MX2014011850A - Catalyst systems containing a bridged metallocene reference to related application. - Google Patents

Abstract

The present invention provides polymerization processes utilizing a catalyst system containing an ansa-metallocene and a second metallocene compound for the production of olefin polymers.

Description

CATALYST SYSTEMS CONTAINING A BRIDGE METALOCENE REFERENCE TO THE RELATED APPLICATION This application is a continuation application in part of a co-pending United States Patent Application No. 12 / 899,753, filed on October 7, 2010, which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION The present invention relates in general to the field of olefin polymerization catalysis, metallocene catalyst compositions, methods for the polymerization and copolymerization of olefins, and polyolefins.

BRIEF DESCRIPTION OF THE INVENTION Described herein are catalyst systems employing polymerization processes containing a bridged metallocene and at least one additional metallocene compound for the production of olefin polymers. The olefin polymers produced from the described polymerization processes demonstrate unexpected properties due to the presence of bridged metallocene in the catalyst system.

In accordance with one aspect of the present invention, a catalyst composition is provided, and this catalyst composition comprises an ansa-metallocene compound, a second metallocene compound, and an activator (eg, a support 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 monomer under polymerization conditions to produce an olefin polymer, in wherein the catalyst composition comprises an ansa-metallocene compound, a second metallocene compound, and an activator (e.g., a support activator).

In these catalyst compositions and polymerization processes, the ansa-metallocene compound has formula (I): E (CpARAm) (CpBRBn) MXq; where: M is Ti, Zr, Hf, Cr, Se, Y, La, or a lanthanide; CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group; each RA and RB independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxy group having up to 18 carbon atoms; E is a bridged chain of 3 to 8 atoms carbon or 2 to 8 silicon, germanium or tin atoms, wherein any substituent on independently bridged chain atoms is H or a hydrocarbyl group having up to 18 carbon atoms; each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; m is O, 1, 2, 3, or 4; n is 0, 1, 2, 3, or 4; q is 2 when M is Ti, Zr, or Hf; Y q is 1 when M is Cr, Se, Y, La, or a lanthanide.

Polymers produced from the polymerization of olefins using these catalyst systems containing an ansa-metallocene compound, resulting in homopolymers, copolymers, and the like, can be used to produce various articles of manufacture.

BRIEF DESCRIPTION OF THE FIGURES Figure 1 illustrates the impact of hydrogen addition on molecular weight in a representative double standard catalyst system.

Figure 2 illustrates the impact of adding hydrogen at the molecular weight in a representative double catalyst system in accordance with one aspect of this invention.

Figure 3 illustrates the definitions of D90 and DIO in a molecular weight distribution curve.

Figure 4 presents a graph of the molecular weight distributions of the polymers of Examples 3, 5, and 7.

Figure 5 presents a graph of the molecular weight distributions of the polymers of Examples 2, 6, and 15.

Figure 6 presents a graph of the molecular weight distributions of the polymers of Examples 2, 3, and 16.

Figure 7 presents a graph of the molecular weight distributions of the polymers of Examples 6-7 and 44-45.

Figure 8 presents a graph of the radius of gyration against the logarithm of molecular weight for a linear standard and the polymers of Examples 2-3 and 6-7.

Figure 9 presents a plot of Delta versus log G * (complex module) for the polymers of Examples 2-3 and 6-7.

Figure 10 presents a graph of catalyst activity against concentration of 1-hexene comonomer initial for Examples 2-7 and 40-45.

Figure 11 presents a graph of first-order models of catalyst activity against initial 1-hexene comonomer concentration for Examples 2-7 and 40-45.

Figure 12 presents a graph of the logarithm of melt index versus hydrogen-fed concentration for the polymers of Examples 4-5, 7, and 17-24.

Figure 13 shows a graph of the high load melt index against the melt index for the polymers of Examples 4 and 17-24.

Figure 14 presents a graph of zero shear viscosity versus average weight molecular weight, specifically, log (r0) against log (Pm), for the polymers of Examples 2-3, 5-7, 18, 44- 45, and 66-67.

Figure 15 presents a graph of the molecular weight distributions of the polymers of Examples 100-102.

DEFINITIONS To define more clearly the terms used herein, the following definitions are provided. To the extent that any of the definitions or uses provided by any document incorporated herein by reference run counter to the definition or use provided herein, the definition or use provided in the present control.

The term "polymer" is used herein generically to include homopolymers, copolymers, olefin terpolymers, and so forth. The copolymer is derived from an olefin monomer and an olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Therefore, "polymer" encompasses copolymers, terpolymers, etc., derived from any monomer and olefin comonomer (s) described herein. Similarly, an ethylene polymer may include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, and the like. As an example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene / l-hexene copolymer.

Likewise, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process may involve contacting an olefin monomer (e.g., ethylene) and an olefin comonomer (e.g., 1-hexene) to produce a copolymer.

Hydrogen in this description can refer to ya is hydrogen (H2) which is used in a polymerization process, or a hydrogen atom (H), which may be present, for example, in a metallocene compound. When used to indicate a hydrogen atom, hydrogen can be shown as "H," whereas if the intention is to describe the use of hydrogen in a polymerization process, it is simply referred to as "hydrogen." The term "co-catalyst" is generally used herein to refer to organoaluminum compounds which may constitute a component of a catalyst composition. Additionally, "co-catalyst" can refer to other components of a catalyst composition including, but not limited to, aluminoxane, organoboron or organoborate compounds, and ionizing ionic compounds, as described herein, when used in addition to a support activator. The term "co-catalyst" is used in spite of the current function of the compound or any chemical mechanism by which the compound can operate. In one aspect of this invention, the term "co-catalyst" is used to distinguish that component of the catalyst composition of the metallocene compound (s).

The terms "chemically treated solid oxide," "support activator," "solid oxide compound treated," and the like, are used herein to denote an inorganic oxide, a solid of relatively high porosity, which it can exhibit Lewis acidic or Br0nsted acidic behavior, and which has been treated with an attractant electron component, typically an anion, and which is calcined. The attractant electron component is typically a compound of the source of the attractant electron anion. Therefore, the chemically treated solid oxide may comprise a calcined contact product of at least one solid oxide with at least one compound from the electron attractant anion source. Typically, the chemically treated solid oxide comprises at least one acidic solid oxide compound. The terms "support" and "support activator" are not used to imply that these components are inert, and these components should not be constructed 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 herein, generally refers to a substance that is capable of converting a metallocene component to a catalyst that can polymerize olefins, or to convert a contact product of a metallocene component and a metallocene component. component that provides an activatable ligand (eg, an alkyl, a hydride) to the metallocene, when the metallocene compound no longer comprises this ligand, in a catalyst that can polymerize olefins. This term is used despite the mechanism of current activation. Illustrative activators include support activators, aluminoxane compounds, organoboron or organoborate, ionizing ionic compounds, and the like. Compounds of aluminoxanes, organoboron or organoborate, and ionizing ionic compounds in general are referred to as activators if they are used in a catalyst composition in which a support activator is not present. If the catalyst composition contains a support activator, then the aluminoxane, organoboron or organoborate, and ionizing ionic materials are typically referred to as co-catalysts.

The term "fluoroorgano boron compound" is used herein with its ordinary meaning to refer to neutral compounds of the form BY3. The term "fluoroorgano borate compound" also has its usual meaning to refer to the monoanionic salts of a fluoroorgano boron compound of the form [cation] + [BY4] wherein Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as "organoboron or organoborate compounds." The term "metallocene," as used herein, describes a compound that comprises at least one cycloalkdienyl-3-a-5-type moiety, wherein the cycloalkadienyl-3 to 5-moieties include cyclopentadienyl ligands, indenyl ligands, ligands of fluorenyl, and the like, including partially saturated or substituted derivatives or analogs of any of these. Possible substituents on these ligands may include H, therefore this invention comprises partially saturated ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially saturated substituted indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, the metallocene is simply referred to as the "catalyst," in the same way the term "co-catalyst" is used herein to refer to, for example, an organoaluminum compound. Metallocene is also used generically herein to encompass dinuclear metallocene compounds, ie, compounds comprising two metallocene moieties joined by a linking group, such as an alkenyl group resulting from an olefin metathesis reaction or a resulting saturated version of hydrogenation or deri atomization.

The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like, not dependent on the current product or composition resulting from the contact or reaction of the initial components of the claimed composition / mixture / catalyst system, of the nature of the active catalytic site, or the fate of the catalyst, the metallocene compound (s), any olefin monomer is used to prepare a previously contacted mixture, or the activator (eg, support activator), after combining these components. Therefore, the terms "catalyst composition," "catalyst mixture," "catalyst system," and the like, encompass the initial starting components of the composition, as well as any product (s) can result from contacting these components. initial starting, and this is included of systems or heterogeneous catalyst compositions as homogeneous.

The term "contact product" is used herein to describe compositions wherein the components are in contact together in any order, in any manner, and for any length of time. For example, the components may be contacted by combination or mixing. In addition, the contact of any component may occur in the presence or absence of any other component of the compositions described herein. The combination of additional materials or components can be carried out by any suitable method. In addition, the term "contact product" includes mixtures, combinations, solutions, suspensions, reaction products, and the like, or combinations thereof. Although "contact product" may include reaction products, it is not required by the respective components to react with another. Similarly, the term "contacting" is used herein to refer to materials which may be combined, mixed, suspended, dissolved, reacted, treated, or otherwise brought into contact in some other way.

The term "pre-contacting" mixture is used herein to describe a first mixture of catalyst components that are in contact for a first period of time before the first mixture is used to form "after-contact" or second mixture. catalyst components that are in contact for a second period of time. Typically, the premixed mixture describes a mixture of metallocene compound (one or more than one), olefin monomer (or monomers), and organoaluminum compound (or compounds), before this mixture is in contact with an activator of support (s) and optional additional organoaluminum compound. Therefore, the previous contact describes components that are used to put them in contact with each other, but before putting the components in contact with the second, subsequent contact mixture. Therefore, this invention can occasionally distinguish between a component that is used to prepare the previously contacted mixture and that the component after the mixture has been prepared. For example, in accordance with this description, it is possible for the organoaluminum compound contacted previously, once it is contacted with the metallocene compound and the olefin monomer, to have reacted to form at least one compound, formulation or chemical structure different from the compound of different organoaluminum used to prepare the mixture put in contact previously. In this case, the previously contacted organoaluminum compound or component is described as comprising an organoaluminum compound which is used to prepare the previously contacted mixture.

Additionally, the premixed mixture can describe a mixture of metallocene compound (s) and organoaluminum compound (s), before contacting this mixture with a support activator (s). This previously contacted mixture can also describe a mixture of metallocene compound (s), olefin monomer (s), and support activator (s), before this mixture is contacted with a co-catalyzing compound or compounds. of organoaluminium.

Similarly, the term "after-contact" mixture is used herein to describe a second mixture of catalyst components that is in contact for a second period of time, and a constituent which is "previously contacted" or first mix of catalytic components that are put in contact for a first period of time. Typically, the term "after-contact" mixture is used herein to describe the mixture of metallocene compound (s), olefin monomer (s), organoaluminum compound (s), and support activator (s) formed to Starting from contacting the previously contacted mixture of a portion of these components with any of these additional components added to compensate for the subsequent contact mixture. Often, the support activator comprises a chemically treated solid oxide. For example, the additional component added to compensate for the subsequent contact mixture may be a chemically treated solid oxide (one or more than one), and optionally, may include an organoaluminum compound which is the same as or different from the compound of organoaluminium which is used to prepare the previously contacted mixture, as described herein. Therefore, this invention can also occasionally distinguish between a component that is used to prepare the subsequent contact mixture and the component after the mixture that has been prepared.

Although any of the methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, typical methods, devices and materials are describe in the present.

All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the structures and methodologies described in the publications, which may be used in conjunction with the presently described invention. The publications discussed through the text are provided only for description before the filing date of the present application. Nothing herein is constructed as an admission that the inventors are not entitled to precede this description by virtue of the foregoing invention.

For any of the particular compounds described herein, any general or specific structure presented also encompasses all conformational isomers, regioisomers and stereoisomers that may arise from a particular series of substituents, unless otherwise described. Similarly, unless otherwise described, the general or specific structure also encompasses all enantiomers, diastereomers, and other optical isomers if in enantiomeric or racemic forms, as well as mixtures of stereoisomers, they can be recognized by a skilled in the art.

