerization of olefins and polyolefins. More specifically, this invention relates to olefin polymers having high Mz / Mw ratios, and the catalyst compositions and polymerization processes used to produce such olefin polymers.
[0002] In the polymer sciences, several measurements of the average molecular weight of a polymer are used. For example, Mn is the average molecular weight of the number, Mw is the average molecular weight of the weight and Mz is the average molecular weight of z. The Mw / Mn ratio is often used as a measure of the amplitude of the polymer's molecular weight distribution, and this relationship is also known as the polydispersity index. The Mz / Mw ratio is a measure of the amplitude of the high molecular weight fraction of the polymer molecular weight distribution.
[0003] Homopolymers, copolymers, terpolymers, etc., of polyolefin can be produced using various combinations of catalyst polymerization systems and processes. A method that can be used to produce such polyolefins employs a metallocene-based catalyst system. Polyolefins having a unimodal molecular weight distribution, produced using a metallocene-based catalyst system, generally have relatively low Mw / Mn and Mz / Mw indices. It would be beneficial for the production of polyolefins to use a metallocene-based catalyst system that has higher Mz / Mw indices than conventional metallocene-based polyolefins. Consequently, it is for this purpose that the present invention is intended. SUMMARY OF THE INVENTION
[0004] The present invention discloses polymerization processes, employing dual catalyst systems for the production of polymers with high rates of Mz / Mw
[0005] According to one aspect of the present invention, a catalyst composition is provided, and that catalyst composition comprises a catalyst component I, a catalyst component II and an activator. In another aspect, an olefin polymerization process is provided and, in this aspect, the process comprises contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, in that the catalyst composition comprises a catalyst component I, a catalyst component II and an activator.
[0006] In these catalyst compositions and polymerization processes, the catalyst component can comprise at least one loop-metallocene compound having the formula (I):
I), where: MA is Ti, Zr, or Hf; X1A and are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; EA is C or Si; R1A and R2As are independently H, a hydrocarbyl group having up to 18 carbon atoms, or R1A and R2A are linked to form a cyclic or heterocyclic group having up to 18 carbon atoms, where R1A and R2A are not aryl groups; R6A and R7A are independently H or a hydrocarbyl group having up to 18 carbon atoms; and CpA is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a heteroatom thereof, any substituent on CpA is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms.
[0007] In these catalyst compositions and polymerization processes, the catalyst component II can comprise at least one loop-metallocene compound with formula (II):
(II), where: MB is Ti, Zr, or Hf; X1B and X2B are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; EB is C or Si; R1B and R2B are independently H or a hydrocarbyl group having up to 18 carbon atoms, wherein at least one of R1B and R2B is an aryl group having up to 18 carbon atoms; R6B and R7B are independently H or a hydrocarbyl group having up to 18 carbon atoms; and CpB is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a heteroatom thereof, any substituent on CpB is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms.
[0008] Polymers produced from the polymerization of olefins using these catalyst systems, resulting in homopolymers, copolymers, and the like, can be used to produce various articles of manufacture. In some respects, of this invention, an ethylene polymer produced in this document can be characterized as having the following properties of the polymer: a non-bimodal molecular weight distribution, a Mw / Mn ratio of about 3 to about 8, a rate of Mz / Mw of about 3 to about 6, and an inverse comonomer distribution. BRIEF DESCRIPTION OF THE FIGURES
[0009] Figure 1 illustrates a representative bimodal molecular weight distribution curve.
[0010] Figure 2 illustrates a representative bimodal molecular weight distribution curve.
[0011] Figure 3 illustrates a representative bimodal molecular weight distribution curve.
[0012] Figure 4 illustrates a representative bimodal molecular weight distribution curve.
[0013] Figure 5 illustrates a representative bimodal molecular weight distribution curve.
[0014] Figure 6 illustrates a representative non-bimodal molecular weight distribution curve.
[0015] Figure 7 illustrates a representative non-bimodal molecular weight distribution curve.
[0016] Figure 8 illustrates a representative non-bimodal molecular weight distribution curve.
[0017] Figure 9 illustrates a representative non-bimodal molecular weight distribution curve.
[0018] Figure 10 illustrates a representative non-bimodal molecular weight distribution curve.
[0019] Figure 11 illustrates a representative non-bimodal molecular weight distribution curve.
[0020] Figure 12 illustrates the definitions of D90 and D10 in a molecular weight distribution curve.
[0021] Figure 13 illustrates the definitions of D85 and D15 in a molecular weight distribution curve.
[0022] Figure 14 illustrates a substantially linear short chain branching distribution.
[0023] Figure 15 illustrates a short chain branch distribution (SCBD) that is not substantially linear.
[0024] Figure 16 shows a graph of the molecular weight distributions of the polymers of Examples 5 and 6.
[0025] Figure 17 presents a graph of the number of short chain branches (SCB) per 1000 carbon atoms as a function of the logarithm of the molecular weight, and a linear regression analysis for the polymers of Examples 5 and 6.
[0026] Figure 18 presents a graph of the number of short chain branches (SCB) per 1000 carbon atoms as a function of the molecular weight logarithm, and a linear regression analysis for the polymer of example 6. DEFINITIONS
[0027] To define more clearly the terms used in this document, the following definitions are provided. Insofar as any definition or use provided by any document incorporated in this document by reference conflicts with the definition or use presented here, the definition or use presented in this document controls.
[0028] The term "polymer" is used throughout this document to include homopolymers, copolymers, olefin terpolymers, and so on. A copolymer is derived from an olefin monomer and an olefin comonomer, although a terpolymer is derived from an olefin monomer and two olefin comonomers. In this sense, "polymer" includes copolymers, terpolymers, etc., derived from any olefin monomer and comonomer (s) disclosed in this document. Similarly, an ethylene polymer includes ethylene homopolymers, ethylene copolymers, ethylene terpolymers and the like. For example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer would be categorized as ethylene 1-hexene copolymer.
[0029] Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process would involve contacting an olefin monomer (for example, ethylene) and an olefin comonomer (for example, 1-hexene) to produce a copolymer.
[0030] The hydrogen in this disclosure can refer to any hydrogen (H2) that is used in a polymerization process, or a hydrogen atom (H), which can be present, for example, in a metallocene compound. When used to denote a hydrogen atom, hydrogen will be displayed as "H", whereas if the intention is to publicize the use of hydrogen in a polymerization process, it will simply be referred to as "hydrogen".
[0031] The term "cocatalyst" is generally used in this document to refer to organoaluminium compounds, which can be a component of a catalyst composition. In addition, "cocatalyst" can refer to other components of a catalyst composition including, but not limited to, aluminoxanes, organoboro or organoborate compounds, and ionic and ionizing compounds, as disclosed in this document, when used, in addition to an activating support . The term "cocatalyst" is used regardless of the actual function of the compound or any chemical mechanism by which the compound can operate. In one aspect of this invention, the term "cocatalyst" is used to distinguish that component of the catalyst composition from metallocene compounds (s).
[0032] The terms "chemically treated solid oxide", "support-activator", "treated solid oxide compound," and the like, are used in this document to indicate an inorganic, solid oxide of relatively high porosity, which may exhibit acidic behavior Lewis or Bronsted acidic, which has been treated with an electron withdrawal component, usually an anion, which is calcined. The electron withdrawal component is usually an anion source compound of electron withdrawal. Thus, the chemically treated solid oxide may include a calcined contact product of at least one solid oxide with at least one electron withdrawing anion source compound. Typically, the chemically treated solid oxide comprises at least one acidic solid oxide compound. The terms "support" and "support-activator" are not used to assign these components to be inert, and such components should not be interpreted as an inert component of the catalyst composition. The support-activator of the present invention can be a chemically treated solid oxide. The term "activator", as used in this document, generally refers to a substance that is capable of converting a metallocene component into a catalyst that can polymerize olefins, or convert a contact product from a metallocene component and a component that provides an activable binder (eg, an alkyl, a hydride) for metallocene, when the metallocene no longer comprises such a binder, in a catalyst that can polymerize olefins. This term is used regardless of the actual activation mechanism. Illustrative activators include activator supports, aluminoxanes, organoboro or organoborate compounds, ionic or ionizing compounds, and the like. Aluminoxanes, organoboro or organoborate compounds, and ionic or ionizing compounds are generally referred to as activators if used in a catalyst composition, where a support-activator is not present. If the catalyst composition contains a support-activator, then aluminoxane, organoboro or organoborate, and ionic or ionizing materials are generally referred to as cocatalysts.
[0033] The term "fluoro-organo boron compound" is used in this document with its common sense to refer to neutral compounds in a BY3 form. The term "fluoro-organo borate compound" also has its usual meaning to refer to monoanonic salts of fluoro-organo boron compound in a [cation] + [BY4] ’form, where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as "organoboro or organoborate compounds".
[0034] The term "metallocene", as used herein, describes a compound comprising at least a η3 to η5-cycloalkadienyl type moiety, wherein η3 to η5-cycloalkadienyl moieties include cyclopentadienyl binders, indenyl binders, fluorenyl binders, and the like, including derivatives substituted by heteroatom or partially saturated, or analogues of any of them. Possible substituents on these linkers can include H, therefore, this invention comprises partially saturated linkers such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, and the like. Heteroatom-substituted versions of cycloalkadienyl moieties are also encompassed, that is, heteroatom-substituted versions of a cyclopentadienyl, indenyl or fluorenyl group, comprising one or more heteroatoms, such as silicone nitrogen, boron, germanium, or phosphorus, in combination with atoms of carbon to form the respective cyclic portion. In some contexts, metallocene is referred to simply as "catalyst", in much the same way that the term "cocatalyst" is used in this document to refer to, for example, an organoaluminium compound.
[0035] The terms "catalyst composition", "catalyst mixture," "catalyst system" and the like, do not depend on the actual composition or product resulting from the reaction or contact of the claimed initial composition / mixtures / catalyst system components, the nature of the active catalytic site, or the target cocatalyst, the metallocene compound (s), any olefin monomer used to prepare a pre-contacted mixture, or the activator (for example, the support-activator), then to combine these components. Therefore, the terms "catalyst composition", "catalyst mixture," "catalyst system", and the like, encompass the initial composition starting components, as well as any products may result in contacting these initial starting components, and these are inclusive of both homogeneous or heterogeneous compositions or catalyst systems.
[0036] The term "contact product" is used in this document to describe compositions in which components are contacted together in any order, in any form, and for any period of time. For example, components can be contacted by combining or mixing. In addition, contact with any component may occur in the presence or absence of any other component of the compositions described here. The combination of additional components or materials 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 the "contact product" may include reaction products, it is not necessary for the respective components to react with each other. Similarly, the term "contact" is used in this document to refer to materials that can be combined, mixed, suspended, dissolved, reacted, treated, or otherwise contacted in any other way.
[0037] The term "pre-contacted" mixture is used in this document to describe a first mixture of catalyst components that are contacted for a first period of time before the first mixture is used to form a "post-contacted" mixture or a second mixture of catalyst components that are contacted for a second period of time. Typically, the pre-contacted mixture describes a mixture of metallocene compounds (one or more than one), olefin monomer (or monomers), and organoaluminium compound (or compounds), before this mixture comes into contact with a support (s ) - optional additional organo-aluminum compound and activator. In this way, pre-contacted describes the components that are used to contact each other, but before coming in contact with the components in the second, post-contacted mixture. Therefore, this invention may occasionally distinguish between a component used to prepare the pre-contacted mixture and that component after the mixture has been prepared. For example, according to this description, it is possible for the pre-contacted organoaluminium compound, as it comes in contact with the olefin compound and the olefin monomer, to have reacted to form at least one compound, formulation, structure different chemistry, from the different organoaluminium compound used to prepare the pre-contacted mixture. In this case, the pre-contacted organoaluminium compound or component is described as comprising an organoaluminium compound that was used to prepare the pre-contacted mixture.
[0038] In addition, the pre-contacted mixture can describe a mixture of metallocene compound (s) and organoaluminium compound (s), before coming into contact with that mixture with an activator support (s). This pre-contacted mixture can also describe a mixture of metallocene compound (s), olefin monomer (s), support-activator (s), before this mixture comes into contact with an organoaluminium cocatalyst compound or compounds.
[0039] Similarly, the term "post-contacted" mixture is used in this document to describe a second mixture of catalyst components that are contacted for a second period of time, and a component that is the first mixture or "pre- Contacted "or catalyst components that have been contacted for a first period of time. Typically, the term "post-contacted" mixture is used in this document to describe the mixture of metallocene compound (s), olefin monomer (s), organoaluminium compound (s), and activator support formed from contact with the pre-contacted mixture of a part of these components with any additional components added to make the mixture post-contacted. Often, the support-activator comprises a chemically treated solid oxide. For example, the additional component added to compensate for the post-contacted mixture may be a chemically treated solid oxide (one or more than one), and, optionally, may include an organoaluminium compound that is the same or different from the organoaluminium compound used for prepare the pre-contacted mixture as described in this document. Consequently, this invention can also occasionally distinguish between a component used to prepare the post-contacted mixture and that component after the mixture has been prepared.
[0040] Although any methods, devices, and materials similar or equivalent to those described in this document can be used in the practice or testing of the invention, typical methods, materials and devices are described here.
[0041] All publications and patents mentioned in this document are incorporated by reference in this document for the purpose of describing and disclosing, for example, methodologies and constructions that are described in publications, which can be used in connection with the currently described invention. The publications discussed throughout the text are provided solely for publication before the date of submission of this application. Nothing here is to be construed as an admission that inventors are not authorized to pre-date such disclosure by virtue of the prior invention.
[0042] For any given compound disclosed in this document, any specific or general structure presented also encompasses all conformational isomers, regioisomers, stereoisomers and that may arise from a certain set of substituents, unless otherwise indicated. Similarly, unless otherwise indicated, the specific or general structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in racemic or enantiomeric forms, as well as mixtures of stereoisomers, as would be recognized by one skilled in the art.
[0043] Applicants disclose several types of gaps in the present invention. These include, but are not limited to a range of number of atoms, a range of weight ratios, a range of molar ratio, a range of surface areas, a range of pore volumes, a range of particle sizes, a range of of catalyst activities, and so on. When claimants disclose or claim a range of any kind, it is the claimants' intention to individually disclose or claim each possible number that that range could reasonably cover, including endpoints of the range, as well as any subintervals and combinations of subintervals covered therein. For example, when applicants disclose or claim a chemical moiety having a certain number of carbon atoms, the applicants' intention is to disclose or individually claim every possible number that that variety could encompass, consistent with the disclosure here. For example, the disclosure that a moiety is a C1- to C12 alkyl group, or in alternative language having an alkyl group up to 12 carbon atoms, as used herein, refers to a moiety that can be selected independently of an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, as well as any interval between these two numbers (for example, a C1 to CΘ alkyl group), and it also includes any combination of intervals between these two numbers (for example, a C2 to C4 alkyl group and CΘa Ce alkyl group).
[0044] Similarly, another representative example follows for the ratio of Mz / Mw to an ethylene polymer, provided in one aspect of this invention. By disclosing that the Mz / Mw of an ethylene polymer can be in the range of about 3 to about 6, applicants intend to recite that Mz / Mw can be about 3, about 3.1, of about 3.2, about 3.3, about 3.4, about 3.5, about 3.6, about 3.7, about 3.7, about 3.8, about 3.9, about 4, about 4.1, about 4.2, about 4.3, about 4.4, about 4.5, about 4, 6, about 4.7, about 4.8, about 4.9, about 5, about 5.1, about 5.2, about 5.3, about about 5.4, about 5.5, about 5.6, about 5.7, about 5.8, about 5.9, or about 6. In addition, the Mz / Mw can be any range from about 3 to about 6 (for example, from about 3 to about 5.2), and this also includes any combination of the range between about 3 and about 6 (for example example, MzMw is in the range of about 3 to about 4 or about 5 to about 6). Similarly, all other intervals disclosed in this document should be interpreted in a similar way to these two examples.
[0045] Applicants reserve the right to disqualify or exclude any individual elements of any group, including any subintervals or combinations of subintervals within the group, which may be required according to an interval or similarly, if for any reason the candidates choose to claim less than the full disclosure measure, for example, for a reference that claimants may be unaware of when filing the application. In addition, claimants reserve the right to the proviso condition or exclude any individual substituents, analogs, compounds, binders, structures, or groups thereof, or all elements of a claimed group, if for any reason the claimants choose to claim less than the full measure of disclosure, for example, the account for a reference that claimants may be unaware of at the time of filing the application.
[0046] The terms "one", "one", "a", "o", etc., are intended to include plural alternatives, for example, at least one, unless otherwise specified. For example, the disclosure of "a support-activator" or "a metallocene compound" is intended to cover one, or mixtures or combinations of more than one support-activator or metallocene compound, respectively.
[0047] Although the compositions and methods are described in terms of "comprising" different components or steps, the compositions and methods can also "consist essentially of" or "consist of" different components or steps. For example, a catalyst composition of the present invention can comprise; alternatively, it can essentially consist of; or, alternatively, it may consist of; (i) catalyst component I, (ii) catalyst component II, and (iii) an activator. DETAILED DESCRIPTION OF THE INVENTION
[0048] The present invention generally relates to catalyst compositions, methods for preparing catalyst compositions, methods for using catalyst compositions to polymerize olefins, polymer resins produced using such catalyst compositions, and articles produced with these polymer resins. In one aspect, the present invention relates to a catalyst composition, said catalyst composition comprising catalyst component I, catalyst component II, and an activator.
[0049] In another aspect, an olefin polymerization process is provided and, in this aspect, the process comprises contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce a polymer of olefin, wherein the catalyst composition comprises catalyst component I, catalyst component II, and an activator.
[0050] Homopolymers, copolymers, olefin terpolymers, and the like, can be produced using the catalyst methods and compositions for the olefin polymerization disclosed in this document. For example, an ethylene polymer of the present invention can be characterized by the following properties of the polymer: a non-bimodal molecular weight distribution, a Mw / Mn ratio of about 3 to about 8, a Mz / Mw ratio of about from 3 to about 6, and an inverse comonomer distribution. CATALYST COMPONENT I
[0051] The catalyst component I can comprise at least one loop-metallocene compound having a formula (I):
I), where: MA is Ti, Zr, or Hf; X1A and X2 ^ are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any having up to 18 carbon atoms; EA is C or Si; R1A and R2A are independently H, a hydrocarbyl group having up to 18 carbon atoms, or R1A and R2A are connected to form a cyclic or heterocyclic group having up to 18 carbon atoms, where R1A and R2A are not aryl groups; R6A and R7As are independently H or a hydrocarbyl group having up to 18 carbon atoms; and CpA is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a hetero atom thereof, any substituent on CpA is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms.
[0052] The formula (I) above, any other structural formulas disclosed here, and any kind of metallocene disclosed here are not designed to show stereochemical or isomeric positioning of the different portions (for example, these formulas are not intended to display cis or trans -isomers, or R or S diastereoisomers), although such compounds are contemplated and encompassed by these structures and / or formulas.
[0053] Hydrocarbyl is used in this document to specify a hydrocarbon radical group that includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkylenyl, alkynyl, aralkyl, aralkenyl, aralquinyl, and the like, and includes all substituted, unsubstituted, linear, and / or branched derivatives thereof. Unless otherwise specified, the hydrocarbyl groups of this invention typically comprise up to 36 carbon atoms. In other respects, hydrocarbyl groups can have up to 24 carbon atoms, for example, up to 18 carbon atoms, up to 12 carbon atoms, up to 10 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms. A hydrocarbiloxide group, therefore, is used generically to include both the alkoxide and aryloxide groups, and these groups can encompass up to approximately 36 carbon atoms. Non-limiting and illustrative examples of alkoxide and aryloxide groups (i.e., hydrocarbiloxide group) include methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like. The term "hydrocarbilamino group" is generically used to refer collectively to alkylamino, arylamino, dialkylamino, and diarylamino groups. Unless otherwise indicated, the hydrocarbilamino groups of this invention comprise up to about 36 carbon atoms. Hydrocarbylsilyl groups include, but are not limited to, alkylsilyl groups, alkenylsilyl groups, arylsilyl groups, arylalkylsilyl groups, and the like, which have up to about 36 carbon atoms. For example, illustrative hydrocarbylsilyl groups can include trimethylsilyl and phenyloctylsilyl. These hydrocarbiloxide, hydrocarbilamino, and hydrocarbylsilyl groups can have up to 24 carbon atoms; alternatively, up to 18 carbon atoms; alternatively, up to 12 carbon atoms; alternatively, up to 10 carbon atoms; or alternatively, up to 8 carbon atoms, in other aspects of the present invention.
[0054] Unless otherwise indicated, alkyl and alkenyl groups described herein are intended to include all structural, linear or branched isomers of a given portion; for example, all enantiomers and all diastereomers are included in this definition. For example, unless otherwise specified, the term propyl should include n-propyl and iso-propyl, while the term butyl should include n-butyl, iso-butyl, tert-butyl, sec-butyl, and so on. . For example, non-limiting examples of octyl isomers include 2-ethyl hexyl and neo-octyl. Suitable examples of alkyl groups that can be employed in the present invention include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. Illustrative examples of alkenyl groups within the scope of the present invention include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like. The alkenyl group may be a terminal alkenyl group, but this is not a requirement. For example, specific alkenyl group substituents may include, but are not limited to, 3-butenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, 7-octenyl, 3-methyl-3-butenyl, 4-methyl-3 - pentenyl, 1,1-dimethyl-3-butenyl, 1,1-dimethyl-4-pentenyl, and the like.
[0055] In this disclosure, aryl is intended to include aryl and arylalkyl groups, and these include, but are not limited to, phenyl, phenyl substituted by alkyl, naphthyl, naphthyl substituted by alkyl, alkyl substituted by phenyl, alkyl substituted by naphthyl, and the like. Accordingly, non-limiting examples of such "aryl" portions that can be used in the present invention include phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like. Unless otherwise indicated, any substituted aryl portion used here is intended to include all regioisomers; for example, the term tolyl should include any possible substituent position, which is, ortho, meta, or para.
[0056] According to one aspect of this invention, in formula (I), at least one of R1A and R2A is a terminal alkenyl group having up to 12 carbon atoms, or at least one substituent on CpA is a terminal alkenyl group or group terminal alkenylsilyl having up to 12 carbon atoms.
[0057] According to another aspect of this invention, catalyst component I comprises at least one loop-metallocene compound having the formula (IA):
IA), where: MA is Ti, Zr, or Hf; X1A and are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 12 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any having up to 12 carbon atoms; EA and YA are independently C or Si; R1A and R2A are independently H, a hydrocarbyl group having up to 12 carbon atoms, or R1A and R2A are linked to form a cyclic or heterocyclic group having up to 12 carbon atoms, where R1A and R2A are not aryl groups; R3A R4A AND R5Asθ0 independently H or a hydrocarbyl group having up to 10 carbon atoms; R6A and R7A are independently H or a hydrocarbyl group having up to 12 carbon atoms; and CpA is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a heteroatom thereof, any additional substituent on CpA is independently H or hydrocarbyl group having up to 12 carbon atoms; wherein at least one of R1A, R2A, R3A, R4A and R5A is an alkenyl group.
[0058] In formulas (I) and (IA), MA is Ti, Zr, or Hf. In some aspects disclosed here, MA is either Zr or Hf. X and X2A can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H, BH4, OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. X and X2A independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X1A and X2A independently are Cl, benzyl, phenyl, or methyl in one aspect of the invention. In another aspect, X1A and X2 ^ independently are benzyl, phenyl, or methyl. In yet another aspect, both X1A and X ^ can be Cl; alternatively, both X1A and X4 may be benzyl; alternatively, both X1A and X ^ may be phenyl; or alternatively, both X1A and X2A can be methyl.
[0059] In formulas (I) and (IA) EA and YA in formula (IA) are independently C or Si. Often, both EA and YA are C
[0060] In formulas (I) and (IA), R1A and R2A are independently H; a hydrocarbyl group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms; or R ^A and R ^ are linked to form a cyclic or heterocyclic group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. However, R1A and R2 ^ are not aryl groups. Cyclic groups include cycloalkyl and cycloalkenyl moieties and these moieties may include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. For example, a bridge atom EA, R1A, and R2A can form a cyclopentyl or cyclohexyl moiety. Heteroatom-substituted cyclic groups can be formed with nitrogen, oxygen, or sulfur heteroatoms, usually when EA is C. Although these heterocyclic groups can have up to 12 or 18 carbon atoms, heterocyclic groups can be groups of 3 elements, 4 elements , 5 elements, 6 elements, or 7 elements in some aspects of this invention.
[0061] In the aspect of the present invention, R1A and R2A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. In another aspect, R 1A and R 2 are independently H or an alkyl or alkenyl terminal group having up to 8 carbon atoms. For example, R2A and R1A independently can be H, methyl, ethyl, propyl, or butyl. In yet another aspect, at least one of R1A and R4 is a terminal alkenyl group having up to 8 carbon atoms or, alternatively, up to 6 carbon atoms. In yet another aspect, at least one of R1A and R4 is a methyl group; therefore, both R1A and R2 ^ may be methyl groups in aspects of this invention.
[0062] R6A and R7A in the fluorenyl group in formulas (I) and (IA) are independently H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Accordingly, R6A and R7A independently can be H or a hydrocarbyl group having up to 6 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, or hexyl, and the like. In some respects, R6A and R7A are independently methyl, ethyl, propyl, n-butyl, tert-butyl, or hexyl, although in other aspects, R6A and R7A are independently H or tert-butyl. For example, both R6A and R7A can be H or, alternatively, both R6A and R7A can be tert-butyl.
[0063] In the formula (IA), R3A, R4A and R5A are independently H or a hydrocarbyl group having up to 10 carbon atoms. Although any of R3A, R4A, and R5A individually can have up to 10 carbon atoms, the total number of carbon atoms in R3A, R4A, R5A, and YA is usually less than or equal to 24; alternatively, less than or equal to 18; or alternatively, less than or equal to 12. In one aspect of this invention, YA is either C or Si, and R3A, R4A, and R5A are independently selected from H, methyl, ethyl, propyl, butyl, pentyl, hexyl , heptyl, octyl, nonyl, decyl, ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. In another aspect, R3A and R4A are independently H or methyl, and R5A is a terminal alkenyl group having up to 8 carbon atoms or, alternatively, having up to 6 carbon atoms.
[0064] In formulas (I) and (IA), CpA is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a heteroatom of the same. Possible substituents on CpA may include H, so this invention comprises partially saturated binders such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, and the like. CpA can be a hetero-substituted version of a cyclopentadienyl, indenyl, fluoroenyl group; in such cases, CpA may comprise one or more heteroatoms, such as nitrogen, silicone, boron, germanium, or phosphorus, in combination with carbon atoms to form the respective cyclic moiety.
[0065] In some aspects of this invention, CpA is a cyclopentadienyl group, an indenyl group, or a fluorenyl group. CpA is often a cyclopentadienyl group.
[0066] Any CpA substituents in formula (I) independently can be H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms, for example, up to 24 carbon atoms, or up to 18 carbon atoms. Illustrative hydrocarbyl and hydrocarbylsilyl groups provided above can be substituents on CpA, such as, for example, alkenyl (ethenyl, propenyl, butenyl, pentenyl, hexenyl, and the like) or alkenylsilyl groups. As for formula (IA), any additional substituents on CpA independently can be H or a hydrocarbyl group having up to 12 carbon atoms.
[0067] In formula (IA), at least one of R1A, R2A, R3A, R4A, and R5A is an alkenyl group, for example, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl, and the like. In some respects, at least one of R1A, R2A, R3A, R4A, and R5A can be a terminal alkenyl group having up to 10 carbon atoms; alternatively, up to 8 carbon atoms; alternatively, up to 6 carbon atoms; or alternatively, up to 5 carbon atoms.
[0068] Non-limiting examples of loop-metallocene compounds that are suitable for use in catalyst component I include, but are not limited to, below:


and the like, or any combination thereof. Applicants have used the abbreviations "Me" for methyl and "t-Bu" for tert-butyl. Other bridged metallocene compounds can be employed in the catalyst component, as long as the compound fits within the formula (I) and / or (IA). Therefore, the scope of the present invention is not limited to the bridged metallocene species provided above.
[0069] Other loop-metallocene loop compounds that can be used in the catalyst component in some aspects of this invention are disclosed in US Patent Nos. 6,524,987, 7,119,153, 7,226,886, and 7,312,283, the disclosures that are incorporated in this document by reference in their entirety. CATALYST COMPONENT II
[0070] The catalyst component II can comprise at least one loop-metallocene compound having the formula (II):
II), where: MB is Ti, Zr, or Hf; X1B and X2B are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any having up to 18 carbon atoms; EBéCouSi; R1B and R2B are independently H or a hydrocarbyl group having up to 18 carbon atoms, wherein at least one of R1B and R2B is an aryl group having up to 18 carbon atoms; R6B and R7B are independently H or a hydrocarbyl group having up to 18 carbon atoms; and CpB is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a heteroatom thereof, any substituent on CpB is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms.
[0071] As noted above, formula (II), any other structural formulas disclosed here, and any kind of metallocene disclosed here are not designed to show the stereochemical or isomeric positioning of the different portions (for example, these formulas are not intended for exhibit cis or trans isomers, or R or S diastereoisomers), although such compounds are contemplated and encompassed by these structures and / or formulas.