The applicant describes various types of ranges in the present invention. These include, but are not limited to a, a range of number of atoms, a range of weight ratios, a range of molar ratios, a range of surface areas, a range of pore volumes, a range of catalyst activities, a range of temperatures, ranges of time, and so on. When the Applicant describes or claims an interval of any kind, the Applicant's intent is to individually describe or claim each possible number of this range that can be reasonably encompassed, which includes endpoints of the interval as well as any sub-intervals and sub combinations. -intervals covered in this. For example, when the applicant describes or claims a chemical portion having a certain number of carbon atoms, the Applicant's intent is to individually describe or claim each possible number of this range that can be encompassed., consistent with the description herein. For example, the description of a portion is a hydrocarbyl group Ci to Ci8, or alternatively a hydrocarbyl group having up to 18 carbon atoms, as used herein, refers to a portion that can be selected independently from a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 15, 17, or 18 carbon atoms, as well as any range between these two numbers (for example, a hydrocarbyl group Ci a CQ), and also including any combination of intervals between these two numbers (for example, a hydrocarbyl group C2 to C4 and one of Ci2 to Ci6) · Similarly, another representative example below for the molar ratio of olefin comonomer to olefin monomer provided in one aspect of this invention. For a description that the comonomer: olefin monomer ratio may be in a range from about 0.01: 1 to about 0.25: 1, the Applt attempts to describe that the comonomer / monomer ratio can be about 0.01: 1, about 0.02: 1, about 0.03: 1, about 0.04: 1, about 0.05: 1, about 0.06: 1, about 0.07: 1, about 0.08: 1 , about 0.09: 1, about 0.1: 1, about 0.12: 1, about 0.14: 1, about 0.16: 1, about 0.18: 1, about 0.20: 1, about 0.22: 1, about 0. 24: 1, or about 0.25: 1. Additionally, the comonomer / monomer ratio can be within any range from about 0.01: 1 to about 0.25: 1 (eg, from about 0.01: 1 to about 0.1: 1), and this also includes any combination of intervals between about 0.01. : 1 and approximately 0. 25: 1 (for example, the comonomer / monomer ratio is in a range of about 0.01: 1 to about 0.1: 1, or about 0.15: 1 to about 0.20: 1). Likewise, all other ranges described herein must be interpreted in a manner similar to these two examples.

The Applt reserves the right to condition or exclude any of the individual elements of any of this group, which includes any sub-intervals or combinations of sub-intervals within the group, which may be claimed in accordance with an interval or in any Similarly, if for any reason the Applt chooses to claim less than the full extent of the description, for example, to take into account a reference that the Applt may be unaware of at the time of filing the applion. In addition, the Applt reserves the right to condition or exclude any of the individual substituents, analogs, compounds, ligands, structures, or groups thereof, or any element of a claimed group, if for any reason the Applt elects to claim less. of the full extent of the description, for example, to take into account a reference that the Applt may not know at the time of this presentation of the applion.

The terms "a," "one," "the," etc., are planned to include plural alternatives, for example, at least one, unless otherwise specified. For example, the description of "a support activator" or "an ansa-metallocene compound" is understood as encompassing one, or mixtures or combinations of more than one, support activator or anne-metallocene compound, respectively.

While the compositions and methods are described in terms of "comprising" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the varied components or steps. For example, a catalyst composition of the present invention may comprise; alternatively, it may consist essentially of; or alternatively, it may consist of; (i) an ansa-metallocene compound; (ii) a second metallocene compound; and (iii) an activator.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed in general to catalyst compositions, methods for preparing catalyst compositions, methods for using catalyst compositions to polymerize olefins, polymer resins produced using these catalyst compositions, and articles produced using these polymer resins. In one aspect, the present invention relates to a catalyst composition, this catalyst composition comprising (or consisting essentially of, or consisting of) an ansa-metallocene compound, a second metallocene compound, and an activator (e.g. a support activator).

In another aspect, an olefin polymerization process is provided and, in taspect, the process comprises (or consists essentially of, or consists of) contacting a catalyst composition with an olefin monomer and optionally an olefin monomer under of polymerization to produce an olefin polymer, wherein the catalyst composition comprises (or consists essentially of, or consists of) an ansa-metallocene compound, a second metallocene compound, and an activator.

Homopolymers, copolymers, olefin terpolymers, and the like, can be produced using the catalyst compositions and methods for olefin polymerization described herein.

ANSA-METALOCENE COMPOUND A catalyst composition of the present invention may comprise an ansa-metallocene compound having the formula (I). Formula (I) is: E (CpARAm) (CpBRBn) MXq; where: M is Ti, Zr, Hf, Cr, Se, Y, La, or a lanthanide; CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group; each RA and RB independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxy group having up to 18 carbon atoms; E is a bridged chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium or tin atoms, wherein any substituent on independently bridged chain atoms is H or a hydrocarbyl group having up to 18 carbon atoms; each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; m is 0, 1, 2, 3, or 4; n is 0, 1, 2, 3, or 4; q is 2 when M is Ti, Zr, or Hf; Y q is 1 when it is Cr, Se, Y, La, or a lanthanide Unless otherwise specified, formula (I) above, any other of the structural formulas are described herein, and any of the metallocene species or compounds described herein are not designed to show stereochemical or isomeric positioning of the different portions (for example, these formulas are not planned to exhibit cis or trans isomers, or diastereomers R or S), although these compounds are contemplated and encompassed by these formulas and / or structures.

Hydrocarbyl is used herein to specify a radical hydrocarbon group including, but not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like, and includes all substituted derivatives , unsubstituted, linear and / or branched thereof. Unless otherwise specified, the hydrocarbyl groups of tinvention typically comprise up to about 18 carbon atoms. In another aspect, the carbyl groups can have up to 12 carbon atoms, for example, up to 10 carbon atoms, up to 8. carbon atoms, or up to 6 carbon atoms. A hydrocarbyloxide group, therefore, is used generically to include alkoxide, aryloxide, and - (alkyl or aryl) -0- (alkyl or aryl) groups, and these groups may comprise up to about 18 carbon atoms. Illustrative and non-limiting examples of alkoxide and aryloxide groups (ie, hydrocarbyloxide groups) include methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like. The term "hydrocarbylamino group" is used generically to refer collectively to alkylamino, arylamino, dialkylamino, diarylamino, and - (alkyl or aryl) -N- (alkyl or aryl) groups, and the like. Unless otherwise specified, the hydrocarbylamino groups of tinvention comprise up to about 18 carbon atoms. Hydrocarbylsilyl groups include, but are not limited to, alkylsilyl groups, alkenylsilyl groups, arylsilyl groups, arylalkysilyl groups, and the like, which have up to about 18 carbon atoms. For example, illustrative hydrocarbylsilyl groups may include trimethylsilyl and phenyloctylsilyl. These hydrocarbyloxide, hydrocarbylamino, and hydrocarbylsilyl groups can have 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.

Unless otherwise specified, groups 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 within this definition. As an example, unless otherwise specified, the term propyl is understood to include n-propyl and iso-propyl, while the term "butyl" is understood to include n-butyl, iso-butyl, t-butyl, sec. -butyl, and so on. For example, non-limiting examples of octyl isomers include 2-ethyl hexyl and neooctyl. Suitable examples of alkyl groups which may 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 can be a terminal alkenyl group, but this is not a requirement. For example, substituents of the specific alkenyl group can 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.

In this description, arilo is understood as including aryl and alkylaryl groups, and these include, but are not limited to, phenyl, substituted alkyl-phenyl, naphthyl, substituted-alkyl-naphthyl, substituted-phenyl-alkyl, substituted-naphthyl-alkyl, and the like. Therefore, non-limiting examples of these "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 specified, any portion of substituted aryl that is used herein is meant to include all regioisomers; for example, the term "tolyl" is understood to include any possible substituent position, which is, ortho, meta, or para.

In formula (I), it is Ti, Zr, Hf, Cr, Se, Y, La, or a lanthanide. In one aspect of this invention, M is Ti, Zr, Hf, or Cr. In another aspect, M is Se, Y, or La. In yet another aspect, M is a lanthanide. Still, in some aspects described herein, M is Ti, Zr, Hf, Cr, or a lanthanide; alternatively, M is Ti or Cr; alternatively, M is Ti, Zr, or Hf; alternatively, M is Ti; alternatively, M is Zr; or alternatively, M is Hf.

When M is Ti, Zr, or Hf, q is 2. However, when M is Cr, Se, Y, La, or a lanthanide, q is 1.

CpA and CpB in the formula (I) can independently be a cyclopentadienyl, indenyl, or fluorenyl. In one aspect of this invention, at least one of CpA and CpB is a cyclopentadienyl group. In another aspect, at least one of CpA and CpB is an indenyl group. In yet another aspect, at least one of CpA and CpB is a fluorenyl group. In yet another aspect, CpA and CpB independently are a cyclopentadienyl or indenyl group. For example, CpA can be a cyclopentadienyl group and CpB can be an indenyl group, or CpA as well as CpB can be an indenyl group.

In formula (I), each RA and RB independently can be H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxy group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. In some aspects, each RA and RB independently can be H or an alkyl group, an alkenyl group (e.g., a terminal alkenyl group), or an aryl group having up to 12 carbon atoms; alternatively, having up to 10 carbon atoms; or alternatively, having up to 8 carbon atoms. Therefore, each RA and RB independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl , phenyl, tolyl, or benzyl.

Each substituent Rft and RB, independently, may be different. For example, CpA can have both a methyl substituent and a propenyl substituent. As another example, Cp may have two t-butyl substituents. Therefore, a CpAR¾2 group can be an indenyl group with both a methyl substituent as well as a propenyl substituent, while a CpBRB2 group can be a fluorenyl group with two t-butyl substituents.

In the formula (I), m can be 0, 1, 2, 3, or 4, while independently n can be 0, 1, 2, 3, or 4. The integers m and n reflect the total number of substituents in CpA and CpB, respectively (excluding group E of bridging, to be discussed further below), regardless of whether the substituents are the same or different. When m is equal to 0, CpA can be, for example, an unsubstituted cyclopentadienyl group or an unsubstituted indenyl group, that is, without different substitutions than bridging group E.

Each X independently can be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 (-OBR2) or S03R (-OS02R), wherein R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The hydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. It is contemplated that each X independently may be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, each X independently can be Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, each X independently can be benzyl, phenyl, or methyl. Still, in another aspect, each X can be Cl; alternatively, each X can be benzyl; alternatively, each X can be phenyl; or alternatively, each X can be methyl.

The bridging group E can be a bridging chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium or tin atoms. For example, E can be a bridging chain of 3 to 8 carbon atoms, 3 to 6 carbon atoms, 3 to 4 carbon atoms, 3 carbon atoms, or 4 carbon atoms. Alternatively, E may be a bridging chain of 2 to 8 silicon, germanium or tin atoms, of 2 to 6 silicon, germanium or tin atoms, of 2 to 4 silicon, germanium or tin atoms, of 2 to 4 atoms of silicon, of 2 silicon atoms, of 3 silicon atoms, or of 4 silicon atoms.

Any substituent on independently bridged chain atoms are H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Suitable substituents may include, but are not limited to, H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl. , phenyl, tolyl, or benzyl In one aspect, the substituents independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, butenyl, pentenyl, hexenyl, phenyl, or benzyl. In another aspect, the substituents independently can be methyl, ethyl, propyl, butyl, allyl, butenyl, pentenyl, or phenyl.

In accordance with one aspect of this invention, E is a bridged chain having the formula - (CR10AR10B) u-, where u is an integer from 3 to 8 (e.g., u is 3, 4, 5, or 6). ), and R10A and R10B are independently H or a hydrocarbyl group having up to 18 carbon atoms; alternatively, up to 12 carbon atoms; or alternatively, up to 8 carbon atoms. It is contemplated that R10A and R10B independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl , tolyl, or benzyl; alternatively, H, methyl, ethyl, propyl, butyl, allyl, butenyl, pentenyl, phenyl, or benzyl; or alternatively, H, methyl, ethyl, propyl, or butyl. In some aspects, u is 3, 4, 5, or 6, and R10A and R10B are both H, or methyl, or ethyl, or propyl, or butyl, or allyl, or butenyl, or pentenyl, or phenyl, or benzyl.

In accordance with another aspect of this invention, E is a bridged chain having the formula - (SiR11AR11B) v ~ wherein v is an integer from 2 to 8 (for example, v is 2, 3, 4, 5, or 6), and R11A and R11B are independently H or a hydrocarbyl group having up to 18 carbon atoms; alternatively, up to 12 carbon atoms; or alternatively, up to 8 carbon atoms. It is contemplated that R11A and R11B independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl , tolyl, or benzyl; alternatively, H, methyl, ethyl, propyl, butyl, allyl, butenyl, pentenyl, phenyl, or benzyl; or alternatively, H, methyl, ethyl, propyl, or butyl. In some aspects, v is 2, 3, 4, 5, or 6 (for example, v is 2), and R11A and R11B both are H, or methyl, or ethyl, or propyl, or butyl, or allyl, or butenyl , or pentenyl, or phenyl, or benzyl.

It is contemplated in aspects of the invention that M in formula (I) may be Ti, Zr, or Hf; q can be 2; each RA and RB independently can be H or a hydrocarbyl group having up to 12 carbon atoms; and E can be a bridging chain of 3 to 6 carbon atoms or 2 to 4 silicon atoms, wherein any substituent on independently bridged chain atoms can be H or a hydrocarbyl group having up to 12 carbon atoms. Additionally, each X in the formula (I) independently it can be F, Cl, Br, I, methyl, benzyl, or phenyl; m may be 0, 1, or 2; and n can be 0, 1, or 2.