[0072] According to one aspect of this invention, in formula (II), at least one of R1B and R2B is a terminal alkenyl group having up to 12 carbon atoms, or at least one substituent on CpB is a terminal alkenyl or alkenylsilyl group terminal having up to 12 carbon atoms.
[0073] According to another aspect of this invention, the catalyst component II comprises at least one loop-metallocene compound of the formula (IIB):
(IB), where: MB is Ti, Zr, or Hf; X1B and X2B are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 12 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any having up to 12 carbon atoms; EB and YB are independently C or Si; R1B and R2B are independently H or a hydrocarbyl group having up to 12 carbon atoms, wherein at least one of R1B and R2B is an aryl group having up to 12 carbon atoms; R3B, R4B, and R5B are independently H or a hydrocarbyl group having up to 10 carbon atoms; R6B and R7B are independently H or a hydrocarbyl group having up to 12 carbon atoms; and CpB is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a hetero atom thereof, any additional substituent on CpB is independently H or hydrocarbyl group having up to 12 carbon atoms; wherein at least one of R1B, R2B, RBB, R4B and RSBθ is an a | quenj | a group.
[0074] In formulas (II) and (IIB), MB is Ti, Zr, or Hf. In some aspects disclosed in this document, MB is either Zr or Hf. X1B and X2B independently can be F; Cl; Br; I; methyl; benzyl; phenyl; H, BH4, OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. X1BeX2B independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X1B and X2B independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X1B and X2B are independently benzyl, phenyl, or methyl. In yet another aspect, both X1B and X2B can be Cl; alternatively, both X1BeX2B may be benzyl; alternatively, both X1B and X2B may be phenyl; or alternatively, both X1B and X2B can be methyl.
[0075] In formulas (II) and (IIB) EB and YB in formula (IIB) are independently C or Si. Often, both EB and YB are C.
[0076] In formulas (II) and (IIB), R1B and R2B are independently H; a hydrocarbyl group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. However, at least one of R1B and R2B is an aryl group, and the aryl group can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. Illustrative non-limiting examples of "aryl" moieties suitable for R1B and / or R2B include phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like.
[0077] In one aspect of the present invention, at least one of R1B and R2B is an aryl group having up to 10 carbon atoms. For example, the aryl group can be a phenyl group. In another aspect, R1B is an aryl group having up to 8 carbon atoms, and R2B is an alkyl or alkenyl terminal group having up to 8 carbon atoms. In yet another aspect, R1B is phenyl, and R2B is ethylene, propenyl, butenyl, pentenyl, or hexenyl. In yet another aspect, R1B and R2B are phenyl. R6B θ R7B in the fluoroenyl group in formulas (II) and (IIB) are independently H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Consequently, R6B and R7B independently can be H or a hydrocarbyl group having up to 6 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, or hexyl, and the like. In some respects, R6B and R7B are independently methyl, ethyl, propyl, n-butyl, tert-butyl, or hexyl, although in other aspects, R6B and R7B are independently H or tert-butyl. For example, both R6Be R7B can be H or, alternatively, both R6Be R7B can be tert-butyl.
[0078] In the formula (IIB), R3B, R4B, and R5B are independently H or a hydrocarbyl group having up to 10 carbon atoms. Although any of R3B, R4B, and R5B individually can have up to 10 carbon atoms, the total number of carbon atoms in R3B, R4B, R5B, and yB is typically less than or equal to 24; alternatively, less than or equal to 18; or alternatively, less than or equal to 12. In one aspect of this invention, YB is either C or Si, and R3B, R4B, and R5B are independently selected from H, methyl, ethyl, propyl, butyl, pentyl, hexyl , heptyl, octyl, nonyl, decyl, ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. In another aspect, R3B and R4B are independently H or methyl, and R5B is a terminal alkenyl group having up to 8 carbon atoms or, alternatively, having up to 6 carbon atoms.
[0079] In formulas (II) and (IIB), CpB is a cyclopentadienyl, indenyl, or fluorenyl group, or a derivative substituted by a heteroatom of the same. Possible substituents on CpB can include H, so this invention comprises partially saturated binders such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, and the like. CpB can be a hetero-substituted version of a cyclopentadienyl, indenyl, or fluorenyl group; in such cases, CpB can comprise one or more heteroatoms, such as nitrogen, silicone, boron, germanium, or phosphorus, in combination with carbon atoms to form the respective cyclic portion.
[0080] In some aspects of this invention, CpB is a cyclopentadienyl group, an indenyl group, or a fluorenyl group. Often, CpB is a cyclopentadienyl group.
Any CpB substituents in formula (II) independently can be H or a hydrocarbyl or hydrocarbyl group having up to 36 carbon atoms, for example, up to 24 carbon atoms, or up to 18 carbon atoms. Illustrative hydrocarbyl and hydrocarbylsilyl groups provided above can be substituents on CpB, such as, for example, alkenyl (ethenyl, propenyl, butenyl, pentenyl, hexenyl, and the like) or alkenylsilyl groups. As for formula (UB), any additional substituents on CpB independently can be H or hydrocarbyl group having up to 12 carbon atoms.
[0082] In formula (IIB), at least one of R1B, R2B, R3B, R4B, and R5B is an alkenyl group, for example, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl, and the like. In some respects, at least one of R1B, R2B, R3B, R4B, and R5B can be a terminal alkenyl group having up to 10 carbon atoms; alternatively, up to 8 carbon atoms; alternatively, up to 6 carbon atoms; or alternatively, up to 5 carbon atoms.
[0083] Non-limiting examples of loop-metallocene that are suitable for use in catalyst component II include, but are not limited to, the following:


and the like, or any combination thereof. Applicants have used the abbreviations "Ph" for phenyl and "t-Bu" for tert-butyl. Other bridged metallocene compounds can be used in the catalyst component II, while the compound fits the formula (II) and / or (IIB). Therefore, the scope of the present invention is not limited to the bridged metallocene species provided above.
[0084] Other representative loop-metallocene compounds that can be employed in a catalyst component II in some aspects of this invention are disclosed in US Patent Nos. 7,226,886, 7,312,283, 7,517,939, and 7,619,047, the disclosures which are incorporated herein by reference in their entirety. ACTIVATOR SUPPORT
[0085] The present invention comprises several catalyst compositions containing an activator, which can be a support-activator. In one aspect, the support-activator comprises a chemically treated solid oxide. Alternatively, the support-activator may include a clay mineral, pillar clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a silicate mineral layered aluminum, a non-layered aluminum silicate mineral, or any combination thereof.
[0086] Generally, chemically treated solid oxides have greater acidity compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide also functions as a catalyst activator in comparison to the corresponding untreated solid oxide. Although chemically treated solid oxide activates metallocene in the absence of cocatalysts, it is not necessary to eliminate cocatalysts from the catalyst composition. The activation function of the support-activator is evident in the enhanced activity of the catalyst composition as a whole, compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator, even in the absence of an organoaluminium compound, aluminoxanes, organoboro or organoborate compounds, ionic or ionizing compounds, and the like.
[0087] The chemically treated solid oxide may comprise a solid oxide treated with an anion removed from electron. Although it is not intended to be linked to the following instruction, it is believed that the treatment of the solid oxide with an electron withdrawing component enlarges or increases the acidity of the oxide. Thus, the support-activator has Bronsted or Lewis acidity that is normally greater than the Lewis or Bronsted acid strength of the untreated solid oxide, or the support-activator has a greater number of acidic sites than the untreated solid oxide. treated, or both. One method to quantify the acidity of untreated and chemically treated solid oxide materials is by comparing the polymerization activities of treated and untreated oxides under acid catalyzed reactions.
The chemically treated solid oxides of this invention generally of an inorganic solid oxide which exhibits acidic Lewis or acidic Bronsted behavior and has a relatively high porosity are formed. The solid oxide is chemically treated with an electron withdrawing component, typically an electron withdrawing anion, to form an activator support.
[0089] According to one aspect of the present invention, the solid oxide used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc / g. According to another aspect of the present invention, the solid oxide has a pore volume greater than about 0.5 cc / g. In accordance with yet another aspect of the present invention, the solid oxide has a pore volume greater than about 1.0 cc / g.
[0090] In another aspect, the solid oxide has a surface area of about 100 to about 1000 m2 / g. In yet another aspect, the solid oxide has a surface area of about 200 to about 800 m2 / g. In yet another aspect of the present invention, the solid oxide has a surface area of about 250 to about 600 m2 / g.
[0091] The chemically treated solid oxide may include a solid inorganic oxide comprising oxygen and one or more elements selected from the group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or comprising oxygen and one or more elements selected from actinide or lanthanide elements (see: Hawleys 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, inorganic oxide may include oxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr.
[0092] Suitable examples of solid oxide compounds or materials that can be used to form chemically treated solid oxide include, but are not limited to, AI2O3, B2O3, BeO, BÍ2O3, CdO, CO3O4, C ^ Os, CuO, Fβ2θ3 , Ga2θ3, La2θs, Mn2θ3, MoOs, NiO, P2O5, Sb2θs, SÍO2, Snθ2, SrO, Thθ2, TÍO2, V2O5, WO3, Y2O3, ZnO, Zrθ2, and the like, including mixed oxides thereof, and combinations thereof. For example, the solid oxide may include silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination of these. themselves.
[0093] The solid oxide of the present invention comprises oxide materials such as alumina, compounds of "mixed oxide" thereof such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds such as silica-alumina can be a single or several chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activator support of the present invention include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc aluminate, and the like. The solid oxide of this invention also encompasses oxide materials such as silica-coated alumina, as described in U.S. Patent Application No. 12,565,257, the disclosure of which is incorporated herein by reference in its entirety.
[0094] The electron withdrawal component used to treat the solid oxide can be any component that increases the Lewis or Bnansted acidity of the solid oxide until treatment (in comparison with the solid oxide that is not treated with at least one electron withdrawing anion). According to one aspect of the present invention, the electron withdrawal component is an electron withdrawal anion derived from a salt, acid, or other compound, such as a volatile organic compound, which serves as a precursor or source for that anion. Examples of electron withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and the like, including mixtures and combinations, including mixtures of the same. In addition, other non-ionic or ionic compounds that serve as sources for these electron withdrawing anions can also be employed in the present invention. It is contemplated that the electron withdrawing anion may be, or may include, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and the like, or any combination thereof, in some respects this invention. In other respects, the electron withdrawing anion can include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and the like, or any combination thereof.
[0095] Thus, for example, the support-activator (e.g., chemically treated solid oxide) used in catalyst compositions of the present invention can be, or can include, fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, silica -Fluorinated alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated silica coated alumina, phosphate silica coated alumina, and the like, or combinations thereof. In some respects, the support-activator comprises fluorinated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, it comprises fluorinated silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, it comprises fluorinated silica-zirconia; alternatively, it comprises chlorinated silica-zirconia; or alternatively, it comprises alumina coated with fluorinated silica.
[0096] When the electron withdrawing component comprises a salt from an electron withdrawing anion, the cation or counterion of such a salt that can be selected from any cation that allows the salt to revert or decompose back to the acid during calcination. Factors that determine the suitability of the special salt to serve as a source for the electron withdrawing anion include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse cation reactivity, ion pairing effects between anion and cation, hygroscopic properties transmitted to salt, cation, and the like, and anion's thermal stability. Examples of suitable cations in the electron withdrawal anion salt include, but are not limited to, ammonium, ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H +, [H (OEt2) 2] +, and the like.
[0097] In addition, combinations of one or more different electron withdrawing anions, in varying proportions, can be used to adjust the specific acidity of the activator support to the desired level. Combinations of electron withdrawal components can come in contact with the oxide material simultaneously or individually, and in any order that provides the desired acidity of chemically treated solid oxide. For example, one aspect of this invention is to employ two or more electron withdrawing anion source compounds in two or more separate steps.
[0098] Thus, an example of such a process by which a chemically treated solid oxide is prepared is as follows: a selected solid oxide, or combination of solid oxides, comes in contact with a first anion-withdrawing source compound electron to form a first mixture; this first mixture is calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture is then calcined to form a treated solid oxide. In this process, the first and second electron withdrawing anion source compounds can be either the same or different compounds.
[0099] In accordance with another aspect of the present invention, the chemically treated solid oxide comprises an inorganic solid oxide material, a mixed oxide material, or a combination of inorganic oxide materials, which are chemically treated with a dewatering component electron, and optionally treated with a metal source, including metal salts, metal ions, or other metal-containing compounds. Non-limiting examples of metal or metal ion include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, or combinations thereof. Examples of chemically treated solid oxides that contain a metal or metal ion include, but are not limited to, zinc-impregnated chlorinated alumina, titanium-impregnated fluorinated alumina, zinc-impregnated fluorinated alumina, zinc-impregnated chlorinated silica-alumina, silica- chlorinated alumina impregnated with zinc, sulfated alumina impregnated with zinc, chlorinated zinc aluminate, fluorinated zinc alumate, sulfated zinc aluminate, silica-coated alumina with hexafluorotitanic acid, silica-coated alumina, treated with zinc and then fluorinated, and the like , or any combination thereof.
[0100] Any method of impregnating the solid oxide material with a metal can be used. The method by which the oxide comes into contact with a metal source, usually a compound containing salt or metal, may include, but is not limited to, gelation, cogelification, impregnation of one compound into another, and the like. If desired, the metal-containing compound is added to or impregnated in the solid oxide in the form of a solution, and later converted to supported metal until calcination. Thus, the solid inorganic oxide may additionally include a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals. For example, zinc is often used to impregnate solid oxide, as this provides enhanced catalytic activity at a low cost.
[0101] The solid oxide can be treated with metal salts or compounds containing metals before, after, or at the same time as the solid oxide treated with the electron anion. Following any contact method, the contacted mixture of solid compound, electron withdrawing anion, and metal ion is normally calcined. Alternatively, a solid oxide material, an electron anion source, and the metal salt or metal-containing compound come into contact and are calcined simultaneously.
[0102] Several processes are used to form the chemically treated solid oxide useful in the present invention. The chemically treated solid oxide may comprise the contact product of one or more solid oxides with one or more electron anion sources. It is not necessary for the solid oxide to be calcined before coming into contact with the electron anion source. The product comes into contact normally and is calcined either during or after the solid oxide comes into contact with the electron anion source. The solid oxide can be calcined or non-calcined. Several processes for preparing solid oxide support-activators that can be used in the present invention have been reported. For example, such methods are described in U.S. Patent Nos. 6,613,712, 6,632,894, 6,667,274, and 6,750,302, the disclosures of which are incorporated herein by reference in their entirety.
[0103] In accordance with one aspect of the present invention, the solid oxide material is chemically treated by contacting an electron component, usually an electron anion source. In addition, the solid oxide material is optionally chemically treated with a metal ion, and then calcined to form a chemically treated solid oxide impregnated with metal or containing metal. According to another aspect of the present invention, the solid oxide material and electron withdrawing anion source come into contact and are calcined simultaneously. The method by which the oxide comes into contact with the electron component, is usually a salt or acid from an electron anion, may include, but is not limited to, gelation, cogelification, impregnation of one compound into another, and similar ones. Thus, after contacting any method, the contacted mixture of solid oxide, electron anion, and optional metal ions is calcined.
[0104] The solid oxide support-activator (i.e., chemically treated solid oxide) can thus be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with an anion source compound electron (or compounds) to form a first mixture; and 2) the calcination of the first mixture to form the solid oxide support-activator.
[0105] According to another aspect of the present invention, the support-activator of solid oxide (chemically treated solid oxide) is produced by a process comprising: 3) contact of a solid oxide (or solid oxides) with a first compound of an electron anion source to form a first mixture; 4) calcining the first mixture to produce a first calcined mixture; 5) contacting the first calcined mixture with a second electron anion source compound to form a second mixture; and 6) calcination of the second mixture to form the support-activator of the solid oxide.
[0106] In accordance with yet another aspect of the present invention, chemically treated solid oxide is produced or formed by making the solid oxide come into contact with the electron anion source compound, in which the solid oxide compound is calcined before, during, after contact with the electron withdrawing anion source, where there is a substantial absence of aluminoxanes, organoboro or organoborate compounds, and ionic or ionizing compounds.
[0107] The calcination of the treated solid oxide is generally conducted in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature of about 200 ° C to about 900 ° C, and for a time of about 1 minute at about 100 hours. The calcination can be conducted at a temperature of about 300 ° C to about 800 ° C, or alternatively, at a temperature of about 400 ° C to about 700 ° C. The calcination can be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350 ° C to about 550 ° C. Any suitable ambient atmosphere can be used during calcination. Calcination is generally conducted in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.
[0108] According to one aspect of the present invention, the oxide material is treated with a source of halide ion, sulfate ion, or a combination of anions, optionally treated with a metal ion, and then calcined to provide the chemically treated solid oxide as a particulate solid. For example, the solid oxide material can be treated with a sulfate source (called a "sulfating agent"), a chloride ion source (called a "chlorinating agent"), a fluoride ion source (called a "agent" fluorination "), or a combination thereof, and calcined to provide the solid oxide activator. The use of acidic support-activators includes, but is not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, silica-zirconia brominated, chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina treated with hexafluorotitanic acid, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconium acid, alumina-boria silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillar clay, such as a pillar montmorillonite, optionally treated with fluoride, chloride, or sulfate; phosphate alumina or other aluminophosphates, optionally treated with sulfate, fluoride, or chloride; or any combination thereof. In addition, any of these activator supports can optionally be treated with a metal ion.
[0109] The chemically treated solid oxide may comprise a fluorinated solid oxide in the form of a particulate solid. Fluorinated solid oxide can be formed by contacting a solid oxide with a fluorination agent. The fluoride ion can be added to the oxide by forming a slurry of the oxide in a solvent such as alcohol or water including, but not limited to, one to three carbon alcohols due to its volatility and low surface tension. Examples of suitable fluorination agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) (( NH4) 2SiFθ), ammonium hexafluorophosphate (NH4PF6), hexaluorotitanic acid (H2TIFF), hexafluorotitanic ammonium acid ((NH4) 2TiFe), hexafluorozirconic acid (H2ZrFθ), AIF3, NH4AIF4, and the same analogues. Triflic acid and ammonium triflate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as a fluorination agent, due to its ease of use and availability.
[0110] If desired, the solid oxide is treated with a fluorination agent during the calcination step. Any fluorination agent capable of completely coming into contact with the solid oxide during the calcination step can be used. For example, in addition to those fluorination agents described above, volatile organic fluorination agents can be used. Examples of volatile organic fluorination agents useful in this aspect of the invention include, but are not limited to, freon, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. The calcination temperatures should generally be high enough to decompose the release fluoride and the compound. Hydrogen gas fluoride (HF) or fluorine itself (F2) can also be used with solid oxide if fluorinated during calcination. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4) can also be used. A convenient method for contacting the solid oxide with a fluorination agent is to vaporize a fluorination agent in a gas stream used to fluidize the solid oxide during calcination.
[0111] Similarly, in another aspect of this invention, the chemically treated solid oxide comprises a chlorinated solid oxide in the form of a particulate solid. Chlorinated solid oxide is by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide to form a slurry of the oxide in a suitable solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a chloride source and completely coming into contact with the oxide during the calcination step can be used, such as SiCk, SiMe2Cl2, TiCk, BCIs, and the like, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to, certain freon, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like, or any combination thereof. Hydrogen chloride gas or chlorine itself can also be used with solid oxide during calcination. A convenient method for contacting the oxide with the chlorinating agent is to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.
[0112] The amount of fluoride or chloride ion present before calcining the solid oxide is generally about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, for example, silica-alumina, before calcination. According to another aspect of this invention, the amount of fluoride or chloride ion present before calcining the solid oxide is about 1 to about 25% by weight, and according to another aspect of this invention, about from 2 to about 20% by weight. According to yet another aspect of this invention, the amount of fluoride or chloride ion present before calcining the solid oxide is from about 4 to about 10% by weight. Once impregnated with a halide, the halide oxide can be dried by any suitable method, including, but not limited to, suction filtration, followed by evaporation, vacuum drying, spray drying and the like, although it is also possible to start the calcination step immediately without drying the impregnated solid oxide.
[0113] The silica-alumina used to prepare the treated silica-alumina, normally has a pore volume greater than about 0.5 cc / g. According to one aspect of the present invention, the pore volume is greater than about 0.8 cc / g, and according to another aspect of the present invention, greater than about 1.0 cc / g. In addition, silica-alumina generally has a surface area of more than about 100 m2 / g. According to another aspect of the present invention, the surface area is greater than about 250 m2 / g. However, in another aspect, the surface area is greater than about 350 m2 / g.
[0114] The silica-alumina used in the present invention normally has an alumina content from about 5 to about 95% by weight. According to one aspect of the present invention, the silica-alumina alumina content is from about 5 to about 50%, or from about 8% to about 30% by weight of alumina. In another aspect, silica-alumina compounds with a high alumina content can be employed, in which the alumina content of these silica-alumina compounds is normally in the range of about 60% to about 90%, or about from 65% to about 80% by weight of alumina. In accordance with yet another aspect of this invention, the solid oxide component comprises silicon-free alumina, and in accordance with another aspect of this invention, the solid oxide component comprises silica-free alumina.
[0115] The sulfated solid oxide comprises sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide is additionally treated with a metal ion that the calcined sulfated oxide comprises a metal. According to one aspect of the present invention, the sulfated solid oxide comprises sulfate and alumina. In some cases, sulfated alumina is formed by a process in which the alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt, such as ammonium sulfate. This process is carried out generally by forming a slurry of alumina in a suitable solvent, such as alcohol or water, to which the desired concentration of the sulfating agent has been added. Suitable organic solvents include, but are not limited to, one to three carbon alcohols because of their volatility and low surface tension.
[0116] According to one aspect of this invention, the amount of sulfate ion present before calcination is about 0.5 to about 100 parts by weight per sulfate ion of about 100 parts by weight of solid oxide. According to another aspect of this invention, the amount of sulfate ion present before calcination is from about 1 to about 50 parts by weight per sulfate ion to about 100 parts by weight per solid oxide, and according to yet another aspect of this invention, from about 5 to about 30 parts by weight per sulfate ion to about 100 parts by weight per solid oxide. These weight ratios are based on the weight of the solid oxide before calcination. Once impregnated with sulfate, the sulfate oxide can be dried by any suitable method, including, but not limited to, suction filtration, followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible start the calcination step immediately.
[0117] According to another aspect of the present invention, the support-activator used to prepare the catalyst compositions of the present invention comprises an ion-exchangeable support-activator, including but not limited to, silicate and aluminosilicate compounds or minerals, with layers or non-layered structures, and combinations thereof. Another aspect of this invention, the replaceable ion, aluminosilicates layered as pillar clays are used as support-activators. When the support-activator acid comprises an ion-exchangeable support-activator, it can optionally be treated with at least one electron withdrawing anion such as those disclosed here, although normally replaceable ion-activating support is not treated with an electron withdrawing anion.
[0118] According to another aspect of the present invention, the activator support of the present invention comprises layered clay minerals and replaceable cations capable of expanding. Typical clay mineral support-activators include, but are not limited to, aluminosilicates in ion-exchange layers, such as pillar clays. Although the term "support" is used, it should not be interpreted as an inert component of the catalyst composition, but rather is to be considered an active portion of the catalyst composition, due to its close association with the metallocene component.
[0119] In accordance with another aspect of the present invention, the clay materials of this invention include materials in their natural state or which have been treated with various ions by wetting, ion exchange, or pillaring. Typically, the clay material activator support of the present invention comprises clays that have been exchanged for ions with large cations, including polynuclear, highly charged metal complex cations. However, the clay material activator supports of this invention also encompass clays that have been exchanged for ions with simple salts, including, but not limited to, Al (lll), Fe (ll), Felll, and Zn ( ll) with binders such as iodides, acetate, sulfate, nitrate, or nitrite.
[0120] According to another aspect of the present invention, the activator support comprises a pillar clay. The term "pillar clay" is used to refer to clay materials that have been exchanged for ions with high, highly charged, complex, normally polynuclear metal complex cations. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometalates, and other large ions. In this way, the term pillarization refers to a simple exchange reaction in which the replaceable cations of a clay material are replaced by large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within clay interlayer and when calcined they are converted into metal oxide "in a pillar", effectively supporting the clay layers as structures similar to the column. In this way, after the clay is dried and calcined to produce the pillars between layers of clay, the enlarged interlaced structure is maintained and the porosity is reinforced. The resulting pores can vary in shape and size as a function of the pillar material and the main clay material used. Examples of pillar and pillar clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent No. 4,060,480; the disclosures that are incorporated into this document by reference in their entirety.
[0121] The pillaring process uses clay minerals having replaceable layers and cations capable of expanding. Any pillar clay that can enhance the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, clay minerals suitable for pillaring include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and derivatives thereof, such as montmorillonites (bentonites), nontronites, hectorites, or laponites; Heloisites; vermiculites; micas; fluoromics; chlorites; clay mixing layer; fibrous clays, including but not limited to sepiolites, atapulgites, and paligorskites; a serpentine clay; illita; laponite; saponite; and any combination thereof. In one aspect, the pillar clay activator support comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
[0122] The pillar clay can be pretreated if desired. For example, pillar bentonite is pre-treated by drying at about 300 ° C under an inert atmosphere, usually dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although an exemplary pretreatment is described herein, it should be understood that heating can be carried out at many other temperatures and periods, including any combination of temperature and time steps, all of which are encompassed by this invention.
[0123] The support-activator used to prepare the catalyst compositions of the present invention can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, phosphate inorganic oxides, and the like. In one aspect, typical support materials that are used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thorium, aluminum phosphate, aluminum phosphate, silica-titania, coprecipitated silica-titania , mixtures thereof, or any combination thereof.
[0124] According to another aspect of the present invention, one or more of the metallocene compounds can be pre-contacted with an olefin monomer and an organoaluminium compound for a first period of time before coming into contact with this mixture with the support-activator. Once the pre-contacted mixture of the metallocene compound (s), olefin monomer, and organoaluminium compound comes into contact with the support-activator, the composition additionally comprising the support-activator is called a "post- contacted ". The post-contacted mixture can be allowed to remain in contact additionally for a second period of time before being loaded into the reactor where the polymerization process will be carried out.
[0125] According to another aspect of the present invention, one or more of the metallocene compounds can be pre-contacted with an olefin monomer and a support-activator for a first period of time before coming into contact with this mixture with the composed of organoaluminium. Once the pre-contacted mixture of the metallocene compound (s), olefin monomer, support-activator comes into contact with the organoaluminium compound, the composition additionally comprising the organoaluminium is called a "post-contacted" mixture. The post-contacted mixture can be allowed to remain in contact additionally for a second period of time before being introduced into the polymerization reactor. ORGANOALUMINUM COMPOUNDS
[0126] In some respects, the catalyst compositions of the present invention may comprise one or more organoaluminium compounds. Such compounds can include, but are not limited to, compounds having the formula: (RC) 3AI; where Rc is an aliphatic group having 1 to 10 carbon atoms. For example, Rc can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl. Other organoaluminium compounds that can be used in catalyst compositions disclosed herein may include, but are not limited to, compounds of the formula: AI (X3) m (X4) 3-m, where X3 is a hydrocarbyl; X4 is an alkoxide or an aryloxide, a halide, or a hydride; and m is 1 to 3, inclusive. Hydrocarbyl is used here to specify a radical hydrocarbon group and includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkylenyl, alkynyl, aralkyl, aralkenyl, aralquinyl, and the like, and includes all substituted derivatives, unsubstituted, branched, linear, and / or hetero-atom-derived derivatives thereof.
[0127] In one aspect, X3 is a hydrocarbyl having from 1 to about 18 carbon atoms. In another aspect of the present invention, X3 is an alkyl having 1 to 10 carbon atoms. For example, X3 can be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet another aspect of the present invention.
[0128] According to one aspect of the present invention, X4 is an alkoxide or an aryloxide, any one having 1 to 18 carbon atoms, a halide, or a hydride. In another aspect of the present invention, X4 is independently selected from chlorine and fluorine. In yet another aspect, X4 is chlorine.
[0129] In the formula, AI (X3) m (X4) 3-m, m is an integer from 1 to 3 inclusive, and usually, m is 3. The value of m is not restricted to being an integer; therefore, this formula includes sesquihalide compounds or other compounds of the organoaluminium group.
[0130] Examples of organoaluminium compounds suitable for use in accordance with the present invention include, but are not limited to, trialkylaluminium compounds, dialkylaluminium halide compounds, dialkylaluminium alkoxide compounds, dialkylaluminum hydride compounds, and combinations of the same. Specific non-limiting examples of suitable organoaluminium compounds include trimethylaluminium (TMA), triethylaluminium (TEA), tri-n-propylaluminium (TNPA), tri-n-butylalumin (TNBA), triisobutylaluminum (TIBA), tri hydride -n-hexylalumin, tri-n-octylalumin, diisobutylaluminum, diethylaluminum ethoxide, diethylaluminium chloride, and the like, or combinations thereof.
[0131] The present invention contemplates a method of pre-contacting a metallocene with an organoaluminium compound and an olefin monomer to form a pre-contacted mixture, before contacting that pre-contacted mixture with an activator support to form a composition of catalyst. When the catalyst composition is prepared in this way, normally, but not necessarily, a portion of the organoaluminum compound is added to the pre-contacted mixture and another portion of the organoaluminium compound is added to the post-contacted mixture prepared when the pre-contacted mixture contacts the solid oxide activator support. However, the entire organoaluminium compound can be used to prepare the catalyst composition in the pre-contact or post-contact stage. Alternatively, all catalyst components are contacted in one step.