In a further aspect, M may be Zr or Hf; each RA and RB independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl , or benzyl; E may be a bridging chain of 3 to 4 carbon atoms or 2 to 3 silicon atoms, wherein any substituent on independently bridged chain atoms may be H or methyl; m can be 0 or 1; and n can be 0 or 1. Even further, Cp¾ and CpB can independently be a cyclopentadienyl group or an indenyl group, E can be -SiMe 2 -SiMe 2-, and each X can be Cl, in other aspects of this invention.

Non-limiting examples of ansa-metallocene compounds having the formula (I) that are suitable for use in catalyst compositions and polymerization processes described herein, either singly or in combination, include, but are not limited to, the following compounds : , which include combinations thereof.

According to another aspect of this invention, the ansa-raetalocene compound having the formula (I) may comprise (or consist essentially of, or consist of) an ansa-metallocene compound having the formula (II), or formula (III) ), or formula (IV), or formula (V), or formula (VI), or formula (VII), or combinations thereof: formula (II) formula (III) formula (VI) formula (VII).

In the formulas (II), (III), (IV), (V), (VI), and (VII), X, RA, RB, m, and n are as described above by the formula (I) · In some aspects, for example, each X in formulas (II), (III), (IV), (V), (VI), and (VII) independently can be F, Cl, Br, I, methyl, benzyl, or phenyl, while each RA and RB independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl , phenyl, tolyl, or benzyl.

M can be Ti, Zr, or Hf in formulas (II), (III), (IV), (V), (VI), and (VII), while m '+ m "= m and n' + n "= n The substituents on silicon bridging chain atoms, RE, RF, RG, and RH, can independently be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 atoms Thus, RE, RF, RG, and RH independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl; alternatively, RE, RF, RG, and RH independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, butenyl, pentenyl, hexenyl, phenyl, or benzyl; alternatively, RE, RF, RG, and RH independently can be methyl, ethyl, propyl, butyl, allyl, butenyl, pentenyl, or phenyl; alternatively, RE, RF, RG, and RH can be H; alternatively, RE, RF, RG, and RH can be methyl; alternatively, RE, RF, RG, and RH can be ethyl; alternatively, RE, RF, RG, and RH can be propyl; alternatively, RE, RF, RG, and RH can be butyl; alternatively, RE, RF, RG, and RH can be allyl; alternatively, RE, RF, RG, and RH can be butenyl; alternatively, RE, RF, RG, and RH can be pentenyl; or alternatively, RE, RF, RG, and RH can be phenyl.

In accordance with another aspect of this invention, the ansa-metallocene compound having the formula (I) can comprising (or consisting essentially of, or consisting of) an ansa-metallocene compound having the formula (C), formula (D), formula (E), or combinations thereof.

Formula (C) is ; where: M3 is Zr or Hf; X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; E3 is a bridging group that has the formula -SiR R -SiR R-, wherein R, R, R, and are independently H or a hydrocarbyl group having up to 10 carbon atoms; R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; Y Cp1 is a cyclopentadienyl or indenyl group, any substituent on Cp1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.

In formula (C), M3 can be Zr or Hf, while X4 and X5 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R can be an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The hydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.

X4 and X5 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X4 and X5 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X4 and X5 independently are benzyl, phenyl, or methyl. Still, in another aspect, both X4 and X5 can be Cl; alternatively, both X4 and X5 can be benzyl; alternatively, both X4 and X5 can be phenyl; or alternatively, both X4 and X5 can be methyl.

In formula (C), E3 can be a bridging group having the formula -SiR7DR8D-SiR7ER8E-, wherein R7D, R8D, R7E, and R8E are independently H or a hydrocarbyl group having up to 10 carbon atoms or, alternatively, up to 6 carbon atoms. Therefore, in aspects of this invention, RD, R8D, R7E, and R8E independently may be H or an alkyl group or an alkenyl having up to 6 carbon atoms; alternatively, R7D, R8D, R7E, and R8E independently can be H, methyl, ethyl, propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R7D, R8D, R7E, and R8E independently can be H, methyl, or ethyl; alternatively, R7D, R8D, R7E, and RSE can be H; or alternatively, R7D, R8D, R7E, and R8 can be methyl.

R9 and R10 in the fluorenyl group in the formula (C) independently can be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Therefore, R9 and R10 independently can be H or a hydrocarbyl group having up to 8 carbon atoms, such as, for example, alkyl groups: methyl, ethyl, propyl, butyl, pentyl, or hexyl, and the like. In some aspects, R9 and R10 are independently methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl, while in other respects, R9 and R10 are independently H or t-butyl. For example, both R9 and R10 can be H or, alternatively, both R9 and R10 can be t-butyl.

In the formula (C), Cp1 is a cyclopentadienyl or indenyl group. Often, Cp1 is a cyclopentadienyl group. Any substituent on Cp1 can be H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; or alternatively, any substituent may be H or a hydrocarbyl or hydrocarbylsilyl group having up to 12 carbon atoms. Possible substituents on Cp1 may include H, therefore this invention comprises partially saturated ligands such such as tetrahydroindenyl, partially saturated indenyl, and the like.

In one aspect, Cp1 has no additional substitutions other than those shown in formula (C), for example, without different substituents than bridging group E3. In another aspect, Cp1 may have one or two substituents, and each substituent independently is H or an alkyl, alkenyl, alkylsilyl, or alkenylsilyl group having up to 8 carbon atoms, or alternatively, up to 6 carbon atoms. Still, in another aspect, Cp1 may have a substituent H, methylethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, or octenyl alone.

In accordance with one aspect of this invention, X4 and X5 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl, while R9 and R10 independently can be H or t-butyl, and Cp1 either has no substituents Additional or Cp1 may have a substituent selected only from H or an alkyl, alkenyl, alkylsilyl, or alkenylsilyl group having up to 8 carbon atoms. In these and other aspects, E3 may be a bridging group having the formula -SiR7DR8D-SiR7ER8E-, wherein R7D, R8D, R7E, and R8E are independently H or methyl. ; where: M4 is Zr or Hf; X6 and X7 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; E4 is a bridging group having the formula -SiR12DR13D-SiR12ER13E-, wherein R12D, R13D, R12E, and R13E are independently H or a hydrocarbyl group having up to 10 carbon atoms; Y R14, R15, R16, and R17 are independently H or a hydrocarbyl group having up to 18 carbon atoms.

In the formula (D), M4 can be Zr or Hf, while X6 and X7 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH; OBR2 or S03R, wherein R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The hydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.

X6 and X7 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X6 and X7 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X6 and X7 independently are benzyl, phenyl, or methyl. Still, in another aspect, both X6 and X7 can be Cl; alternatively, both Xs and X7 can be benzyl; alternatively, both X6 and X7 can be phenyl; or alternatively, both X6 and X7 can be methyl.

In formula (D), E4 can be a bridging group having the formula -SiR12DR13D-SiR12ER13E-, wherein R12D, R13D, R12E, and R13E independently can be H or a hydrocarbyl group having up to 10 carbon atoms or , alternatively, up to 6 carbon atoms. Therefore, in aspects of this invention, R12D, R13D, R1 E, and R13E independently may be H or an alkyl group or an alkenyl having up to 6 carbon atoms; alternatively, R12D, R13D, R1 E, and R13 independently may be H, methyl, ethyl, propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R12D, R13D, R12E, and R13E independently can be H, methyl, ethyl, propyl, or butyl; alternatively, R12D, R13D, R12E, and R13 independently may be H, methyl, or ethyl; alternatively, R12D, R13D, R12E, and R13E can be H; or alternatively, RL¿D, R, R1, and R can be methyl.

R14, R15, R16, and R17 in the fluorenyl groups in the formula (D) independently can be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Thus, R14, R15, R16, and R17 can independently be H or a hydrocarbyl group having up to 8 carbon atoms, such as, for example, alkyl groups: methyl, ethyl, propyl, butyl, pentyl, or hexyl, and the like. In some aspects, R14, R15, R16, and R17 are independently methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl, while in other aspects, R14, R15, R16, and R17 are independently H or t- butyl. For example, R14, R15, R16, and R17 may be H or, alternatively, R14, R15, R16, and R17 may be t-butyl.

It is contemplated that X6 and X7 independently may be F, Cl, Br, I, benzyl, phenyl, or methyl in the formula (D), and R14, R15, R16, and R17 independently may be H or t-butyl. In these and other aspects, E4 can be a bridging group having the formula -SiR12DR13D-SiR12ER13E-, wherein R12D, R13D, R12E, and R13E are independently H or methyl.

Formula (E) is; where M5 is Zr or Hf; X8 and X9 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; Y E5 is a bridging group selected from: a bridging group having the formula - (CH2) W-, where w is an integer from 3 to 8, inclusive, or a bridging group having the formula -SiR20BR21B- SiR20cR21c-, wherein R20B, R21B, R0c, and R21c are independently H or a hydrocarbyl group having up to 10 carbon atoms.

In the formula (E), M5 can be Zr or Hf, while X8 and X9 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The group hydrocarbyloxide, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.

X8 and X9 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X8 and X9 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X8 and X9 independently are benzyl, phenyl, or methyl. Still, in another aspect, both X8 and X9 can be Cl; alternatively, both X8 and X9 can be benzyl; alternatively, both X8 and X9 can be phenyl; or alternatively, both X8 and X9 can be methyl.

In the formula (E), E5 is a bridging group. In accordance with one aspect of this invention, E5 can be a bridging group having the formula - (CH2) W-, where w is an integer from 3 to 8, inclusive. The integer w may be 3, 4, 5, or 6 in some aspects of this invention. In accordance with another aspect of this invention, E5 can be a bridging group having the formula -SiR20BR21B- SiR20cR21c-, wherein R20B, R2B, R20c, and R21c independently can be H or a hydrocarbyl group having up to 10 carbon atoms. carbon or, alternatively, up to 6 carbon atoms. Therefore, in aspects of this invention, R20B, R21B, R20c, and R21c independently may be H or an alkyl group or an alkenyl having up to 6 carbon atoms; alternatively, R20B, R 21b, R 20c, and R21c may independently be H, methyl, ethyl, propyl, butyl, allyl, butenyl, pentenyl or; alternatively, R20B, R21B, R20c, and R21c independently may be H, methyl, ethyl, propyl, or butyl; alternatively, R20B, R21B, R20c, and R21c independently may be H, methyl, or ethyl; alternatively, R20B, R21B, R20c, and R21c can be H; or alternatively, R20B, R21B, R20c, and R21c can be methyl.

In one aspect of this invention, X8 and X9 in formula (E) independently may be F, Cl, Br, I, benzyl, phenyl, or methyl, and in some aspects, E5 may be a bridging group having the formula - (CH2) W-, where w is equal to 3, 4, or 5, or alternatively, E5 can be a bridging group having the formula -SiR R - SiR20cR21c-, wherein R20B, R21B, R20c, and R21c are independently H or methyl.

Non-limiting examples of metallocene-containing compounds having formula (E) that are suitable for use herein include, but are not limited to, the following: and the like, or combinations thereof.

As noted above, unless otherwise specified, formulas (C), (D), and (E), or any other structural formulas are described herein, and any of the metallocene species described herein are not designed to show stereochemistry or isomeric positioning of the different portions (for example, these formulas are not intended to exhibit cis or trans isomers, or diastereomers R or S), although these compounds are contemplated and encompassed by these formulas and / or structures.

SECOND METALOCENE COMPOUND A catalyst composition of the present invention may comprise an alpha-metallocene compound having the formula (I), as described herein above, and a second metallocene compound. The Applicant contemplates that the catalyst composition may contain one or more than one ansa-metallocene compound having the formula (I), and / or one or more than one second metallocene compound. Therefore, the catalyst composition can contain two metallocenes (for example, a double catalyst system), three metallocenes, four metallocenes, and so on. In general, there is no limitation in the selection of the second metallocene compound or compounds, which can be used in combination with the ansa-metallocene compound having the formula (I) described herein, different from the second metallocene compound being different from the Ansa-metallocene compound having the formula (I) · In accordance with one aspect of the invention, the second metallocene compound can comprise a bridged metallocene compound. In another aspect, the second metallocene compound may comprise an unbridged metallocene compound. In yet another aspect, the second metallocene compound may comprise a dinuclear metallocene compound. In yet another aspect of the invention, the second metallocene compound may comprise a metallocene compound (or dinuclear compound) containing an alkenyl portion. For example, the second metallocene compound, if it is unbridged or bridged, may contain an alkenyl substituent on a cyclopentadienyl, indenyl, and / or fluorenyl group.

Alternatively, or in addition, the bridged metallocene may contain an alkenyl substituent in the bridging group (or the bridging atom).

Often, with the second metallocene compound, the transition metal can be Ti, Zr, Hf, Cr, Se, Y, La, or a lanthanide (or it can be more than one, for example, if a dinuclear metallocene compound is employed). For example, the second metallocene, whether bridged or unbridged, may contain a transition metal such as Ti, Zr, or Hf; alternatively, the transition metal is Ti; alternatively, the transition metal is Zr; or alternatively, the transition metal is Hf.

In one aspect, the second metallocene may comprise a bridged metallocene compound, and in this regard, the bridged metallocene compound may comprise a bridged carbon atom alone, or alternatively, a single silicon bridging atom. However, the bridged metallocene compound may comprise a substituted fluorenyl group.

In accordance with another aspect of this invention, the second metallocene may comprise a bridged metallocene compound having the formula (C2): (C2); where : M3 is Ti, Zr, or Hf; X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 (-OBR2) or S03R (-OS02R), wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; E3 is a bridging group that has the formula > EAR1AR8A, wherein E3a is C or Si, and R7A and R8A are independently H or a hydrocarbyl group having up to 18 carbon atoms; R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; Y Cp1 is a cyclopentadienyl or indenyl group, any substituent on Cp1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.

In the formula (C2), M3 can be Ti, Zr, or Hf (for example, Zr or Hf), while X4 and X5 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R can be an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The hydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.

X4 and X5 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X4 and X5 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X4 and X5 independently are benzyl, phenyl, or methyl. Still, in another aspect, both X4 and X5 can be Cl; alternatively, both X4 and X5 can be benzyl; alternatively, both X4 and X5 can be phenyl; or alternatively, both X4 and X5 can be methyl.

In the formula (C2), E3 can be a bridging group having the formula > E3AR7AR8A, wherein E3A is a bridging atom C or Si, and R7A and R8A are independently H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. For example, R7A and R8A independently may be H or an alkyl, alkenyl (eg, a terminal alkenyl), or aryl group having up to 12 carbon atoms. In one aspect, R7A and R8A independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like. In another aspect, R7A and R8A independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, phenyl, tolyl, or benzyl. In yet another aspect, at least one of R7A and R8A is phenyl. In yet another aspect, at least one of R7A and R8A is a terminal alkenyl group having up to 6 carbon atoms.

R9 and R10 in the fluorenyl group in the formula (C2) independently can be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Therefore, R9 and R10 independently can be H or a hydrocarbyl group having up to 8 carbon atoms, such as, for example, alkyl groups: methyl, ethyl, propyl, butyl, pentyl, or hexyl, and the like. In some aspects, R9 and R10 are independently methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl, while in other aspects, R9 and R10 are independently H or t-butyl. For example, both R9 and R10 may be H or, alternatively, both R9 and R10 may be t-butyl.

In the formula (C2), Cp1 is a cyclopentadienyl or indenyl group. Often, Cp1 is a cyclopentadienyl group. Any substituent on Cp1 can be H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; or alternatively, any substituent may be H or a hydrocarbyl or hydrocarbylsilyl group having up to 12 carbon atoms. Possible substituents on Cp1 may include H, therefore this invention comprises partially saturated ligands such as tetrahydroindenyl, partially saturated indenyl, and the like.

In one aspect, Cp1 has no additional substitutions other than those shown in formula (C2), for example, without substituents other than bridging group E3. In another aspect, Cp1 may have one or two substituents, and each substituent independently is H or an alkyl, alkenyl, alkylsilyl, or alkenylsilyl group having up to 8 carbon atoms, or alternatively, up to 6 carbon atoms. Still, in another aspect, Cp1 may have a substituent H, methylethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, or octenyl alone.

According to one aspect of this invention, X4 and X5 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl, while R9 and R10 independently can be H or t-butyl, and Cp1 either has no substituents Additional or Cp1 may have a substituent selected only from H or an alkyl, alkenyl, alkylsilyl, or alkenylsilyl group having up to 8 carbon atoms. In these and other aspects, E3 can be a bridging group that has the formula > E3AR7AR8A, wherein E3A is C or Si, and R7A and R8A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl.

According to another aspect of this invention, the second metallocene can comprise a bridged metallocene compound having the formula (D2): (D2); where : M4 is Ti, Zr, or Hf; X6 and X7 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; E4 is a bridging group that has the formula > E4AR12AR13A, wherein E A is C or Si, and R12A and R13A are independently H or a hydrocarbyl group having up to 18 carbon atoms; Y R14, R15, R16, and R17 are independently H or a hydrocarbyl group having up to 18 carbon atoms.

In the formula (D2), M4 can be Ti, Zr, or Hf (for example, Zr or Hf), while X6 and X7 can independently be be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The hydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.

X6 and X7 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X6 and X7 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X6 and X7 independently are benzyl, phenyl, or methyl. Still, in another aspect, both X6 and X7 can be Cl; alternatively, both X5 and X7 can be benzyl; alternatively, both X6 and X7 can be phenyl; or alternatively, both X6 and X7 can be methyl.

In the formula (D2), E4 can be a bridging group having the formula > E AR12AR13A, wherein E A is a C or Si bridging atom, and R12A and R13A are independently H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. For example, R12A and R13A can independently be H or an alkyl, alkenyl (for example, a terminal alkenyl), or aryl group having up to 12 carbon atoms. In one aspect, R12A and R13A independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl 2-phenylethyl, and the like. In another aspect, R12A and R13A independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, phenyl, tolyl, or benzyl. In yet another aspect, at least one of R12A and R13A is phenyl. In yet another aspect, at least one of R12A and R13A is a terminal alkenyl group having up to 6 carbon atoms.

R14, R15, R16, and R17 in the fluorenyl groups in the formula (D2) independently can be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Therefore, R14, R15, R16, and R17 independently may be H or a hydrocarbyl group having up to 8 carbon atoms, such as, for example, alkyl groups: methyl, ethyl, propyl, butyl, pentyl, or hexyl, and similar. In some aspects, R14, R15, R16, and R17 are independently methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl, while in other aspects, R14, R15, R16, and R17 are independently H or t- butyl. For example, R14, R15, R16, and R17 can be H or, alternatively, R14, R15, R16, and R17 can be t-butyl.

It is contemplated that X6 and X7 can independently to be F, Cl, Br, I, benzyl, phenyl, or methyl in the formula (D2), and R14, R15, R16, and R17 independently may be H or t-butyl. In these and other aspects, E4 can be a bridging group having the formula > E4AR12AR13A, wherein E4A is C or Si, and R12A and R13A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl.

In accordance with another aspect of this invention, the second metallocene can comprise a bridged metallocene compound having the formula (E2): (E2); where : M5 is Ti, Zr, or Hf; Xs and X9 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; E5 is a bridging group that has the formula > E5AR20AR21A, wherein EA is C or Si, and R20A and R21A are independently H or a hydrocarbyl group having up to 18 carbon atoms; Y Cp2 and Cp3 are independently a cyclopentadienyl or indenyl group, any substituent on Cp2 and Cp3 is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.

In the formula (E2), M5 can be Ti, Zr, or Hf (for example, Zr or Hf), while X8 as X9 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The hydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.

X8 and X9 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X8 and X9 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X8 and X9 independently are benzyl, phenyl, or methyl. Still, in another aspect, both X8 and X9 can be Cl; alternatively, both X8 and X9 can be benzyl; alternatively, both X8 and X9 can be phenyl; or alternatively, both X8 and X9 can be methyl.

In the formula (E2), E5 can be a bridging group having the formula > E5AR20AR21A, where E5A is a bridging atom C or Si, and R20A and R21A are independently H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. For example, R20 and R21A can independently be H or an alkyl, alkenyl (for example, a terminal alkenyl), or aryl group having up to 12 carbon atoms. In one aspect, R20A and R21ft independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like. In another aspect, R20A and R21A independently may be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, phenyl, tolyl, or benzyl. In yet another aspect, at least one of R20A and R21A is phenyl. In yet another aspect, at least one of R20A and R21A is a terminal alkenyl group having up to 6 carbon atoms.

In the formula (E2), Cp2 and Cp3 are independently a cyclopentadienyl group or an indenyl. Often, Cp2 and Cp3 are both a cyclopentadienyl group or both are an indenyl group. Any substituent on Cp2 and Cp3 independently can be H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; or alternatively, any substituent may be H or a hydrocarbyl or hydrocarbylsilyl group having up to 12 carbon atoms. Possible substituents on Cp2 and Cp3 may include H, therefore this invention comprises partially saturated ligands such as tetrahydroindenyl, partially saturated indenyl, and the like.

In one aspect, Cp2 and Cp3 have no substitutions other than those shown in formula (E2), for example, without substituents other than bridging group E5. In another aspect, Cp2 and / or Cp3 may have one or two substituents, and each substituent independently may be H or an alkyl, alkenyl, alkylsilyl, or alkenylsilyl group having up to 8 carbon atoms, or alternatively, up to 6 carbon atoms . Still, in another aspect, Cp2 and / or Cp3 may have a substituent H, methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, tolyl, or benzyl alone.

As noted above, unless otherwise specified, formulas (C2), (D2), and (E2), or any other structural formulas are described herein, and any of the metallocene species described herein are not designed to show stereochemical or isomeric positioning of the different portions (for example, these formulas are not planned to exhibit cis or trans isomers, or diastereomers R or S), although these compounds are contemplated and encompassed by these formulas and / or structures.

Non-limiting examples of bridged metallocenes which are suitable for use as the second metallocene compound include, but are not limited to, the following (Ph = phenyl; Me = methyl; and t-Bu = tere-butyl): ?? ?? 62 ?? ?? ?? combination of them.

In accordance with other aspects of the invention, the second metallocene compound may comprise an unbridged metallocene compound. In one aspect, the unbridged metallocene compound may comprise a cyclopentadienyl group and an indenyl group. In another aspect, the unbridged metallocene compound may comprise two cyclopentadienyl groups. In still another aspect, the unbridged metallocene compound may comprise two indenyl groups.

In accordance with certain aspects of this invention, the second metallocene can comprise a non-bridged metallocene compound having the formula (F2): c? • S? E1 ° Cp5 (F2); where : 6 is Ti, Zr, or Hf; X10 and X11 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; Y Cp4 and Cp5 are independently a cyclopentadienyl, indenyl or fluorenyl group, any substituent on Cp4 and Cp5 is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.

In the formula (F2), M6 is Ti, Zr, or Hf (for example, Zr or Hf), while X10 and X11 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylsilyl group. The hydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.

X10 and X11 independently may be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X10 and X11 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X10 and X11 independently are benzyl, phenyl, or methyl. Still, in another aspect, both X10 and X11 can be Cl; alternatively, both X10 and X11 can be benzyl; alternatively, both X10 and X11 can be phenyl; or alternatively, both X10 and X11 can be methyl.

In the formula (F2), Cp4 and Cp5 are independently a cyclopentadienyl, indenyl or fluorenyl group. Often, Cp4 and Cp5 are independently a cyclopentadienyl or indenyl group. Any substituent on Cp4 and Cp5 independently can be H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; or alternatively, any substituent may be H or a hydrocarbyl or hydrocarbylsilyl group having up to 12 carbon atoms. Possible substituents on Cp4 and Cp5 can include H, therefore this invention comprises partially saturated ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, and the like.

In one aspect, Cp4 and Cp5 have no substitutions other than those shown in the formula (F2), for example, Cp4 and Cp5 independently can be an unsubstituted cyclopentadienyl or unsubstituted indenyl. In another aspect, Cp4 and / or Cp5 may have one or two substituents, and each substituent independently may be H or a hydrocarbyl group having up to 10 carbon atoms, such as, for example, an alkyl, alkenyl, or aryl group. Still, in another aspect, Cp4 and / or Cp5 can have one or two substituents, and each substituent independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, tolyl, or benzyl, while in other aspects, each substituent can independently be methyl, ethyl, propyl, butyl, ethenyl, propenyl, butenyl, or pentenyl.

In some aspects of this invention, X10 and X11 independently may be F, Cl, Br, I, benzyl, phenyl, or methyl, while Cp4 and Cp5 are independently a group unsubstituted cyclopentadienyl or unsubstituted indenyl. Alternatively, Cp4 and Cp5 independently can be substituted with one or two substituents, and these substituents independently can be H or a hydrocarbyl group having up to 10 carbon atoms, such as, for example, methylethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, tolyl, or benzyl.

Non-limiting examples of unbridged metallocenes that are suitable for use as the second metallocene compound include, but are not limited to, the following: similar, or any combination thereof.

Additional bridged and unbridged metallocene compounds can be employed as the second metallocene compound in catalyst compositions of the present invention. Therefore, the scope of the present invention is not limited to the bridged and unbridged metallocene species provided above. Other bridged and / or non-bridged and / or representative dinuclear metallocene compounds which can be employed as the second metallocene compound in some aspects of this invention are disclosed in U.S. Patent Nos. 7,026,494, 7,041,617, 7,119,153, 7,148,298, 7,226,886, 7,294,599, 7,312,283, 7,468,452, 7,517,939, 7,521,572, 7, 619, 047, 7, 863,210, 7, 884, 163, 7, 919, 639, 8,012, 900, 8,080,681, and 8,114,946; and US Patent Publications Nos. 2010/0331505, 2011/0257348, and 2012/0010375; the descriptions of these patents and publications are hereby incorporated by reference in their entirety.