[0132] In addition, more than one organoaluminium compound can be used in the pre-contact or the post-contact step. When an organoaluminium compound is added in several stages, the amounts of organoaluminium compounds disclosed here include the total amount of organoaluminium compound used in the pre-contacted and post-contacted mixtures, and any additional organoaluminium compound added to the polymerization reactor. Therefore, the total amounts of organoaluminium compounds are disclosed regardless of whether a single organoaluminium compound or organoaluminium more than one compound is used. ALUMINOXAN COMPOUNDS
[0133] The present invention further provides a catalyst composition that can include an aluminoxane compound. As used herein, the term "aluminoxane" refers to distinct aluminoxane compounds, compositions, mixtures or species, regardless of how these aluminoxanes are prepared, formed or otherwise disposed. For example, a catalyst composition, comprising an aluminoxane compound can be prepared in which aluminoxane is provided as the poly (hydrocarbyl aluminum oxide), or in which aluminoxane is provided as the combination of an alkyl aluminum compound and a source of active protons such as water. Aluminoxanes are also referred to as poly (hydrocarbon aluminum oxides) or organoaluminoxanes.
[0134] The other components of the catalyst are normally contacted with aluminoxane in a solvent composed of saturated hydrocarbons, although any solvent that is substantially inert to the reactants, intermediates, and products of the activation step can be used. The catalyst composition formed in this way is collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition is introduced into the polymerization reactor without being isolated.
[0135] The aluminoxane compound of this invention can be a compound consisting of linear structures, cyclic structures, or cage structures or mixtures of all three oligomeric aluminum. Cyclic aluminoxane compounds, having the formula:
where R in this formula is linear or branched alkyl having 1 to 10 carbon atoms and p is an integer from 3 to 20, are encompassed by this invention. The portion shown here also forms the repeat unit in a linear aluminoxane. Thus, linear aluminoxanes, having the formula:
where R in this formula is a linear or branched alkyl having 1 to 10 carbon atoms and q is an integer 1 to 50, are also encompassed by this invention.
[0136] In addition, aluminoxanes may have cage structures of the formula R '5r + αRbr-cAl4rθ3r, where R 'is a terminal linear or branched alkyl group having from 1 to 10 carbon atoms; Rb is a straight or branched alkyl group bridge having 1 to 10 carbon atoms; r is 3 or 4; and α is equal to ΠAI (3) - no (2) + no (4), where ΠAI (3) is the number of aluminum atoms of three coordinates, no (2) is the number of oxygen atoms of two coordinates, and no (4) is the number of oxygen atoms of four coordinates.
[0137] Thus, aluminoxanes that can be used in the catalyst compositions of the present invention are generally represented by formulas such as (R-AI-O) p, R (R-AI-O) qAIR2, and the like. In these formulas, the group R is typically a straight or branched C-i-Cε alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. EXAMPLES of aluminoxane compounds that can be used in accordance with the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, sec-butylaluminoxane, sec-butylalinoalane , 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane, and iso-butylaluminoxane are prepared from trimethylaluminum, triethylaluminium, or triisobutylalumin, respectively, and are sometimes referred to as poly (methyl aluminum oxide), poly (ethyl aluminum oxide), and poly (isobutyl aluminum oxide), respectively . It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminium, such as that mentioned in U.S. Patent No. 4,794,096, incorporated herein by reference in its entirety.
[0138] The present invention contemplates many values of p and q in the formulas aluminoxane (R-AI-O) P and R (R-AI-O) qAIR2, respectively. In some respects, p and q are at least 3. However, depending on how organoaluminoxane is prepared, stored, and used, the value of p and q can vary within a single sample of aluminoxane, and these combinations of organoaluminoxanes are contemplated in this document.
[0139] In the preparation of a catalyst composition containing an aluminoxane, the molar ratio of the aluminum moles in the aluminoxane (or aluminoxanes) to the total moles of the metallocene compound (s) in the total composition is generally between about 1:10 and about 100,000: 1. In another aspect, the molar ratio is in the range of about 5: 1 to about 15, 000: 1. Optionally, aluminoxane can be added to a polymerization zone at intervals from about 0.01 mg / L to about 1000 mg / L, from about 0.1 mg / L to about 100 mg / L, or from about 1 mg / L L at about 50 mg / L.
[0140] Organoaluminoxanes can be prepared by several procedures. EXAMPLES of organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, the disclosures that are incorporated herein by reference in their entirety. For example, water in an inert organic solvent can be reacted with an alkyl aluminum compound, such as (RC) 3AI, to form the desired organoaluminoxane compound. While not intending to be bound by this instruction, it is believed that this synthetic method can afford a mixture of both linear and cyclic R-AI-0 aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes are prepared by reacting an alkyl aluminum compound, such as (RC) 3AI, with a hydrated salt, hydrated as copper sulfate in an inert organic solvent. ORGANOBORO / ORGANOBORATE COMPOUNDS
[0141] According to another aspect of the present invention, the composition of the catalyst can include an organoboro or compound organoborate. Such compounds include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, fluoroorgane boron compounds and fluoroorgane borate compounds are contemplated.
[0142] Any fluoroorgane boron or fluoroorgane borate compound can be used with the invention of the present. EXAMPLES of fluoroorgan borate compounds that can be used in the present invention include, but are not limited to, fluorinated aryl borates such as N, N-dimethylanilinium tetrakis- (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, lithium tetrakis ) borate, N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, and the like, or mixtures thereof. EXAMPLES of fluoroorgan boron compounds that can be used as co-catalysts in the present invention include, but are not limited to, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and the like, or the like mixtures. Although not intended to respect the following theory, these EXAMPLES of boron compounds and fluoroorgane fluoroorgane borates, and related compounds, are thought to form "poorly coordinated" anions when combined with organometal or metallocene compounds, as disclosed in 5,919,983 of a United States patent, the disclosure of which is incorporated herein by reference in its entirety. Candidates also contemplate the use of diboro, or bis-boron, compounds or other bifunctional compounds containing two or more boron atoms in the chemical structure, as disclosed in J. Am. Chem. Soc., 2005, 127, pp. 14756-14768, the content of which is incorporated herein by reference in its entirety.
[0143] Generally, any amount of organoboro compounds can be used. According to one aspect of this invention, the molar ratio of total moles of organoboro or organoborate (or more compounds) to the total metallocene moles composed of the catalyst composition is in the range of about 0.1: 1 to about 15: 1 . Typically, the amount of the fluoroorgan boron or fluoroorgan borate compound used is about 0.5 moles to about 10 moles of boroborate composed of mole of metallocene compounds (catalyst component, catalyst component II, and any other compound (s)) metallocene. According to another aspect of this invention, the amount of fluoroorgane boron or fluoroorgane borate is from about 0.8 moles to about 5 moles of boroborate composed of moles of metallocene compounds. IONIZING IONIC COMPOUNDS
[0144] The present invention further provides a catalyst composition that can include an ionizing ionic compound. An ionizing ionic compound is an ionic compound that can function as a co-catalyst to improve the composition activity of the catalyst. While not intending to be bound by theory, it is believed that the ionizing compound is capable of reacting with a metallocene compound, converting the metallocene into one or more cationic metallocene compounds, or incipient cationic metallocene compounds. Again, while not intending to be bound by theory, he believes that the ionizing compound can function as an ionizing compound by completely or partially extracting an anionic binder, possibly a non-alkadienyl binder, metallocene. However, the ionizing compound is a co-catalyst of or activator regardless of whether it ionizes metallocene, summarizes a ligand to form an ion pair, weakens the metallocene bond in Metallocene, simply the coordinates for a ligand, or activates the metallocene by some other mechanism.
[0145] Furthermore, it is not necessary for the ionizing ionic compound to activate the metallocene compound (s) only. The activation function of the ionizing ionic compound may be evident in the increased catalyst composition activity as a whole, compared to a catalyst composition that does not contain an ionizing ionic compound.
[0146] EXAMPLES of ionizing ionic compounds include, but are not limited to, the following compounds: tri (n-butyl) ammonium tetrakis (p-tolyl) borate, tri (n-butyl) ammonium tetrakis (m-tolyl) borate, tri (n-butyl) ammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) - ammonium tetrakis [3,5-bis ( trifluoromethyl) phenyl] borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (p-tolyl) borate, N, N-dimethylanilinium tetrakis (m-tolyl) borate, N, N-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbene tetrakis (p-tolyl) borate, triphenylcarbene tetrakis (m-tolyl) borate, triphenylcarbene tetrakis (2,4-dimethylphenyl) borate, triphenylcarbene tetrakis (3,5-dimethylphenyl, 3-dimethylphenyl, 3-dimethylphenyl] 5-bis (trifluoromethyl) phenyl] borate, t rifenylcarbene tetrakis (pentafluorophenyl) borate, tropilium tetrakis (p-tolyl) borate, tropilium tetrakis (m-tolyl) borate, tropilium tetrakis (2,4-dimethylphenyl) borate, tropilium tetrakis (3,5-dimethylphenyl) borate, 3,5-bis (trifluoromethyl) phenyl] borate, tropilium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, lithium tetrafenylborate, lithium tetrakis (p-tolyl) borate, lithium tetrakis (m-tolil) borate, lithium 2,4-dimethylphenyl) borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluoroborate, sodium tetrakis (pentafluorophenyl) borate, sodium tetrafenylborate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, sodium tetrakis (2,4-dimethylphenyl) borate, sodium tetrakis (3,5-dimethylphenyl) borate, sodium tetrafluoroborate, potassium tetrakis (pentafluorophenyl) borate, potassium tetrafenylborate, potassium tetrakis (p-tolyl) borate, potassium t ) borate, potassium tetrakis (2,4-dimethylphenyl) borate, potassium tetrakis (3,5-dimethylphenyl) borate, p otassium tetrafluoroborate, lithium tetrakis (pentafluorophenyl) alum innate, lithium tetrafenilalum innate, lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate, lithium tetrakis (2,4-dimethylphenyl) aluminate, -dimethylphenyl) aluminate, lithium tetrafluoroalum innate, sodium tetrakis (pentafluorophenyl) aluminate, sodium tetrafenylaluminate, sodium tetrakis (p-tolyl) - aluminate, sodium tetrakis (m-tolyl) aluminate, sodium tetrakis (2,4-dimethyl) tetrakis (3,5-dimethylphenyl) aluminate, sodium tetrafluoroaluminate, potassium tetrakis (pentafluorophenyl) aluminate, potassium tetrafenylaluminate, potassium tetrakis (p-tolyl) aluminate, potassium tetrakis (m-tolyl) dimethalisethenate, potassium tetra) aluminate, potassium tetrakis (3,5-dimethylphenyl) aluminate, potassium tetrafluoroaluminate, and the like, or combinations thereof. Ionizing ion compounds useful for this invention are not limited to these; other EXAMPLES of ionizing ionic compounds are disclosed in U.S. Patent Nos. 5,576,259 and 5,807,938, the disclosures that are incorporated herein by reference, in their entirety. OLEFINE MONOMERS
[0147] Unsaturated reagents that can be employed with the polymerization processes of the catalyst compositions and this invention typically include olefin compounds, having 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. This invention encompasses homopolymerization processes using a simple olefin such as ethylene or Dibutylamine, as well as copolymerization, terpolymerization, etc., reactions using an olefin monomer with at least one different olefinic compound. For example, the resulting ethylene copolymers, terpolymers, etc., generally contain a large amount of ethylene (> 50 mole%) and a smaller amount of comonomer (<50 mole percent), although this is not a requirement. Comonomers that can be copolymerized with ethylene often have 3 to 20 carbon atoms in their molecular chain.
[0148] Acyclic, cyclic, polycyclic, terminal (a), olefins without added internal, linear, branched, substituted, substituted, functional, and can be employed in this invention. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention 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 (for example, 1-octene), the four normal nonenes, to five normal decines, and the like, or mixtures of two or more of these compounds. Bicyclic and cyclic olefins, including, but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above. Styrene can also be used as a monomer in the present invention. In one aspect, the olefin monomer is a C2-C10 olefin; Alternatively, the olefin monomer is ethylene; or alternatively, the olefin monomer is propylene.
[0149] When a copolymer (or, alternatively, a terpolymer) is desired, the olefin monomer may include, for example, ethylene or propylene, which is copolymerized with at least one comonomer. According to one aspect of this invention, the olefin monomer in the polymerization process is composed of ethylene. In this regard, EXAMPLES of appropriate olefin comonomers include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1- pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like , or combinations thereof. According to one aspect of the present invention, it can include the comonomer 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof.
[0150] Generally, the amount of comonomer introduced into a reactor zone to produce the copolymer is about 0.01 per about 50 percent of the comonomer based on the total weight of the monomer and comonomer. According to another aspect of the present invention, the amount of comonomer introduced into a reactor zone is about 0.01 to about 40 percent weight comonomer based on the total weight of the comonomer and the monomer. In yet another aspect, the amount of comonomer introduced into a reactor zone is about 0.1 to about 35 percent comonomer weight based on the total comonomer weight of the monomer. In yet another aspect, the amount of comonomer introduced into a reactor zone is about 0.5 to about 20 percent weight comonomer based on the total weight of the comonomer and the monomer.
[0151] While not intending to be bound by this theory, where branched, substituted, or added with olefins are used as reagents, it is believed that a spherical can prevent the and / or slow the polymerization process. Thus, and / or cyclic branched has some of the carbon-carbon double bond removed from the olefin should not prevent the reaction in the way that the same olefin substituent closest to the carbon carbon double bond can. According to an aspect of the present invention, at least one ethylene monomer reagent, thus the polymerizations are a homopolymerization involving ethylene only, or copolymerizations with different acidic, cyclic, terminal, internal, linear, branched, substituted, or substituted olefin. In addition, the catalyst compositions of this invention can be used in polymerizing diolefin compounds including, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene. CATALYST COMPOSITION
[0152] The present invention employs Catalyst Compositions containing catalyst component, catalyst component II, and at least one activator. These compositional catalysts can be used to produce polyolefins - homopolymers, copolymers, and the like - for a variety of end-use applications. Catalyst components I and II have been discussed above. In aspects of the present invention, a catalyst component is contemplated which may contain more than one compound Metallocene catalyst component and / or which II may contain more than one compound metallocene. In addition, one more activator can also be used.