SUPPORT ACTIVATOR The present invention encompasses various catalyst compositions containing an activator, which can be a support activator. In one aspect, the support activator comprises chemically treated solid oxide. Alternatively, the support activator may comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated gelled clay in another oxide matrix, a layered silicate mineral, a silicate mineral without layers, an aluminosilicate mineral in layers, an aluminosilicate mineral without layers or any of combinations thereof.

In general, chemically treated solid oxides exhibit improved acidity compared to the corresponding untreated solid oxide compound. The solid oxide chemically treated also functions as a catalyst activator compared to the corresponding untreated solid oxide. While the chemically treated solid oxide activates the metallocene (s) in the absence of co-catalysts, it is not necessary to remove co-catalysts from the catalyst composition. The activation function of the support activator is evident in the improved activity of 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 organoaluminum compound, aluminoxane compounds, organoboron or organoborate, ionizing ionic compounds, and the like.

The chemically treated solid oxide may comprise a solid oxide treated with an electron attracting anion. While not intending to be bound by the following statements, it is believed that the treatment of solid oxide with an electron attractant component increases or improves the acidity of the oxide. Therefore, either the support activator exhibits Lewis or Brønsted acidity that is typically greater than the Lewis or Brønsted acid strength of the untreated solid oxide, or the support activator has a higher number of acid sites than the solid oxide not treated, or both. A method to quantify the acidity of materials of solid oxide chemically treated and untreated is comparing the polymerization activities of the treated and untreated oxides under catalyzed acid reactions.

Chemically treated solid oxides of this invention are generally formed of an inorganic solid oxide that exhibits acidic Lewis or Brønsted acidic behavior and has a relatively high porosity. The solid oxide is chemically treated with an attractant electron component, typically an attractant electron anion, to form a support activator.

In accordance with one aspect of the present invention, the solid oxide that is used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc / g. In accordance with another aspect of the present invention, the solid oxide has a pore volume greater than about 0.5 cc / g. According to yet another aspect of the present invention, the solid oxide has a pore volume greater than about 1.0 cc / g.

In another aspect, the solid oxide has a surface area of about 100 to about 1000 mz / 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 approximately 600 m2 / g.

The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and one or more elements selected from 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 the lanthanide or actinide elements (See: Ha ley's Condensed Chemical Dictionary, IIth Ed., John Wiley &Sons, 1995; Cotton, FA, Wilkinson, G. , Murillo, CA, and Bochmann,., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, the inorganic oxide may comprise 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.

Suitable examples of solid oxide materials or compounds that can be used to form the chemically treated solid oxide include, but are not limited to, A1203, B203, BeO, Bi203, CdO, Co304, Cr203, CuO, Fe203, Ga203, La203, Mn203, o03, NiO, P205, Sb205, Si02, Sn02, SrO, Th02, Ti02, V205, W03,? 2? 3, ZnO, Zr02, and the like, including mixed oxides thereof, and combinations thereof. For example, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides of the same, or any combination thereof.

The solid oxide of this invention encompasses oxide materials such as alumina, "mixed oxide" compounds thereof such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds such as silica-alumina may be single or multiple 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 support activator 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, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide of this invention also encompasses oxide materials such as silica-coated alumina, as described in U.S. Patent Publication No. 2010-0076167, the disclosure of which is hereby incorporated by reference in its entirety.

The attractant electron component is used to treat the solid oxide which can be any component that increases the Lewis or Brønsted acidity of the solid oxide under treatment (compared to the solid oxide that is not treated with at least one electron attractant anion). In accordance with one aspect of the present invention, the component of "attractant electron" is an attractant electron anion derived from a salt, an acid, or other compound, such as a volatile organic compound, which serves as a source or precursor for the anion. Examples of attractant electron anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, and the like, which they include mixtures and combinations thereof. In addition, other ionic and non-ionic compounds that serve as sources for these attractant electron anions can also be employed in the present invention. It is contemplated that the attractant electron anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and the like, or any combination thereof, in some aspects of this invention. In other aspects, the attractant electron anion may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and the like, or any combination thereof.

Thus, for example, the support activator (e.g., chemically treated solid oxide) is used in the catalyst compositions of the present invention which may be, or may comprise, fluorinated alumina, alumina chlorinated, brominated alumina, sulphated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated alumina-silica, silica-fluorinated zirconia, silica-chlorinated zirconia, silica-brominated zirconia, silica-sulfated zirconia, silica fluorinated titania, fluorinated coated silica-alumina, coated sulfated alumina-silica, phosphatized silica-coated alumina, and the like, or combinations thereof. In one aspect, the support activator may be, or may comprise, fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-coated alumina, coated sulfated silica-alumina, phosphatized silica-coated alumina, and similar, or any combination thereof. In another aspect, the support activator comprises fluorinated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulphated 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, comprises coated fluorinated silica-alumina.

When the attractant electron component comprises a salt of an attractant electron anion, the counter ion or cation of this salt can be selected from any cation that allows the salt to return or decompose again to the acid during the calcination. Factors dictating the suitability of the particular salt to serve as a source for the attractant electron anion include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse reactivity of the cation, mating effects of the ion between the cation and anion, hygroscopic properties given to the salt by the cation, and the like, and thermal stability of the anion. Examples of suitable cations in the salt of the electron attracting anion include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H +, [H (OEt2) 2] +, and the like.

In addition, combinations of one or more different attractant electron anions, in varying proportions, can be used as long as the specific acidity of the support activator reaches the desired level. Combinations of attractive electron components can be contacted with the oxide material simultaneously or individually, and in any order that provides the acidity to the desired chemically treated solid oxide. For example, in one aspect of this invention, it employs two or more compounds from the source of the attractant electron anion in two or more separate contact steps.

Therefore, an example of this process by the which a chemically treated solid oxide is prepared as follows: a selected solid oxide, or combinations of solid oxides, are contacted with a first compound from the source of the attractant electron anion to form a first mixture; this first mixture is calcined and then contacted with a second compound from the source of the attractant electron anion to form a second mixture; the second mixture is then calcined to form a solid oxide treated. In this process, the first and second compound of the anion source of the attractant electron can be either the same or different compounds.

In accordance with another aspect of the present invention, the chemically treated solid oxide comprises a solid inorganic oxide material, a mixed oxide material, or a combination of inorganic oxide materials, which is chemically treated with an electron attractant component, and optionally treated with a metal source, including metal salts, metal ions, or other metal-containing compounds. Non-limiting examples of the 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 oxide containing a metal or metal ion include, but are not limited to, zinc- chlorinated impregnated alumina, fluorinated impregnated titanium-alumina, fluorinated zinc-alumina impregnated, zinc-silica-impregnated chlorinated alumina, zinc-silica-fluorinated alumina impregnated, zinc-silica-sulphated alumina impregnated, chlorinated zinc aluminate, fluorinated zinc aluminate, sulfated zinc aluminate, silica-coated alumina treated with hexafluorotitanic acid, silica-coated alumina treated with zinc and then fluorinated, and the like, or any combination thereof.

Any method of impregnating the solid oxide material with a metal can be used. The method by which the oxide is contacted with a source of the metal, typically a salt or metal-containing compound, can include, but is not limited to, gelled, co-gelled, impregnation of one compound into another, and the like. . If desired, the metal-containing compound is added to or impregnated in the solid oxide as a solution, and subsequently converted to the metal supported on the calcination. Therefore, the solid inorganic oxide may further comprise 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 because it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containing compounds before, after, or at the same time that the solid oxide is treated with the electron attracting anion. After any contact method, the contact mixture of the solid compound, attractant electron anion, and the metal ion is typically calcined. Alternatively, a solid oxide material, a source of the attractant electron anion, and the metal salt or metal-containing compound are in contact and calcined simultaneously.

Various 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 oxide with one or more sources of the attractant electron anion. It is not required that the solid oxide be calcined before contacting the source of the attractant electron anion. The contact product is typically calcined either during or after the solid oxide is contacted with the source of the attractant electron anion. The solid oxide can be calcined or not calcined. Several processes for preparing solid oxide support activators that can be employed in this invention have been reported. For example, these methods are described in U.S. Patent Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, and 6,750,302, the descriptions of which are incorporated herein by reference in their entirety.

In accordance with one aspect of the present invention, the solid oxide material is chemically treated by contacting it with an attractant electron component, typically a source of the attractant electron anion. 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. In accordance with another aspect of the present invention, the solid oxide material and source of the attractant electron anion are in contact and calcined simultaneously.

The method by which the oxide is brought into contact with the attractant electron component, typically a salt or an acid of an attractant electron anion, can include, but is not limited to, gelled, co-gelled, impregnation of a compound in another, and similar. Therefore, after any contact method, the contact mixture of the solid oxide, the attractant electron anion, and the optional metal ion, are calcined.

The solid oxide support activator (ie chemically treated solid oxide) can therefore be produced by a process that includes: 1) contacting a solid oxide (or solid oxides) with a compound of the electron attractant anion source (or compounds) to form a first mixture; Y 2) calcining the first mixture to form the solid oxide support activator.

In accordance with another aspect of the present invention, the solid oxide support activator (chemically treated solid oxide) is produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with a first compound from the source of the attractant electron anion to form a first mixture; 2) calcining the first mixture to produce a first calcined mixture; 3) contacting the first calcined mixture with a second compound from the source of the attractant electron anion to form a second mixture; Y 4) calcining the second mixture to form the solid oxide support activator.

According to yet another aspect of the present invention, the chemically treated solid oxide is produced or formed by contacting the solid oxide with the source compound of the electron attracting anion, wherein the solid oxide compound is calcined before, during, or after contacting the source of the attractant electron anion, and where there is a substantial absence of aluminoxane, organoboron or organoborate compounds, and ionizing ionic compounds.

The calcination of the solid oxide treated in general is conducted in an atmospheric environment, typically in a dry atmospheric environment, at a temperature of about 200 ° C to about 900 ° C, and for a time of about 1 minute to 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 may be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Therefore, 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 atmospheric environment can be used during calcination. In general, the calcination is 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.

In accordance with one aspect of the present invention, the solid oxide material is treated with a source of the halide ion, sulfate ion, or a combination of anions, optionally treated with a metal ion, and then calcined to provide the chemically solid oxide. treated in the form of a particulate solid. For example, the solid oxide material can be treated with a sulphate source (referred to as a "sulfation agent"), a source of the chloride ion (referred to as a "chlorinating agent"), a fluoride ion source (referred to as a "chlorine"). fluorinating agent "), or a combination thereof, and calcined to provide the solid oxide activator. Useful acidic acid activator includes, but is not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, silica-sulfated alumina, silica-brominated zirconia, silica-chlorinated zirconia, silica-fluorinated zirconia, silica-sulfated zirconia, fluorinated silica-titania, alumina treated with hexafluorotitanic acid, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid , fluorinated-alumina binder, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pilarized montmorillonitis, optionally treated with fluoride, chloride, or sulfate; phosphated alumina or other aluminophosphates optionally treated with sulfate, fluoride, or chloride; or any combination of the above. In addition, any of these media activators can optionally be treated with a metal ion.

The chemically treated solid oxide may comprise a fluorinated solid oxide in the form of a particulate solid. The fluorinated solid oxide can be formed by contacting a solid oxide with a fluorinating agent. The fluoride ion can be added to the oxide by forming a suspension of the oxide in a suitable 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 fluorinating agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (H4BF4), ammonium silicofluoride (hexafluorosilicate) ((NH4) ) 2SiFg), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2 iF6), hexafluorotitanic ammonium acid ((NH4) 2TiF6), hexafluorozirconic acid (H2ZrF6), A1F3, NH4AIF4, analogues thereof, and combinations thereof. Triflic acid and ammonium triflate can also be employed. For example, ammonium bifluoride (NH4HF2) can be used as the agent of fluoride, due to its easy use and availability.

If desired, the solid oxide is treated with a fluorinating agent during the calcination step. Any fluorinating agent capable of completely contacting the solid oxide during the calcination step can be used. For example, in addition to these fluorinating agents previously described, volatile organic fluorinating agents can be used. Examples of volatile organic fluorinating agents useful in this aspect of the invention include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. The calcination temperatures in general must be quite high to decompose the compound and release fluoride. Gaseous hydrogen fluoride (HF) or fluorine (F2) by itself can also be used with the solid oxide if it is fluorinated while it is being calcined. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF ~) may also be employed. A convenient method of contacting the solid oxide with the fluorinating agent is to vaporize a fluorinating agent in a gas stream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically treated solid oxide comprises a chlorinated solid oxide in the form of a particulate solid. He Chlorinated solid oxide is formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide by forming a suspension 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 source of the chloride and completely contacting the oxide during the calcination step can be used, such as SiCl4, SiMe2Cl2, T1CI4, BCI3, and the like, which include mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like, or any combination thereof. Chloride of gaseous hydrogen or chlorine by itself can also be used with the solid oxide during calcination. A convenient method of contacting the oxide with the chlorinating agent is to vaporize a chlorinating agent in a gas stream which is used to fluidize the solid oxide during calcination.

The amount of fluoride or chloride ion present before the solid oxide is calcined in general is from about 1 to about 50% by weight, wherein the weight percentage is based on the weight of the solid oxide, eg, silica-alumina, before of the calcination. From In accordance with another aspect of this invention, the amount of fluoride or chloride ion present before the solid oxide is calcined is from about 1 to about 25% by weight, and in accordance with another aspect of this invention, from about 2 to about 20%. in weigh. According to still another aspect of this invention, the amount of fluoride or chloride ion present before the solid oxide is calcined is from about 4 to about 10% by weight. Once impregnated with 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 stage immediately without drying the impregnated solid oxide.

The silica-alumina is used to prepare the typically treated silica-alumina having a pore volume greater than about 0.5 cc / g. In accordance with one aspect of the present invention, the pore volume is greater than about 0.8 cc / g, and in accordance with another aspect of the present invention, greater than about 1.0 cc / g. In addition, silica-alumina in general has a surface area greater than about 100 m2 / g. In accordance with another aspect of this invention, the surface area is greater than about 250 m2 / g. Still in another aspect, the surface area is greater than about 350 m2 / g.

The silica-alumina used in the present invention typically has an alumina content of about 5 to about 95% by weight. In accordance with one aspect of this invention, the alumina content of the silica-alumina is from about 5 to about 50%, or from about 8% to about 30%, alumina by weight. In another aspect, high alumina silica-alumina compounds can be employed, in which the alumina content of these silica-alumina compounds typically ranges from about 60% to about 90%, or from about 65% to about 80%. %, alumina by weight. According to yet another aspect of this invention, the solid oxide component comprises alumina without silica, and in accordance with another aspect of this invention, the solid oxide component comprises silica without alumina.

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 further treated with a metal ion such that the calcined sulphated oxide comprises a metal. In accordance with one aspect of the present invention, the oxide Sulfated solid comprises sulfate and alumina. In some cases, the sulfated alumina is formed by a process wherein the alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt such as ammonium sulfate. This process is generally carried out by forming an alumina suspension in a suitable solvent, such as alcohol or water, in which the desired concentration of the sulphated 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.

In accordance with one aspect of this invention, the amount of sulfate ion present before calcination is from about 0.5 to about 100 parts by weight of sulfate ion to 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 of sulfate ion to about 100 parts by weight of solid oxide, and in accordance with yet another aspect of the invention. this invention, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of the solid oxide before calcination. Once impregnated with sulfate, the oxide Sulphated 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.

In accordance with another aspect of the present invention, the support activator is used in the preparation of the catalyst compositions of this invention, comprising an exchangeable ion support activator, including but not limited to silicate compounds and minerals and aluminosilicate, either with layered structures and without layers, and combinations thereof. In another aspect of this invention, aluminosilicates in interchangeable ion layers such as pillared clays are used as support activators. When the acidic support activator comprises an exchangeable ion support activator, it can optionally be treated with at least one attractant electron anion such as those described herein, although typically the interchangeable ion support activator is not treated with an anion of attractive electron.

In accordance with another aspect of the present invention, the support activator of this invention comprises clay minerals having interchangeable cations and layers capable of expanding. Activators of Typical clay mineral support include, but are not limited to, aluminosilicates in interchangeable ion layers such as pillared clays. Although the term "support" is used, it does not mean that it is interpreted as an inert component of the catalyst composition, but rather is considered an active part of the catalyst composition, due to its intimate association with the metallocene components.

In accordance with another aspect of the present invention, the clay minerals of this invention encompass materials either in their natural state or that have been treated with various ions by wetting, ion exchange, or pillaging. Typically, the clay mineral support activator of this invention comprises clays that have been ionically exchanged with large cations, which include cations of the highly charged, polynuclear metal complex. However, the clay mineral support activator of this invention also encompasses clays that have been ionically exchanged with simple salts, including, but not limited to, salts of Al (III), Fe (II), Fe (III) ), and Zn (II) with ligands such as halide, acetate, sulfate, nitrate, or nitrite.

In accordance with another aspect of the present invention, the support activator comprises a pillared clay. The term "clay pilarizada" is used for refer to clay materials that have been ionically exchanged with highly charged, typically polynuclear, large metal complex cations. Examples of these ions include, but are not limited to, Keggin ions which may have charges such as 7+, various polyoxometalates, and other large ions. Therefore, the term "pillary" refers to a simple exchange reaction in which the interchangeable cations of a clay material are replaced with highly charged, large ions, such as Keggin ions. These polymeric cations are then immobilized within the interlayers of the clay and when they are calcined they are converted to "pillars" of metal oxide effectively supporting the clay layers as column-like structures. Therefore, once the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded lattice structure is maintained and the porosity is improved. The resulting pores can vary in shape and size as a function of the material pillars and the precursor clay material used. Examples of pilarized and pillared 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 Patent United States No. 4,060,480; the descriptions of which are incorporated herein by reference in their entirety.

The piling process uses clay minerals that have interchangeable cations and layers capable of expanding. Any pillared clay that can improve the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, clay minerals suitable for pillary include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; haloisites; vermiculites; micas; fluoromics; chlorites; clays of mixed layers; Fibrous clays include but are not limited to sepiolites, attapulgites, and paligorsquitas; a clay in serpentine; illite; laponite; saponite; and any combination thereof. In one aspect, the pillared clay support activator comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.

The pillared clay can be pretreated if desired. For example, a pillared bentonite is pretreated by drying at about 300 ° C under an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although exemplary pretreatment is described herein, it must be understand that preheating can be carried out at many other temperatures and times, including any combination of temperature and time stages, all of which are encompassed by this invention.

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, inorganic phosphated 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, thoria, aluminophosphate, aluminum phosphate, silica-titania, silica / titania coprecipitated, mixtures thereof, or any combination thereof.

According to another aspect of the present invention, one or more of the metallocene compounds can be previously contacted with an olefin monomer and an organoaluminum compound for a first period of time before contacting this mixture with the activator of support. Once the previously contacted mixture of the metallocene compound (s), olefin monomer, and organoaluminum compound is contacted with the support activator, the composition further comprising the support activator is termed a "after contact" mixture. The subsequent contact mixture can be allowed to remain in additional contact for a second period of time before being charged into the reactor in which the polymerization process will be carried out.

According to yet another aspect of the present invention, one or more of the metallocene compounds can be previously contacted with an olefin monomer and a support activator for a first period of time before contacting this mixture with the composed of organoaluminum. Once the pre-contact mixture of the metallocene compound (s), olefin monomer, and support activator is contacted with the organoaluminum compound, the composition further comprises the organoaluminium is referred to as a "post-contact" mixture. The subsequent contact mixture can be allowed to remain in contact for a second period of time before being introduced into the polymerization reactor.

ORGANOALUMINUM COMPOUNDS In some aspects, the catalyst compositions of the present invention may comprise one or more organoaluminum compounds. These compounds may include, but are not limited to, compounds having the formula: (RC) 3A1; wherein Rc is an aliphatic group having 1 to 10 carbon atoms. For example, R c can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which may be used in catalyst compositions described herein may include, but are not limited to, compounds having the formula: Al (XA) P (XB) 3-p, wherein Xa is a hydrocarbyl; XB is an alkoxide or an aryloxide, a halide, or a hydride; and p is from 1 to 3, inclusive. The hydrocarbyl is used herein to specify a radical hydrocarbon group and includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like, and includes all substituted, unsubstituted, branched, linear, and / or substituted heteroatom derivatives thereof.

In one aspect, Xa is a hydrocarbyl having 1 to about 18 carbon atoms. In another aspect of the present invention, Xa is an alkyl having 1 to 10 carbon atoms. For example, Xa can be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet another aspect of the present invention.

In accordance with one aspect of this invention, X is an alkoxide or an aryloxide, any of some of which have 1 to 18 carbon atoms, a halide, or a hydride. In another aspect of the present invention, XB is independently selected from fluorine and chlorine. Still, in another aspect, XB is chlorine.

In the formula, Al (XA) P (XB) 3_p, p is a number from 1 to 3, inclusive, and typically, p is 3. The value of p is not restricted to being an integer; therefore, this formula includes sesquihalide compounds or other compounds in organoaluminum grouping.

Examples of organoaluminum compounds suitable for use in accordance with the present invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkyl aluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. Specific non-limiting examples of suitable organoaluminum compounds include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri -n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof.

The present invention contemplates the method of pre-contacting a metallocene compound (s) with a composed of organoaluminium and an olefin monomer to form a pre-contact mixture, before contacting this prior contact mixture with a support activator to form a catalyst composition. When the catalyst composition is prepared in this manner, typically, although not necessarily, a portion of the organoaluminum compound is added to the previously contacted mixture and another portion of the organoaluminum compound is added to the subsequent contact mixture prepared when the mixture of previous contact is put in contact with the solid oxide support activator. However, the complete organoaluminum compound can be used to prepare the catalyst composition in either the previous contact or subsequent contact stage. Alternatively, all the catalyst components are in contact in a single step.

In addition, more than one organoaluminum compound can be used in either the previous contact or subsequent contact stage. When an organoaluminum compound is added in multiple steps, the amounts of organoaluminum compound described herein include the total amount of organoaluminum compound used in both the pre-contact and post-contact mixtures, and any additional organoaluminium compound added thereto. polymerization reactor. Therefore, they are described total amounts of organoaluminum compounds regardless of whether an organoaluminum compound alone or more than one organoaluminium compound is used.

COMPOUNDS OF ALU INOXANO The present invention further provides a catalyst composition which may comprise an aluminoxane compound. As used herein, the term "aluminoxane" refers to aluminoxane compounds, compositions, mixtures, or discrete species, regardless of how these aluminoxanes are prepared, formed or otherwise provided. 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 aluminum alkyl compound and a source of active protons such as water. Aluminoxanes are also referred to as poly (hydrocarbyl aluminum oxides) or organoaluminoxanes.

The other catalyst components are typically in contact with the aluminoxane in a solvent of the saturated hydrocarbon compound, although any solvent that is substantially inert to the reactants, intermediates, and products of the activation step can be used. The catalyst composition formed of 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.

The aluminoxane compound of this invention can be an oligomeric aluminum compound comprising linear structures, cyclic structures, or cage structures, or mixtures of all three. The cyclic aluminoxane compounds having the formula: wherein R in this formula is a linear or branched alkyl having from 1 to 10 carbon atoms, and p in this formula is an integer from 3 to 20, are encompassed by this invention. The AIRO portion shown here also constitutes the repeating unit in a linear aluminoxane. Therefore, linear aluminoxanes that have the formula: wherein R in this formula is a linear or branched alkyl having from 1 to 10 carbon atoms, and q in this formula is an integer from 1 to 50, are also encompassed by this invention.

In addition, the aluminoxanes may have cage structures of the formula Rt5r + aRbr- -Al4r03r, wherein Rfc is a terminal linear or branched alkyl group having from 1 to 10 carbon atoms; Rb is a branched linear or branched alkyl group having from 1 to 10 carbon atoms; r is 3 or 4; and OI is equal to nAi. { 3) - n0 (2) + n0. { i), where? 1 (3) is the number of three coordinated aluminum atoms, r00 < 2) is the number of two coordinated oxygen atoms, and n0 (4> is the number of 4 coordinated oxygen atoms.

Therefore, aluminoxanes which may be employed in the catalyst compositions of the present invention are generally represented by formulas such as (R-Al-O) p, R (R-Al-O) qAlR2, and the like. In these formulas, the R group is typically a straight or branched C1-C6 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, iso-butylaluminoxane. , 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane are trimethylaluminum preparations, triethylaluminum, or triisobutylaluminum, 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, as described in U.S. Patent No. 4,794,096, incorporated herein by reference in its entirety.

The present invention contemplates any value of p and q in the formulas of aluminoxane (R-A1-0) P and R (R-A1-0) qAlR2, respectively. In some aspects, p and q are at least 3. However, depending on how the organoaluminoxane is prepared, stored, and used, the value of p and q may vary within a single sample of aluminoxane, and these combinations of organoaluminoxanes are contemplated herein .

In the preparation of a catalyst composition containing an aluminoxane, the molar ratio of the total moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of metallocene compounds in the composition is generally between about 1:10 and about 100,000. :1. In another aspect, the molar ratio is in a range of about 5: 1 to about 15,000: 1. Optionally, aluminoxane can be added to a polymerization zone at intervals of approximately 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 to about 50 mg / L.