[0153] Generally, the Catalyst Compositions of the present invention comprise catalyst component, catalyst component II, and at least one activator. In aspects of the invention, at least one activator can include at least one activator-support. Activator-support useful for the present invention has been disclosed above. Catalysts making this composition can still comprise one or more an organoaluminium compound or compounds (suitable organoaluminium compounds have also been discussed above). Thus, a catalyst composition of this invention can include catalyst component I, catalyst component II, at least one supporting activator, and at least one compound organoaluminum. For example, it can include at least one support activator fluoridated alumina, chlorinated alumina, bromidated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, bromidated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, fluorinated silica-zirconia, chlorinated silica - zirconia, bromidated silica-zirconia, sulfated silica-zirconia, fluoridated silica-titania, fluoridated silica-coated alumina, sulfated silica-coated alumina, phosphate silica-coated alumina, and the like, or combinations thereof. In addition, at least one organoaluminium compound can include trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminium ethoxide, diethylaluminum chloride, and similar, or combinations thereof.
[0154] Another aspect of the present invention, a compositing catalyst is provided that comprises catalyst component I, catalyst component II, at least one activator-support, and at least one compound organo-aluminum, wherein the compositing catalyst is substantially free of aluminoxanes, organoboro or organoborate compounds, ionizing ionic compounds, and / or other similar materials; Alternatively, substantially free of aluminoxanes; alternatively, substantially free or organoboro or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the composition of the catalyst has catalytic activity, to be discussed below, in the absence of these additional materials. For example, a catalyst composition of the present invention may consist essentially of catalyst component I, catalyst component II, an activator support, and an organoaluminium compound, where other materials are not present in the catalyst composition that increases / decreases the activity of the catalyst composition. for more than 10% of the catalyst composition activity in the absence of said materials.
[0155] However, in other aspects of the present invention, these activators / co-catalysts can be employed. For example, a composition making catalyst comprising catalyst component I, catalyst component II, and an activator support can further comprise an optional co-catalyst. Suitable co-catalysts in this regard include, but are not limited to, aluminoxane compounds, organoboro or organoborate compounds, ionizing ionic compounds, and the like, or any combination thereof. More than one co-catalyst can be present in the catalyst composition.
[0156] In a different aspect, a composition making catalyst is provided that does not require an activator support. Such a catalyst composition can include catalyst component, catalyst component II, and at least one activator, wherein at least one activator comprises at least one compound aluminoxane, at least one compound organoboro or organoborate, at least one ionizing ionic compound, or combinations of the same.
[0157] In a certain aspect contemplated in this document, the catalyst composition is a double composition catalyst composed of an activator (one or more than one), component only an ansa-metallocene catalyst, and only one component II catalyst Metallocene. For example, the catalyst composition can include at least one activator, only one loop-metallocene having formula (I), and only one loop-metallocene having formula (II). Alternatively, the catalyst composition can include at least one activator, only one loop-metallocene having formula (IA), and only one loop-metallocene having formula (IIB). In these aspects, metallocene only two compounds are present in the catalyst composition, that is, the component of a catalyst or a metallocene loop and a catalyst compound a component II loop-metallocene. It is also envisaged that a dual metallocene catalyst composition may contain small amounts of an additional metallocene compound (s), but this is not a requirement, and generally the dual catalyst composition may consist essentially of the above two metallocene compounds, and in substantial absence of any additional metallocene compounds, wherein any additional metallocene compounds that do not increase / decrease the activity of the catalyst composition by more than about 10% of the catalyst composition activity make the catalyst in the absence of the additional metallocene compounds.
[0158] This invention further encompasses methods of making this catalyst composition, such as, for example, coming into contact with the respective catalysts components in any order or sequence.
[0159] The metallocene composed of catalyst component, the metallocene composed of catalyst component II, or both, can be pre-contacted with an olefinic monomer, if desired, not necessarily the olefin monomer being polymerized, and an organoaluminium compound for a first time before contacting this pre-contacted mixture with a support activator. The first contact time period, Alaska, between the compound metallocene, the olefinic monomer, and the compound organoaluminium typically ranges from a time period of about 1 minute to about 24 hours, for example, about 0, 05 hours to about 1 hour. Pre-contact times of about 10 minutes to about 30 minutes are also employed. Alternatively, the pre-contact process is carried out in several stages, instead of a single stage, in which several mixtures are prepared, each containing a different set of catalyst components. For example, at least two catalyst components are contacted forming a first mixture, followed by contacting the first mixture with at least one other catalyst component forming a second mixture, and so on.
[0160] Several pre-contact steps can be carried out in a single container or in several containers. In addition, several pre-contact steps can be performed in series (sequentially), in parallel, or a combination of these. For example, a first mixture of two catalyst components can be formed in a first container, a second mixture comprising the first mixture, plus an additional catalyst component can be formed in the first vessel or in a second container, which is normally placed at downstream of the first container.
[0161] In another aspect, one or more of the components of the catalyst can be divided and used in different pre-contact treatments. For example, part of a catalyst component is fed into a first pre-contact container with at least one other catalyst component, while the remainder of that same catalyst component is fed into a second pre-contact container with at least one other catalyst component. , or is fed directly into the reactor, or a combination of these. Pre-contact can be carried out on any suitable equipment, such as tanks, stirred mixing tanks, various static mixing devices, a balloon, a vessel of any kind, or combinations of these devices.
[0162] Another aspect of this invention, the various catalyst components (eg, catalyst component I, catalyst component II, activator support, organoaluminium co-catalyst, and, optionally, an unsaturated hydrocarbon) are contacted in the polymerization reactor simultaneously while the polymerization reaction is process. Alternatively, any two or more of these components of the catalyst can be pre-contacted in a container before entering the reaction zone. This pre-contact step can be continuous, in which the pre-contacted product is fed continuously to the reactor, or it can be a batch process or in stages in which a batch of pre-contacted product is added to make a catalyst composition. This pre-contact step can be performed over a period of time that can vary from a few seconds to as many as several days or more. In this respect, the continuous pre-contact step generally lasts from about 1 second to about 1 hour. In another aspect, the continuous pre-contact step lasts for about 10 seconds to about 45 minutes, or about 1 minute to about 30 minutes.
[0163] Once a pre-mix of a metallocene catalyst component and / or metallocene component II catalyst compound, olefin monomer, and co-catalyst organoalumin is contacted with the activator support, this composition (with the addition of activator- support) is called "contact powder mix." The contact powder mixture optionally remains in contact for a second period of time, the post contact time, before starting the polymerization process. Post-contact times between the pre-contacted mixture and activator-support generally range from about 1 minute to about 24 hours. Another aspect, the post-contact time is in the range of about 0.05 hours to about 1 hour. The pre-contact step, the post-contact step, or both, can increase the polymer productivity compared to the same catalyst-making composition that is prepared without pre- or post-contact contact. However, a pre-contact step or a post-contact step is required.
[0164] The contacted powder mixture can be heated to a temperature and for a period of time sufficient to allow adsorption, impregnation, interaction or pre-contacted mixture and activator-support, such that a part of the components of the pre- contacted is immobilized, adsorbed, or deposited therein. Where heating is employed, the contacted powder mixture is generally heated to a temperature of between about 0 ° F to about 150 ° F, or from about 40 ° F to about 95 ° F.
[0165] According to one aspect of this invention, the weight ratio of the catalyst component to catalyst component II to the catalyst composition is generally in the range of about 100: 1 to about 1: 100. In another aspect, the weight ratio is in the range of about 75: 1 to about 1:75, about 50: 1 to about 1:50, or about 30 by about 1:30. In yet another aspect, the weight ratio of the catalyst component to catalyst component II to the catalyst making composition is in the range of about 25 to about 1:25. For example, the weight ratio can be in the range of about 20: 1 to about 1:20, about 15: 1 to about 1:15, about 10: 1 to about 1:10 , or from about 5: 1 to about 1: 5.
[0166] When a pre-contact step is used, the molar ratio of the total molar olefin monomers to the total metallocene moles (s) the pre-contacted mixture is typically in the range of about 1:10 to about 100, 000: 1. Total moles of each component are used in this proportion taking into account aspects of this invention where more than one olefin monomer and / or more than one metallocene is employed in a pre-contact step. In addition, this molar ratio can be in the range of about 10: 1 to about 1,000: 1 in another aspect of the invention.
[0167] Generally, the weight ratio of organo-aluminum compound activator-support is in the range of about 10: 1 to about 1: 1000. If more than one compound organoaluminium and / or more than one support activator is used, this proportion is based on the total weight of each respective component. In another aspect, it is the ratio of the weight of the compound to the organo-aluminum activator support in a range of about 3: 1 to about 1: 100, or from about 1: 1a to about 1:50.
[0168] In some respects, this invention, the weight ratio of metallocene compounds (total catalyst component and catalyst component II) to activator support is in a range of about 1: 1 to about 1: 1,000. , 000. If more than one support activator is employed, this proportion is based on the total weight of the support activator. In another aspect, this weight ratio is in the range of about 1: 5 to about building, 000, or about 01:10 to about 01:10, 000. Still, in another aspect, the The weight of the compounds for the metallocene activator support is in the range of about 1:20 to about 1: 1000.
[0169] Catalyst compositions of the present invention generally have a catalytic activity greater than about 100 grams of polyethylene (homopolymer, copolymer, etc., as the context requires) per gram of activator-support per hour (abbreviated gPZ (gAS-hr )). In another aspect, the activity of the catalyst is greater than about 150, greater than about 200, or greater than gP / (gAS.hr) about 250. Yet another aspect, catalysts for making the composition of this invention are characterized by have a catalytic activity greater than about 500, greater than about 1000, or greater than gPZ (gAS.hr) about 2000. Still, in another aspect, the activity of the catalyst is greater than about 3000 gPZ (gAS. hr). This activity is measured under slurry polymerization conditions using isobutane as a diluent, at a polymerization temperature of over-80 ° C and a reactor pressure of about 350 psig.
[0170] As discussed above, any combination of the metallocene composed of catalyst component eu and / or catalyst component II, the activator support, the organoaluminium compound, and the olefin monomer, can be pre-contacted in some respects, this invention . When any pre-contact occurs with an olefinic monomer, it is not necessary for the olefin monomer used in the pre-contact step to be the same as for the olefin to be polymerized. In addition, when a pre-contact step between any combination of the catalyst components is employed for a first period of time, that pre-contacted mixture can be used in a later post-contact step between any combination of catalyst components for a second time period. For example, one or more metallocene compounds, the organoaluminium compound, and 1-hexene can be used in a pre-contact step for a first period of time, and this pre-contacted mixture can then be contacted with the activator support to form a contacted powder mixture that is contacted for a second period of time before starting the polymerization reaction. For example, the first contact period, the pre-contact time, between any combination of the Metallocene compound (s), the olefinic monomer, the support activator, and the organoaluminium compound can be about 1 minute, about 24 hours, about 3 minutes to about 1 hour, or about 10 minutes to about 30 minutes. The contacted powder mix is optionally allowed to remain in contact for a second t period. POLYMERIZATION PROCESS
[0171] Catalyst compositions of the present invention can be used to olefins polymerize to form homopolymers, copolymers, terpolymers, and the like. One of those olefin processes to polymerize in the presence of a catalyst composition of the present invention comprises contacting the catalyst to make composition with an olefin monomer and optionally a comonomer olefin under polymerization conditions to produce an olefin polymer, in which the composition catalyst comprises catalyst component, catalyst component II, and at least one activator. Catalyst component which can include at least one loop-metallocene compound of formula (I) or, alternatively, at least one loop-metallocene having formula (IA). Catalyst component II can include at least one loop-metallocene compound of formula (II) or, alternatively, at least one loop-metallocene having formula (I IB).
[0172] In accordance with an aspect of the invention, the polymerization process employs a composition-making catalyst comprising catalyst component, catalyst component II, and at least one activator, wherein at least one activator comprises at least one support activator. Catalyst making this composition can still include at least one organoaluminum compound. Suitable organoaluminium compounds may include, but are not limited to, trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylaluminium, tri-n-hexylaluminium, tri-n-octylaluminium, diisobutylaluminum hydride, diethylaluminum ethoxide , diethylaluminum chloride, and the like, or any combination thereof.
[0173] In accordance with another aspect of the invention, the polymerization process employs a catalyst to make a composition composed of only one component of a loop-metallocene catalyst (i.e., a metallocene having any formula (I) or formula (IA) ), only a component II loop-metallocene catalyst (i.e., a metallocene having any formula (II) or formula (IIB)), at least one activator-support, and at least one compound organo-aluminum.
[0174] According to yet another aspect of the invention, the polymerization process employs a composition-making catalyst comprising catalyst component, catalyst component II, and at least one activator, wherein at least one activator comprises at least one compound aluminoxane, at least one organoboro or organoborate compound, at least one ionizing ionic compound, or combinations thereof.
[0175] The catalyst composition of the present invention is intended for any method of olefin polymerization using various types of polymerization reactors. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more of a comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of reactors include those that can be referred to as a batch reactor, slurry reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations thereof. The polymerization conditions for the various types of the reactor are well known in the art. Gas phase reactors can include fluidized bed reactors or staged horizontal reactors. Slurry reactors can include horizontal or vertical loops. High pressure reactors can include tubular or autoclave reactors. Reactor types can include batch or continuous processes. Continuous processes could use continuous or intermittent product discharge. Processes may include partial or complete direct recycling of the unreacted monomer, reacted comonomer, and / or diluent.
[0176] Polymerization reactor systems of the present invention may include one type of reactor in one or multiple reactor systems of the same or different types. Production of polymers in several reactors can include several stages in at least two separate polymerization reactors, interconnected by a transfer device, making possible the transfer of polymers resulting from the first polymerization reactors in the second reactors. The desired polymerization conditions in one of the reactors may differ from the operational conditions in other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from reactors to subsequent reactors for continuous polymerization. Various reactor systems may include any combination, including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a high pressure loop combination and / or gas phase reactors. The multiple reactors can be operated in series, in parallel, or both.
[0177] According to one aspect of the invention, the polymerization reactor system can include at least one reactor slurry loop comprising horizontal or vertical loops. Monomer, diluent, catalyst, comonomer and can be continuously fed with loop reactors where polymerization takes place. Generally, continuous processes may include the continuous introduction of monomer / comonomer, a catalyst and diluent into polymerization reactors and the continuous removal of these reactors from a suspension of polymer particles and the diluent. Reactor effluent can be flashed to remove the solid polymer from the liquids that make up the diluent, comonomer and / or monomer. Various technologies can be used for this separation step including but not limited to, intermittent, which can include any combination of pressure reduction and heat addition; separation by central action or a cyclone or hydrocyclone; or separation by centrifugation. A typical slurry polymerization process (also known as the particle form process) is disclosed, for example, in 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 incorporated herein by reference in its entirety.
[0178] Suitable diluents used in the slurry polymerization include, but are not limited to, the monomer being polymerized from hydrocarbons and which are liquid under reaction conditions. EXAMPLES of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, Neopentane, and n-hexane. Some loop polymerization reactions can occur under dough conditions where no diluents are used. One example is the polymerization of the propylene monomer as disclosed in U.S. Patent No. 5,455,314, which is incorporated by reference here in its entirety.