The organoaluminoxanes can be prepared by various methods. Examples of organoaluminoxane preparations are described in U.S. Patent Nos. 3,242,099 and 4,808,561, the disclosures of which are hereby incorporated by reference in their entirety. For example, water in an inert organic solvent can be reacted with an alkyl aluminum compound, such as (RC) 3A1, to form the desired organoaluminoxane compound. While not intended to be bound by this statement, it is believed that this synthetic method can provide a mixture of both linear and cyclic aluminoxane R-Al-0 species, both of which are encompassed by this invention. Alternatively, the organoaluminoxanes are prepared by reacting an alkyl aluminum compound, such as (RC) 3A1, with a hydrated salt, such as hydrous copper sulfate, in an inert organic solvent.

COMPOUNDS OF ORGANOBQRO / ORGANOBORATE In accordance with another aspect of the present invention, the catalyst composition may comprise an organoboron or organoborate compound. These compounds include neutral boron compounds, borate salts, and similar, or combinations thereof. For example, fluoroorgano boron compounds and fluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be used with the present invention. Examples of fluoroorgano borate compounds that may 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, tetrakis (tetrakis). pentafluorophenyl) lithium borate, tetrakis [3, 5-bis (trifluoromethyl) phenyl] borate of N, N-dimethylanilinium, triphenyl [3, 5-bis (trifluoromethyl) phenyl] borate of triphenylcarbenium, and the like, or mixtures thereof . Examples of fluoroorgano 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 mixtures thereof. Although not intended to be bound by the following theory, these examples of fluoroorgano borate and fluoroorgano boron compounds, and related compounds, are considered to form "weakly coordinating" anions when combined with organometal or metallocene compounds, as described in the patent. American 5, 919, 983, the description of which is incorporated in the present by reference in its entirety. Applicants 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 described in J. Am. Chem. Soc, 2005, 127, pp. . 14756-14768, the content of which is incorporated herein by reference in its entirety.

In general, any amount of the organoboron compound can be used. In accordance with one aspect of this invention, the molar ratio of the total moles of the organoboron compound or organoborate (or compounds) to the total moles of metallocene compounds in the catalyst composition is in a range of about 0.1: 1 to about 15. :1. Typically, the amount of the fluoroorgano boron or fluoroorgano borate compound used is from about 0.5 moles to about 10 moles of the boron / borate compound per mole of metallocene compounds. In accordance with another aspect of this invention, the amount of the fluoroorgano boron or fluoroorgano borate compound is from about 0.8 moles to about 5 moles of the boron / borate compound per mole of metallocene compounds.

IONIZING IONIC COMPOUNDS The present invention also provides a catalyst composition which may comprise a ionizing ionic compound. An ionizing ionic compound is an ionic compound that can function as a co-catalyst to improve the activity of the catalyst composition. While not intended to be bound by theory, it is believed that the ionizing ionic compound is capable of reacting with a metallocene compound and converting the metallocene to one or more cationic metallocene compounds, or incipient cationic metallocene compounds. Again, while not intended to be bound by theory, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or partially removing an anionic ligand, possibly a non-alkadienyl ligand, from the metallocene. However, the ionizing ionic compound is an activator or co-catalyst, although it ionizes the metallocene, removes a ligand in a form to form an ion pair, weakens the metal-ligand bound in the metallocene, simply coordinates a ligand, or activates the metallocene by some other mechanism.

In addition, it is not necessary for the ionizing ionic compound to activate the metallocene compounds only. The activation function of the ionizing ionic compound can be evident in the improved activity of the catalyst composition as a whole, compared to a catalyst composition that does not contain an ionizing ionic compound.

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, tetrakis (2,4-dimethylphenyl) tri (n-butyl) ammonium borate, tri (n-butyl) ammonium tetrakis (3, 5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tetra (pentafluorophenyl) borate of tri (n-butyl) ammonium, tetrakis (p-tolyl) borate of N, N-dimethylanilinium, tetrakis (m-tolyl) borate of N, N-dimethylanilinium, tetrakis (2,4-dimethylphenyl) N, -dimethylanilinium borate, N, -dimethylanilinium tetrakis (3,5-dimethylphenyl) borate, N, -dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate], N-N tetrakis (pentafluorophenyl) borate -dimethylanilinium, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethylphenyl) borate, triphenylcarboxy (3, 5-dimethylphenyl) borate) enio, triphenylcarbenium tetrakis [3, 5-bis (trifluoromethyl) phenyl] borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tetrakis (p-tolyl) borate of tropillo, tetrakis (m-tolyl) borate of tropillo, tetrakis (2, 4-dimethylphenyl) trickle borate, tetrakis (3, 5-dimethylphenyl) borate of trickle, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate of tropylium, tetrakis (pentafluorophenyl) borate of tropylium, tetrakis (pentafluorophenyl) borate of lithium, tetraphenylborate lithium tetrakis (p-tolyl) borate, lithium tetrakis (m-tolyl) orato lithium tetrakis (2, dimethylphenyl) borate, lithium tetrakis (3, 5-dimethylphenyl) borate lithium, lithium tetrafluoroborate, tetrakis (pentafluorophenyl) borate, sodium tetraphenylborate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, sodium tetrakis (2, 4-dimethylphenyl) borate, sodium tetrakis (3, 5- dimethylphenyl) borate, sodium tetrafluoroborate, sodium tetrakis (pentafluorophenyl) borate, potassium tetraphenylborate, potassium tetrakis (p-tolyl) borate, potassium tetrakis (m-tolyl) borate, potassium tetrakis (2, 4-dimethylphenyl) potassium borate, tetrakis (3, 5-dimethylphenyl) borate, potassium tetrafluoroborate, potassium tetrakis (pentafluorophenyl) aluminate, lithium tetrafenilaluminato lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate lithium, tetrakis (2,4-dimethylphenyl) lithium aluminate, tetrakis (3, 5- dimethylphenyl) aluminate, lithium tetrafluoroaluminato lithium tetrakis (pentafluorophenyl) aluminate, sodium tetrafenilaluminato sodium tetrakis (p-tolyl) aluminate, sodium tetrakis (m-tolyl) aluminate, sodium tetrakis (2, dimethylphenyl) aluminate sodium, tetrakis (3, 5-dimethylphenyl) sodium aluminate, sodium tetrafluoroaluminate, potassium tetrakis (pentafluorophenyl) aluminate, potassium tetraphenylaluminate, tetrakis (p-tolyl) aluminate potassium tetrakis (m-tolyl) aluminate, potassium tetrakis (2, 4-dimethylphenyl) aluminate, potassium tetrakis (3, 5-dimethylphenyl) aluminate, potassium tetrafluoroaluminato potassium, and the like, or combinations thereof. Ionizing ionic compounds useful in this invention are not limited thereto; other examples of ionizing ionic compounds are described in U.S. Patent Nos. 5,576,259 and 5,807,938, the descriptions of which are hereby incorporated by reference in their entirety.

MONOMER OF OLEFINS Unsaturated reagents that can be employed with catalyst compositions and polymerization processes of this invention typically include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. This invention encompasses homopolymerization processes using an olefin alone such as ethylene or propylene, 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 greater amount of ethylene (> 50 mol percent) and a smaller amount of comonomer (< 50 mol percent), although this It is not a requirement. Comonomers that can be copolymerized with ethylene often have 3 to 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins 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-l-pentene, 4-methyl-l-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-l-hexene, 1-heptene, 2-heptene, 3 -heptene, the four normal octenes (for example, 1-octene), the four normal nonenes, the five normal tens, and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above. Styrene can also be employed as a monomer in the present invention. In one aspect, the olefin monomer is a C2-Ci0 olefin; alternatively, the olefin monomer is ethylene; or alternatively, the olefin monomer is propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer may comprise, for example, ethylene or propylene, which is copolymerized with at least one comonomer. In accordance with one aspect of this invention, the olefin monomer in the polymerization process comprises ethylene. In this regard, examples of suitable olefin comonomers include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl- l-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1 -cenene, styrene, and the like, or combinations thereof. In accordance with one aspect of the present invention, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof.

In general, the amount of comonomer introduced into the reactor zone to produce the copolymer is from about 0.01 to about 50 weight percent of the comonomer based on the total weight of the monomer and comonomer. In accordance with another aspect of the present invention, the amount of comonomer introduced into the reactor zone is from about 0.01 to about 40 weight percent of the comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into the reactor zone is from about 0.1 to about 35 percent in weight of the comonomer based on the total weight of the monomer and comonomer. Still, in another aspect, the amount of comonomer introduced into the reactor zone is from about 0.5 to about 20 weight percent of the comonomer based on the total weight of the monomer and comonomer.

While it is not intended to be bound by this theory, where the branched, substituted, or functionalized definitions are used as reactants, it is believed that a steric hindrance can impede and / or decrease the polymerization process. Therefore, the branched and / or cyclic portion (s) of the olefin removed somewhat from the carbon-carbon double bond would not be expected to be able to impede the reaction in the manner that the same olefin substituents located closest to the double bond carbon-carbon. According to one aspect of the present invention, at least one monomer / reagent is ethylene, thus the polymerizations are either a homopolymerization involving only ethylene, or copolymerizations with a different acyclic, cyclic, terminal, internal, linear, branched olefin, replaced, or unsubstituted. In addition, the catalyst compositions of this invention can be used in the polymerization of diolefin compounds including, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

CATALYST COMPOSITIONS In some aspects, the present invention employs catalyst compositions containing an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator (one or more than one). These catalyst compositions can be used to produce polyolefins-homopolymers, copolymers, and the like-for a variety of end-use applications. The ansa-metallocene compound having the formula (I) and the second metallocene compound are discussed hereinbefore. In aspects of the present invention, it is contemplated that the catalyst composition may contain more than one ansa-metallocene compound having the formula (I) and / or more than one second metallocene compound. In addition, additional catalytic compounds - other than those specified as an ansa-metallocene compound having the formula (I) or a second metallocene compound - can be employed in the catalyst compositions and / or the polymerization processes, provided that the compounds ( s) additional catalytic do not decrease the advantages described herein. Additionally, more than one activator can also be used.

Metallocene compounds having the formula (I) are described above. For example, in one aspect, the ansa-metallocene compound having the formula (I) can comprising (or consisting essentially of, or consisting of) an ansa-metallocene compound having the formula (II), formula (III), formula (IV), formula (V), formula (VI), formula (VII), or combinations thereof. In yet another aspect, the ansa-metallocene compound having the formula (I) may comprise (or consist essentially of, or consist of) an ansa-metallocene compound having the formula (C), formula (D), formula ( E), or combinations thereof.

Second metallocene compounds are discussed above. For example, in one aspect, the second metallocene compound may comprise (or consist essentially of, or consist of) a non-bridged metallocene compound and / or a bridged metallocene compound. Still, in another aspect, the second metallocene compound may comprise (or consist essentially of, or consist of) a metallocene compound having the formula (C2), formula (D2), formula (E2), formula (F2), or combinations thereof.

In general, the catalyst compositions of the present invention comprise an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator. In aspects of the invention, the activator may comprise a support activator. Support activators useful in the present invention are described previously. These catalyst compositions may further comprise one or more than one organoaluminum compound or compounds (suitable organoaluminium compounds are also discussed above). Therefore, a catalyst composition of this invention may comprise an ansa-metallocene compound having the formula (I), a second metallocene compound, a support activator, and an organoaluminum compound. For example, the support activator may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina. , silica-fluorinated zirconia, silica-chlorinated zirconia, silica-brominated zirconia, silica-sulfated zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, coated sulfated silica-alumina, phosphatized silica-coated alumina, and the like, or combinations thereof the same. Additionally, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, hydride diisobutylaluminum, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof.

In another aspect of the present invention, provides a catalyst composition which comprises an ansa-metallocene compound having the formula (I), a second metallocene compound, a support activator, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate, ionizing ionic compounds, and / or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, substantially free or organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has catalytic activity, to be discussed later, in the absence of these additional materials. For example, a catalyst composition of the present invention may consist essentially of an ansa-metallocene compound having the formula (I), a second metallocene compound, a support activator, and an organoaluminum compound, wherein no other metallocene compounds are present. materials in the catalyst composition which could increase / decrease the activity of the catalyst composition by more than about 10% from the catalytic activity of the catalyst composition in the absence of such materials.

However, in other aspects of this invention, These activators / co-catalysts can be employed. For example, a catalyst composition comprising an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator-support may further comprise an optional co-catalyst. Suitable co-catalysts in this aspect include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, and the like, or any combination thereof. More than one co-catalyst may be present in the catalyst composition.

In a different aspect, a catalyst composition is provided which does not require a support activator. Such a catalyst composition may comprise an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.

In a particular aspect contemplated herein, the catalyst composition is a dual catalyst composition comprising an activator (one or more than one), only one ansa compound -metallocene having the formula (I), and only a second metallocene compound . In these and other aspects, the catalyst composition can comprising an activator (e.g., a support activator comprising a solid oxide treated with an electron attractant anion); only an amphalo-metallocene compound having the formula (II), formula (III), formula (IV), formula (V), formula (VI), or formula (VII); and only the second metallocene compound having the formula (C2), formula (D2), formula (E2), or formula (F2). In still other aspects, the catalyst composition may comprise an activator (e.g., a support activator comprising a solid oxide treated with an electron attractant anion); only an ansa-metallocene compound having the formula (C), formula (D), or formula (E); and only a second metallocene compound having the formula (C2), formula (D2), formula (E2), or formula (F2).