[0179] According to yet another aspect of this invention, polymerization reactors can include at least one of the gas phase reactors. Such systems can employ a continuous flow of recycle containing one or more monomers Ciciated continuously through a fluidized bed in the presence of catalyst under polymerization conditions. A recycle stream can be removed from the fluidized bed and recycled back to the reactors. Simultaneously, the polymer products can be removed from the reactors and new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors can include a multi-stage process of the olefin polymerization gas phase, in which olefins are polymerized in a gas phase in the polymerization zones of at least two gas-phase independent while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in U.S. Patent Nos. 5,352,749, 4,588,790, and 5,436,304, each of which is incorporated by reference in its entirety here.
[0180] According to yet another aspect of the invention, high pressure polymerization reactors can include a reactor autoclave or a tubular reactor. Tubular reactors can have multiple zones where fresh monomer, initiators, or catalysts are added. Monomer can be entrained in an inert gas stream and introduced into a reactor zone. Primers, catalysts, catalysts and / or components can be dragged into a gaseous stream and introduced into another zone of the reactors. The gas streams can be mixed for polymerization. Heat and pressure can be used properly to obtain ideal polymerization reaction conditions.
[0181] In accordance with yet another aspect of the invention, polymerization reactors can include a polymerization reactor solution in which the monomers / comonomers are in contact with the catalyst composition by suitable or stirring other means. A carrier of an inert organic excess monomer or thinner may be employed. If desired, the monomer / comonomer can be initiated in the vapor phase in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at pressures and temperatures that will result in the formation of a polymer solution in a reaction medium. Stirring can be used to obtain the best temperature control and to keep the polymerization mixes uniform throughout the polymerization zone. Suitable means are used to dissipate exothermic heat from polymerization.
[0182] Reactor polymerization feed system suitable for the present invention may further include any combination of at least one feedstock, at least one feed catalyst system or catalyst components, and / or at least one polymer recovery system. Additional reactor systems suitable for the present invention may include raw material purification, catalyst preparation and storage systems, extrusion, refrigeration reactors, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis, and control of process.
[0183] Polymerization conditions that are controlled for efficiency and provide the desired polymer properties 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 polymerization temperature according to the Gibbs free energy equation. This typically includes about 60 ° C to about 280 ° C, for example, or about 60 ° C to about 110 ° C, depending on the type of polymerization reactors. In some reactor systems, the polymerization temperature is generally in the range of about 70 ° C to about 90 ° C, or from about 75 ° C to about 85 ° C.
[0184] Appropriate pressures will also vary according to the type of polymerization and reactors. The pressure for the liquid phase polymerizations in a reactor loop is typically less than 1000 psig. Pressure for the polymerization gas phase is generally around 200 to 500 psig. High pressure polymerization in autoclave or tubular reactors is generally performed at about 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region occurring at generally high temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
[0185] Aspects of that invention directed to the polymerization process of olefins Understanding the contact with a catalyst to make composition with olefin is a monomer and, optionally, at least one olefin comonomer under polymerization conditions to produce an olefin polymer. The olefin polymer produced by the process can have an Mz / Mw ratio of about 3 to about 6. In addition, or alternatively, the olefin polymer can have an Mw / Mn ratio of about 3 to about 8. In addition, or alternatively, the olefin polymer may have a non-bimodal molecular weight distribution and / or a reverse comonomer distribution, which will be discussed further below.
[0186] Polymerization process this invention can be conducted in the presence of hydrogen, although this is not a requirement. In accordance with one aspect of this invention, a hydrogen ratio to the olefin monomer in the polymerization process is controlled. This weight ratio can vary from 0 ppm to about 10,000 ppm of hydrogen, based on the weight of the olefin monomer. For example, the reagent or hydrogen ratio feed the olefin monomer can be controlled in a weight ratio that falls in a range from 0 ppm to about 7500 ppm, from about 5 ppm to about 5000 ppm, or about from 10 ppm to about 1000 ppm.
[0187] It is also contemplated that hydrogen and / or monomer, comonomer (or comonomers), can be pulsed periodically to the reactors, for example, in a manner similar to that employed in US Patent No. 5,739,220 and EU patent publication n 0 20040059070, the disclosures that are incorporated herein by reference in their entirety.
[0188] In ethylene polymerizations, the hydrogen feed ratio of ethylene monomer, regardless of comonomer (s) employed, is generally controlled in a weight ratio of a range from 0 ppm to about 1000 ppm, or about 0.1 ppm of 500 of a fence, but the destination of the specific weight ratio may depend on the molecular weight of the desired polymer or melt index (Ml). For ethylene polymers (homopolymers, copolymers, etc.) having a Ml of about 1 min of g10, the weight ratio of hydrogen to ethylene is normally in the range of 0 ppm to about 750 ppm, such as, for example, about 5 ppm to about 500 ppm, or about 10 ppm to about 300 ppm.
[0189] The concentration of the reagents in the polymerization reactors can be controlled to produce resins with certain mechanical and physical properties. The proposed final product that will be formed by the polymer resin and the method of formation of which the product can finally determine the desired polymers Properties and attributes. Mechanical properties include tensile strength, bending, impact, creep, relaxation, hardness and stress tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack-growth, long chain branching and rheological measurements.
[0190] This invention is also directed to, and encompasses, polymers produced by any polymerization process disclosed here. Manufacturing articles can be formed from, can include and / or, polymers produced in accordance with this invention. POLYMERS AND ARTICLES
[0191] If the resulting polymer produced in accordance with the present invention, for example, an ethylene polymer or copolymer, its properties can be characterized by different analytical techniques known and used in the polyolefin industry. Manufacturing articles can be formed from, and / or can comprise, the ethylene polymers of this invention, the properties of which are provided below.
[0192] Ethylene polymers (copolymers, terpolymers, etc.) produced according to this invention generally have a melt index of about 0.01 to about 100 g10 min. melt indexes in the range of about 0.05 to about 50 min of g10, from about 0.1 to about 30 min of g10, or from about 0.3 to about 20 min of g10, are contemplated in some aspects, this invention. For example, a polymer of the present invention can have a melt index in the range of about 0.3 to about 10, about 0.5 to about 5, or about 0.5 to about 3 g / 10 min.
[0193] The density of ethylene-based polymers produced using the metallocene compounds disclosed here typically falls within the range of about 0.88 to about 0.97 g / cm3 In one aspect of the present invention, it is the density of an ethylene polymer in a range of about 0.90 to about 0.95 g / cm3. In yet another aspect, the density is in the range of about 0.91 to about 0.94 g / cm3, such as, for example, about 0.91 to about 0.93 g / cm3.
[0194] Ethylene polymers, such as copolymers and terpolymers, within the scope of the present invention generally have a dash - a ratio of the average molecular weight to weight (Mw) the average number to the molecular weight (Mn) - polydispersity index a range of about from 3 to about 8. In some aspects, disclosed here, a ratio of Mw / Mn is in the range of about 3 to about 7.5, about 3 to about 7, about 3 to about 6.5, or about 3 to about 6. For example, the Mw / Mn polymer can be in the range of about 3 to about 5.8, about 3.1 to about 5.6, about 3.1 at about 5.4, about 3.2 to about 5.2, or about 3.2 to about 5.
[0195] The Mz / Mw ratio for the polymers of this invention is often in the range of about 3 to about 6. MZ is the average molecular weight of z, and Mw is the average molecular weight of the weight. According to one aspect, the Mz / Mw of the ethylene polymers of this invention is in the range of about 3 to about 5.8, about 3 to about 5.6, about 3 to about 5.4, from about 3 to about 5.2, or from about 3 to about 5. According to another aspect, Mz / Mw is in the range of about 3 to about 4.8; alternatively, from about 3 to about 4.5; alternatively, from about 3.1 to about 4.5; or alternatively, from about 3.2 to about 4.5.
[0196] Ethylene polymers may, in some respects, have this invention, the Mz in a range of about 100,000 to about 975,000 g / mol, such as, for example, about 125,000 to about 900,000, from about 150,000 to about 850,000 g / mol, or about 175,000 g / mol to 800,000 of a fence. Accordingly, Mz of the ethylene polymer can be in the range of about 200,000 to about 750,000 g / mol in aspects of this invention. In other respects, ethylene polymers of this invention have a molecular weight distribution in which the molecular weight distribution curve does not have a high molecular weight component that extends to a molecular weight above 10,000,000 g / mol.
[0197] Polymers of this invention can also be characterized as having a non-bimodal molecular weight distribution. As used here, non-bimodal means that there are no two peaks distinguishable from the molecular weight distribution curve (as determined using permeation gel chromatography (GPC) or another recognized in the analytical technique). Non-bimodal includes unimodal distributions, where there is only one peak. Peaks are also not distinguishable, if there are two peaks on the molecular weight distribution curve and there is no obvious valley between the peaks, or either of the peaks is not considered to be a distinguishable peak, or two peaks are not considered to be distinguishable peaks. Fig. 1-5 illustrate the representative bimodal molecular weight distribution curves. These numbers, there is a valley between the peaks, and the peaks can be separated or unrolled. Often, a bimodal molecular weight distribution is characterized as having a high molecular weight component (or distribution) and an identifiable low molecular weight component (or distribution). In contrast, Fig. 6-11 illustrate representative non-bimodal molecular weight distribution curves. These include unimodal molecular weight distributions, as well as distribution curves containing two peaks that cannot be easily distinguished, separated or unwound.
[0198] Ethylene polymers (eg, copolymers) produced using the polymerization process and catalyst systems described above have a reverse comonomer distribution. A reverse comonomer distribution, as used herein, refers to a polymer in which the higher molecular weight polymer components have greater comonomer incorporation than the lower molecular weight components. Generally, there is an increasing incorporation of comonomer with increasing molecular weight. Often, the amount of comonomer incorporation in higher molecular weight is about 20% or higher, higher, in molecular weight less than 30%. In one aspect, the amount of the higher molecular weight comonomer incorporation is about 50% higher than the lowest molecular weight. Another feature of a reverse comonomer distribution is that the number of short chain branches (SCB) per 1000 total carbon atoms is greater in Mw than in Mn.
[0199] Furthermore, the SCBD (short chain branch distribution) of polymers of the present invention can be characterized by a number of making the ratio of SCB per 1000 total carbon atoms of the polymer in D10 to the number of SCB per 1000 total carbon atoms of the polymer in D90, i.e. (SCB in D10) / (SCB in D90). D90 is the molecular weight in which 90% polymer by weight has the highest molecular weight, and D10 is the molecular weight in which 10% non-polymer weight has the highest molecular weight. D90 and D10 are plotted in Fig. 12 for a molecular weight distribution curve as a function of the logarithmic increase in molecular weight. In accordance with one aspect of the present invention, a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D10 to the number of SCB per 1000 total carbon atoms of the polymer in D90 is in a range of about 1.1 to about 5. For example, the ratio number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D10 to the number of SCB per 1000 total carbon atoms in D90 can be in the range of about 1.1 to about 4, or about 1.1 to about 3. Generally, polymers disclosed here have about 1 to about 10 short chain branches (SCB) per 1000 total carbon atoms in D90, and this usually varies with the density of the polymer.
[0200] Likewise, the polymer SCBD of the present invention can be characterized by a ratio of the number of SCB per 1000 total carbon atoms of the polymer in D15 to the number of SCB per 1000 total carbon atoms of the polymer in D85, that is, (SCB in D15) / (SCB in D85). D85 is the molecular weight in which 85% polymer by weight has the highest molecular weight, and D15 is the molecular weight in which 15% makes polymer weight has the highest molecular weight. D85 and D15 are plotted in Fig. 13 for a molecular weight distribution curve as a function of the logarithmic increase in molecular weight. In accordance with one aspect of the present invention, a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D15 to the number of SCB per 1000 total carbon atoms in D85 is in a range of about 1.1 to about 4. For example, the ratio of the number of short chain branches (SCB) per 1000 total polymer carbon atoms in D15 to the number of SCB per 1000 total polymer carbon atoms in D85 can be in the range of about 1.1 to about 3.5, or from about 1.1 to about 2.5.
[0201] Furthermore, the polymers of this invention can be characterized as having a number of short-chain branch (SCB) per 1000 total polymer carbon atoms versus the polymer molecular weight logarithm which is substantially linear between D85 and D15. Fig. 14-15 are EXAMPLES illustrative of a linear regression analysis for a respective SCBD. Plot triangles represent measured SCB data given molecular weights. The solid straight lines in the plots are the trend lines from the linear regression analysis of the measured data. Batch equations are for trend lines. R2 is the correlation parameter for the trend line in each plot. For disclosure purposes, polymer resin will have a “substantially linear” SCBD if a linear regression analysis results in a R2 of the trend line for the SCBD measure greater than 0.8. Based on this definition, Fig. 14 is considered to have a substantially linear SCBD using linear regression analysis (R2 is equal to about 0.97). In contrast, Fig. 15 does not have a substantially linear SCBD based on linear regression analysis (R2 is equal to about 0.68). In some aspects, this invention, R2 may be greater than about 0.85, or greater than about 0.90, or greater than about 0.95.
[0202] Generally, the polymers of the present invention have low levels of long chain branching, with generally less than approximately 0.05 long chain branches (LCB) per 1000 total carbon atoms, but greater than zero. In some respects, the number of LCBs per 1000 total carbon atoms is about less than 0.04, less than about 0.03, less than about 0.02, or less than about 0.01 . In addition, polymers of the present invention may have less than approximately 0.009, less than approximately 0.008, less than about 0.007, less than 0.006 about, or less than about 0.005 LCB per 1000 total carbon atoms, in other aspects of the present invention.
[0203] An example of not limiting and illustrative of an ethylene polymer of the present invention can be characterized by a non-bimodal molecular weight distribution; a Mw / Mn ratio of about 3 to about 8; an Mz / Mw ratio of about 3 to about 6; and a reverse comonomer distribution. Another exemplary ethylene polymer has a non-bimodal molecular weight distribution; a Mw / Mn ratio of about 3 to about 6; an Mz / Mw ratio of about 3 to about 5; and a reverse comonomer distribution. However, another ethylene polymer disclosed here has a non-bimodal molecular weight distribution; a Mw / Mn ratio of about 3.2 to about 5; an Mz / Mw ratio of about 3 to about 4.5; and a reverse comonomer distribution. Such illustrative polymers can also be further characterized by an Mz in the range of about 100,000 to about 975,000 g / mol and / or a melt index in the range of about 0.1 to about 30 g / 10 min and / or a density of about 0.90 to about 0.95 g / cm3, and / or less than about 0.008 long chain branches (LCB) per 1000 total carbon atoms, and / or about 1 to about 10 short chain branches (SCB) per 1000 total carbon atoms in D90, and / or a ratio number of short chain branches (SCB) per 1000 total carbon atoms in D10 to the number of SCB per 1000 total atoms of polymer carbon in D90 over a range of 1.1 to about 5, and / or a ratio number of short chain branches (SCB) per 1000 total polymer carbon atoms in D15 to the number of SCB per 1000 total polymer carbon atoms in D85 in a range of 1.1 to about 4 and / or a substantially linear plot of the number of chain branches the short (SCB) per 1000 total polymer carbon atoms versus the polymer molecular weight logarithm, between D90 and D10.
[0204] Ethylene polymers, whether homopolymers, copolymers, terpolymers, and so on, can be formed into various articles of manufacture. Articles that may include polymers of this invention include, but are not limited to, an agricultural film, an automobile part, a bottle, a drum, a fabric or fiber, a container of film or food packaging, a food service article, a fuel tank, geomembrane, domestic container, liner, molded product, medical material or device, tube, tape or foil, toy, and the like. Various processes can be employed to form these articles. Do not limit these processes. EXAMPLES of injection molding, blow molding, rotational molding, extrusion, sheet extrusion, profile extrusion, thermoforming and the like. In addition, additives and modifiers are often added to these polymers to provide beneficial polymer attributes of final product or processing. EXAMPLES
[0205] The invention is further illustrated by EXAMPLES below, which should not be construed in any way as imposing limitations on the scope of the present invention. Various other aspects, incorporations, modifications, equivalents and respective which, after reading the description here, can be suggested to a common skill in the art without departing from the spirit of the present invention or the scope of the attached claims.
[0206] melt index (Ml, g / 10 min) was determined in accordance with ASTM D1238 at 190 ° C with a weight of 2,160 grams.
[0207] Density of the polymer was determined in grams per cubic centimeter (gcm3) in a molded compression sample, refrigerated at about 15 ° C per hour, and conditioned for about 40 hours at temperature according to ASTM D1505 and ASTM D1928 , process C.
[0208] Molecular weight and molecular weight distributions were obtained using a PL 220 SEC high temperature chromatography unit (polymer labs) with trichlorobenzene (TCB) as solvent, at a flow rate of 1 mL / minute at a temperature of 145 ° C. BHT (2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g / L was used as a TCB stabilizer. An injection volume of 200 pL was used with a nominal polymer concentration of 1.5 mg / mL. Dissolving the sample in stabilized TCB was carried out by heating at 150 ° C for 5 hours with occasional, gentle agitation. The columns used were three mixtures of PLgel and columns (7.8x300mm) one LS were calibrated with a wide linear polyethylene standard (Phillips Marlex® BHB 5003) so that the molecular weight was determined.
[0209] Short-chain branching distribution data (SCBD) was obtained using a SEC-FTIR high temperature heated flow cell (polymer labs), as described by PJ DesLauriers, DC Rohlfing, and ET Hsieh, Polymer, 43 , 159 (2002).
[0210] The sulfated alumina-support activator used in EXAMPLES 1-6 was prepared according to the following procedure. W.R. Grace company was obtained under the designation "Alumina A" and, having a surface area of about 300 m2 / g and a pore volume of about 1.3 mL / g. This material was obtained as a powder, having an average particle size of approximately 100 microns. This material was impregnated with incipient moisture with an aqueous solution of ammonium sulphate of about 15% equal. This mixture was then placed on a flat tray and allowed to dry under vacuum at approximately 110 ° C for about 16 hours.
[0211] To calcinate the support, about 10 grams of this powder mixture were placed in a 1.75-inch quartz tube equipped with a synthesized quartz disk beam at the bottom. While the powder was supported on the disc, air (nitrogen can be replaced) dried, passing through a 13 X molecular sieve column, was blown up through the disc at a linear rate of 1.6 to 1.8 standard cubic feet per hour. An electric oven around the quartz tube was then turned on and the temperature was raised at a rate of about 400 ° C per hour at the desired calcination temperature of about 600 ° C. at this temperature, the powder was allowed to fluidize for about three hours in dry air. Then, the sulfated alumina-support activator was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
[0212] The polymerization runs were carried out in a gallon (3.8 liters) stainless steel reactors as follows. First, the reactors were purged with nitrogen and then with isobutane vapor. Approximately 0.5 mL of 1 M triisobutylaluminium (TIBA), 100-130 mg of sulfated activator-alumina support (SA), and the desired amount of and / or met 1 MET 2 (see below for structures of 1 met and MET 2) were added in that order through a loading port while venting isobutane steam. The cargo port was closed and 1.8-2.0 L of isobutane were added. The contents of the reactors were stirred and heated to 75-80 ° C. Then, 30-45 grams of 1-hexene were added in reactors, followed by the introduction of hydrogen and ethylene, with the hydrogen added in a fixed mass ratio to the ethylene flow. Hydrogen was stored in a 340 ml_ pressure vessel and added with ethylene through an automatic feeding system, while the total reactor pressure was maintained at 305 psig or 355 psig by the combined addition of ethylene / hydrogen / isobutane. The reactors were maintained and controlled at 80 ° C or 75 ° C during the polymerization to make 30 minutes of run time. Upon completion, isobutane and ethylene were evacuated from the reactors, the reactors were opened, and the polymer product was collected and dried. EXAMPLES 1-6 Polymers produced using Metallocene MET 1 and / or Metallocene MET 2 Metallocene MET 1 has the following structure:
Metallocene MET 2 has the following structure:

[0213] MET 1 and MET 2 can be prepared in accordance with any suitable method. Representation techniques are described in U.S. Patent Nos. 7,064,225 and 7,517,939, the disclosures that are incorporated herein by reference in their entirety.
[0214] Polymer properties resulting from polymerization conditions and for comparative EXAMPLES 1-3 are shown in Table I. The properties of polymer resulting from polymerization conditions and comparative EXAMPLE 4 and inventive EXAMPLES 5-6 are listed in table II. The weight ratio of MET 1: MET 2 was about 20: 1 in EXAMPLE 5, and about 13: 1 in EXAMPLE 6.
[0215] As shown in Tables II, the Mz / Mw ratio for using 1-4 was less than 3. In contrast, the Mz / Mw ratio for EXAMPLES 5-6 was greater than 3.
[0216] Fig. 16 illustrates the polymers of making molecular weight distributions of EXAMPLES 5-6. EXAMPLES 5-6 polymers both have a unimodal molecular weight distribution. Fig. 17 compares the content of the SCB as a function of the logarithm of the molecular weight of polymers from EXAMPLES 5-6, as well as providing a respective linear regression analysis. Polymers of EXAMPLES 5-6 exhibit a reverse comonomer distribution and, in addition, the SCBD to make polymers of EXAMPLES 5-6 is substantially linear.
[0217] Fig. 18 illustrates a portion of the SCB content - the number of short chain branches (SCB) per 1000 carbon atoms - as a function of the molecular weight logarithm, and a linear regression analysis, for the polymer of EXAMPLE 6. Between D15 and D85, the plot of the number of short chain branches (SCB) per 1000 total polymer carbon atoms versus the polymer molecular weight logarithm is substantially linear. Using linear regression analysis, an R2 of the line trend is equal to about 0.99. Table I. Polymerization Conditions and Polymer Properties of EXAMPLES 1-3.

- Notes in Table I: - Polymerization conditions: 355 psig pressure, 80 ° C, 2 liters of isobutane Table I (continued).
Table II. Polymerization conditions and Polymer properties of EXAMPLES 4-6.
- Notes in Table II: - Polymerization conditions: 305 psig pressure, 75 ° C, 1.8 liters of isobutane Table II (continued).
COMPARATIVE EXAMPLES 7-8 Polymer properties of commercially available polyolefin resins [0218] Comparative example 7 is a LLDPE resin, available from the Dow Chemical Company under the grade Dow Elite® 5100. Comparative example 8 is a resin LLDPE, available from the Dow Chemical Company under the grade Dow Elite® 5400. The polymer properties of Comparative Examples 7-8 are listed in Table III. The data for Mn, Mw, Mz, Mw / Mn, and Mz / Mw were determined in the same way as EXAMPLES 1-6, using the analytical procedure described above. As shown in Table III, the Mz / Mw of these polymers is less than 3, in fact, less than 2.5. Table III. Polymer properties of Comparative Examples 7-8.
- Notes in Table III: - Ml and Density are nominal properties extracted from product literature on specific resin qualities

权利要求:
Claims (15)
[0001]
1. Olefin polymerization process characterized by comprising: contacting a catalyst composition with an olefin monomer and, optionally, at least one olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a catalyst component I, catalyst component II and at least one activator, wherein: the catalyst component I comprises at least one ansa-metallocene compound of formula (I):
[0002]
Process according to claim 1, characterized in that the catalyst composition comprises at least one activator, only one loop-metallocene compound having formula (I), and only one loop-metallocene having formula (II).
[0003]
Process according to claim 1, characterized by at least one activator comprising at least one activator-support comprising a solid oxide treated with an electron withdrawing anion, wherein: the solid oxide comprises silica, alumina, silica-alumina , silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; and the electron withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluozirconate, fluorotitanate, or any combination thereof.
[0004]
Process according to claim 1, characterized in that the catalyst composition further comprises at least one organoaluminium compound having the formula: AI (X3) m (X4) 3-m, wherein: X3 is a hydrocarbyl; X4 is an alkoxide, or an aryloxide, a halide, or a hydride; and m is 1 to 3, inclusive.
[0005]
5. Process according to claim 4, characterized by: at least one organoaluminium compound comprises trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, hydride diisobutylaluminum, diethylaluminum ethoxide, diethylaluminium chloride, or any combination thereof; and at least one activator comprises at least one activator-support, and at least one activator-support comprises fluorinated alumina, chlorinated alumina, bromidized alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, bromidated silica-alumina, sulfated silica-aluminas, fluorinated silica zirconia, chlorinated silica-zirconia, bromidated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, silica-coated fluorinated alumina, silica-coated sulfated alumina, silica-coated phosphate alumina or any silica-coated combination of these.
[0006]
Process according to claim 1, characterized by at least one activator comprising at least one aluminoxane compound, at least one organoboro or organoborate compound, at least one ionizing ionic compound, or any combination thereof.
[0007]
Process according to claim 1, characterized by: in formula (I): at least one of R1A and R2 ^ is a terminal alkenyl group having up to 12 carbon atoms; or at least one CpA substituent is a terminal alkenyl or terminal alkenylsilyl group having up to 12 carbon atoms; and in formula (II): at least one of R1B and R2B is a terminal alkenyl group having up to 12 carbon atoms; or at least one CpB substituent is a terminal alkenyl or terminal alkenylsilyl group having up to 12 carbon atoms.
[0008]
Process according to claim 1, characterized in that the catalyst component I comprises:
[0009]
Process according to claim 1, characterized by: the catalyst component I comprises at least one loop-metallocene compound of formula (IA):
[0010]
Process according to claim 9 characterized by: MA and MB are independently Zr or Hf; X1A, X2A, X1B, and X2B are independently F, Cl, Br, I, methyl, benzyl or phenyl; EA, EB, YA, θ YB are C; R A R4A RSB θ R4B independently H or methyl; R5Ae RSBsθ0 independently a terminal alkenyl group having up to 8 carbon atoms; R6A, R7A, R6B and R7B are independently H or a hydrocarbon group having up to 6 carbon atoms; and CpA and CpB are independently a cyclopentadienyl, indenyl, or fluorenyl group, or wherein: R1B and R2B are phenyl; R6A, R7A, R6B, and R7B are independently H or t-butyl; and CpA and CpB are cyclopentadienyl.
[0011]
Process according to claim 1, characterized by a weight ratio of the catalyst component I to the catalyst component II in the catalyst composition being in a range of 100: 1 to 1: 100, or the olefin monomer being ethylene, and at least one olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.
[0012]
12. Ethylene polymer characterized by having a non-bimodal molecular weight distribution; a Mw / Mn ratio of 3 to 8; a Mz / Mw ratio of 3 to 6; and a reverse comonomer distribution, where the polymer has less than 0.008 long chain branches (LCB) per 1000 total carbon atoms.
[0013]
13. Ethylene polymer according to claim 12, characterized in that: the polymer's Mw / Mn ratio is in the range of 3 to 6; the polymer's Mz / Mw ratio is in the range of 3 to 5; the polymer has an Mz in a range of 100,000 to 975,000 g / mol; the polymer has a melt index in the range of 0.1 to 30 g / 10 min; the polymer has a density of 0.90 to 0.95 g / cm3; or any combination thereof, or the polymer has 1 to 10 short chain branches (SCB) per 1000 carbon atoms in total in D90; a ratio of the number of short chain branches (SCB) per 1000 carbon atoms in the total polymer in D10 to the number of SCB per 1000 carbon atoms in the total polymer in D90 is in the range of 1.1 to 5; a ratio of the number of short chain branches (SCB) per 1000 carbon atoms in the total polymer in D15 to the number of SCB per 1000 carbon atoms in the total polymer in D85 is in the range of 1.1 to 4; or a portion of the number of short chain branches (SCB) per 1000 carbon atoms in the total polymer versus the logarithm of the polymer's molecular weight is substantially linear between D85 and D15; or any combination of these.
[0014]
14. Article characterized by comprising the polymer as defined in claim 12 or 13.
[0015]
15. Catalyst composition characterized by comprising the catalyst component I, the catalyst component II, and at least one activator, wherein: the catalyst component I comprises at least one loop-metallocene compound of formula (I): where: MA is Ti, Zr or Hf; X1A and are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH <OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; EA is C or Si; R1A and R2 ^ are independently H, a hydrocarbyl group having up to 18 carbon atoms, or R1A and R2 ^ are joined to form a cyclic or heterocyclic group having up to 18 carbon atoms, where R1A and R2 ^ are not aryl groups; R6A and R7A are independently H or a hydrocarbon group having up to 18 carbon atoms; and CpA is a cyclopentadienyl, indenyl, or fluorenyl group, or a hetero-substituted derivative thereof, any substituent on CpA is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms; and the catalyst component II comprises at least one ansa-metallocene compound having the formula (II): where: MB is Ti, Zr or Hf; X1B and X2B are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; EB is C or Si; R1B and R2B are independently H or a hydrocarbon group having up to 18 carbon atoms, wherein at least one of R1B and R2B is an aryl group having up to 18 carbon atoms; R6BΘ R BS BS 0 0 n n enc enc enc enc ou ou H or a hydrocarbon group having up to 18 carbon atoms; and CpB is a cyclopentadienyl, indenyl, or fluorenyl group, or a hetero-substituted derivative thereof, any substituent on CpB is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms.

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CA2796737A1|2011-10-27|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-03-31| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-08-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-10-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/04/2011, 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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US12/762,414|US8383754B2|2010-04-19|2010-04-19|Catalyst compositions for producing high Mz/Mw polyolefins|

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US12/762,414|2010-04-19|

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PCT/US2011/032610|WO2011133409A1|2010-04-19|2011-04-15|CATALYST COMPOSITION FOR PRODUCING HIGH Mz/Mw POLYOLEFINS|

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