While not limited thereto, the applicant contemplates the following catalyst compositions: a catalyst composition comprising an activator (eg, a support activator comprising a solid oxide treated with an electron attractant anion), an ansa-metallocene compound which has the formula (II), and a second metallocene compound comprising a non-bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (II), and a second metallocene compound comprising a metallocene compound bridged alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (II), and a second metallocene compound comprising a compound having the formula (C2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (II), and a second metallocene compound comprising a compound having the formula (F2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (III), and a second metallocene compound comprising a non-bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (III), and a second metallocene compound comprising a bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (III), and a second metallocene compound comprising a compound having the formula (C2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (III), and a second metallocene compound comprising a compound having the formula (F2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (IV), and a second metallocene compound comprising a non-bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (IV), and a second metallocene compound comprising a bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (IV), and a second metallocene compound comprising a compound having the formula (C2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (IV), and a second metallocene compound comprising a compound having the formula (F2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (V), and a second metallocene compound comprising a non-bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (V), and a second metallocene compound comprising a bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (V), and a second metallocene compound comprising a compound having the formula (C2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (V), and a second metallocene compound comprising a compound having the formula (F2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (VI), and a second metallocene compound comprising a non-bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (VI), and a second metallocene compound comprising a bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (VI), and a second metallocene compound comprising a compound having the formula (C2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (VI), and a second metallocene compound comprising a compound having the formula (F2); alternatively, a catalyst composition comprising an activator, an amphalo-metallocene compound having the formula (VII), and a second metallocene compound which comprises a non-bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (VII), and a second metallocene compound comprising a bridged metallocene compound; alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (VII), and a second metallocene compound comprising a compound having the formula (C2); alternatively, a catalyst composition comprising an activator, an ansa-metallocene compound having the formula (VII), and a second metallocene compound comprising a compound having the formula (F2); and similar.

This invention also encompasses methods for making these catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.

The ansa-metallocene compound having the formula (I), the second metallocene compound, or both, can be previously contacted with an olefinic monomer if desired, not necessarily that the olefin monomer is polymerized, and a compound of organoaluminum for a first period of time before contacting this mixture previously contacted with a support activator.

The first contact time period, the prior contact time, between the metallocene compound (s), the olefinic monomer, and the organoaluminum compound typically vary from a time period of about 1 minute to about 24 hours. , for example, from about 3 minutes to about 1 hour. Previous contact times of approximately 10 minutes to approximately 30 minutes are also employed. Alternatively, the prior contact process is carried out in multiple stages, instead of a single stage, in which multiple mixtures are prepared, each comprising a different series of catalyst components. For example, at least two catalyst components are contacted to form a first mixture, followed by contacting the first mixture with at least one other catalyst component forming a second mixture, and so on.

The multiple stages of pre-contact can be carried out in a single container or in multiple containers. In addition, the multiple pre-contact stages can be carried out serially (sequentially), in parallel, or a combination thereof. For example, a first mixture of two catalyst components can be formed in a first container, a second mixture comprising the first mixture plus a catalyst component Additional can be formed in the first container or in a second container, which is typically placed downstream of the first container.

In another aspect, one or more of the catalyst components 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 for prior contact with at least one other catalyst component, while the remainder of the same catalyst component is fed into a second pre-contact container for prior contact with the catalyst. minus another catalyst component, or is fed directly into the reactor, or a combination thereof. The prior contact can be carried out in any suitable equipment, such as tanks, stirred mixing tanks, various static mixing devices, a flask, a container of any type, or combinations of these devices.

In another aspect of this invention, the various catalyst components (e.g., an amphalo-metallocene compound having the formula (I), a second metallocene compound, a support activator, an organoaluminum co-catalyst, and optionally a hydrocarbon unsaturated) are contacted in the polymerization reactor simultaneously while the polymerization reaction is proceeding. Alternatively, any two or more of these Catalyst components can be previously contacted in a container prior to entering the reaction zone. This prior contacting step can be continuous, in which the prior contact product is continuously fed to the reactor, or it can be a stepwise or batch process in which a batch of prior contact product is added to make a catalyst composition . This stage of prior contact can be carried out over a period of time that can range from a few seconds to as much as several days, or more. In this aspect, the continuous continuous contact stage generally lasts from about 1 second to about 1 hour. In another aspect, the continuous pre-contact stage lasts from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Once the previously contacted mixture of the ansa-metallocene compound having the formula (I) and / or the second metallocene, the olefin monomer, and the organoaluminum co-catalyst is contacted with the support activator, this composition (with the addition of the support activator) is called the "subsequent contact mixture." The subsequent contact mixture optionally remains in contact for a second period of time, the subsequent contact time, before starting the polymerization process. The subsequent contact times between the previously contacted mixture and the support activator in general vary from about 1 minute to about 24 hours. In a further aspect, the subsequent contact time is in a range from about 3 minutes to about 1 hour. The prior contact stage, the subsequent contact stage, or both, can increase the productivity of the polymer compared to the same catalyst composition that is prepared without prior contact or subsequent contact. However, neither a prior contact stage nor a subsequent contact stage is required.

The subsequent contact mixture can be heated to a temperature and for a period of time sufficient to allow the adsorption, impregnation, or interaction of the prior contact mixture and the support activator, so that a portion of the components of the mixture contacting is previously immobilized, adsorbed, or deposited therein. Where heating is employed, the subsequent contact mixture is generally heated to a temperature from about -17.78 ° C (0 ° F) to about 65.56 ° C (150 ° F), or about 4.44 ° C (40 ° C). ° F) to approximately 35 ° C (95 ° F).

In accordance with one aspect of this invention, the weight ratio of the ansa-metallocene compound having the Formula (I) to the second metallocene compound in the catalyst composition is generally in a range of about 100: 1 to about 1: 100. In another aspect, the weight ratio is in a range of from about 75: 1 to about 1:75, from about 50: 1 to about 1:50, or from about 30: 1 to about 1:30. In yet another aspect, the weight ratio of the ansa-metallocene compound having the formula (I) to the second metallocene compound in the catalyst composition is in a range of about 25: 1 to about 1:25. For example, the weight ratio can be in a range of about 20: 1 to about 1:20, about 15: 1 to about 1:15, about 10: 1 to about 1:10, about 5: 1. up to about 1: 5; from about 4: 1 to about 1: 4, or from about 3: 1 to about 1: 3.

When a prior contacting step is used, the molar ratio of the total moles of the olefin monomer to the total moles of the metallocene (s) in the previously contacted mixture is typically in a range of about 1:10 up to approximately 100,000: 1. The total moles of each component are used in this relationship to consider aspects of this invention where more than one Olefin monomer and / or more than one metallocene compound is employed in a pre-contact step. In addition, this molar ratio can be in a range of about 10: 1 to about 1,000: 1 in another aspect of the invention.

In general, the weight ratio of the organoaluminum compound to the support activator is in a range of about 10: 1 to about 1: 1000. If more than one organoaluminum compound and / or more than one support activator is employed, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminum compound to the support activator is in a range of about 3: 1 to about 1: 100, or about 1: 1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocene compounds (total of the ansa-metallocene compound having the formula (I) and the second metallocene compound) to the support activator is in a range of about 1: 1 to approximately 1: 1, 000, 000. If more than one support activator is used, this ratio is based on the total weight of the support activator. In another aspect, this weight ratio is in a range of from about 1: 5 to about 1: 100,000, or from about 1:10 to about 1: 10,000. Still, in another aspect, the weight ratio of the metallocene compounds to the support activator is in a range of about 1:20 to about 1: 1000.

Catalyst compositions of the present invention generally have a catalyst activity greater than about 100 grams of polyethylene (homopolymer, copolymer, etc., as the context requires) per gram of support activator per hour (abbreviated g / g / hr). In another aspect, the catalyst activity is greater than about 150, greater than about 250, or greater than about 500 g / g / hr. In yet another aspect, catalyst compositions of this invention can be characterized as having a catalyst activity greater than about 550, greater than about 650, or greater than about 750 g / g / hr. Still, in another aspect, the catalyst activity may be greater than about 1000 g / g / hr. This activity is measured under suspension polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90 ° C and a reactor pressure of about 27.42 kgf / cm2 (390 psig).

In accordance with another aspect of the present invention, catalyst compositions described herein may have a greater catalyst activity than about 10 grams of polyethylene (homopolymer, copolymer, etc., as the context requires) per μp ??? of total metallocenes per hour (abbreviated g / ^ mol / hr). An activity of 10 g / ymol / hr equals an activity of 10,000 kg / mol / hr. In another aspect, the catalytic activity of the catalyst composition may be greater than about 15, greater than about 20, or greater than about 25 g / umol / hr. In yet another aspect, catalyst compositions of this invention can be characterized as having a catalyst activity greater than about 30, greater than about 40, or greater than about 50 g / mol / hr. Still, in another aspect, the catalyst activity may be greater than about 100 g / mol / hr. This activity is measured under suspension polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90 ° C and a reactor pressure of about 27.42 kgf / cm2 (390 psig).

As discussed above, any combination of the ansa-metallocene compound having the formula (I) and / or the second metallocene, the support activator, the organoaluminum compound, and the olefin monomer, may be contacted previously in some aspects of this invention. When any previous contact occurs with an olefinic monomer, it is not necessary that the The olefin monomer used in the previous contact step is the same as the olefin to be polymerized. Further, when a prior contacting step between any combination of the catalyst components is employed for a first period of time, this previously contacted mixture can be used in a subsequent subsequent contacting step between any other combination of catalyst components by one second. time frame. For example, one or more metallocene compounds, the organoaluminum compound, and 1-hexene can be used in a prior contacting step for a first period of time, and this mixture contacted previously can then be contacted with the support activator to form the subsequent contact mixture which is contacted for a second period of time before starting the polymerization reaction. For example, the first contact time period, the prior contact time, between any combination of the metallocene compound (s), the olefinic monomer, the support activator, and the organoaluminum compound can be about 1. minute to about 24 hours, from about 3 minutes to about 1 hour, or from about 10 minutes to about 30 minutes. The subsequent contact mixture is optionally left in contact for a second period of time, the subsequent contact time, before starting the process of polymerization. In accordance with one aspect of this invention, the subsequent contact times between the previously contacted mixture and any of the remaining catalyst components is from about 1 minute to about 24 hours, or from about 5 minutes to about 1 hour.

POLYMERIZATION PROCESSES Catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like. One such process for polymerizing olefins in the presence of a catalyst composition of the present invention comprises contacting the catalyst composition with an olefin monomer and optionally an olefin monomer (one or more) under polymerization conditions to produce a polymer of olefin, wherein the catalyst composition comprises an ansa-metallocene compound having the formula (I), a second metallocene, and an activator (eg, a support activator comprising a solid oxide treated with an electron attractant anion). Metallocene compounds having the formula (I): E (CpARAm) (CpBRBn) MXq (I), and second metallocenes are discussed above.

For example, in one aspect, the ansa-metallocene compound having the formula (I) may comprise (or consist essentially of, or consist of) an ansa-metallocene compound having the formula (II), formula (III), formula (IV), formula (V), formula (VI), formula (VII), or combinations thereof. In yet another aspect, the ansa-metallocene compound having the formula (I) may comprise (or consist essentially of, or consist of) an ansa-metallocene compound having the formula (C), formula (D), formula ( E), or combinations thereof. In these and other aspects, the second metallocene compound may comprise (or consist essentially of, or consist of) a non-bridged metallocene compound and / or a bridged metallocene compound. In another aspect, for example, the second metallocene compound may comprise (or consist essentially of, or consist of) a metallocene compound having the formula (C2), formula (D2), formula (E2), formula (F2) , or combinations thereof.

In accordance with one aspect of the invention, the polymerization process employs a catalyst composition comprising an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator, wherein the activator comprises an activator of support. Activators of supports useful in the polymerization process of the present invention are described previously. The catalyst composition may further comprise one or more of an organoaluminum compound or compounds (suitable organoaluminum compounds are also discussed above). Therefore, a process for the polymerization of olefins in the presence of a catalyst composition can employ a catalyst composition comprising an arysa-metallocene compound having the formula (I), a second metallocene compound, a support activator , and an organoaluminum compound. In some aspects, the support activator may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, alumina-fluorinated silica, alumina-chlorinated silica, alumina-brominated silica, alumina-silica. sulphated, zirconia-fluorinated silica, zirconia-chlorinated silica, zirconia-brominated silica, zirconia-sulfated silica, titania-fluorinated silica, coated alumina-fluorinated silica, coated alumina-sulfated silica, coated alumina-phosphate silica, and the like, or combinations from the same. In some aspects, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof.

According to another aspect of the invention, the polymerization process employs a catalyst composition comprising only one ansa compound -metallocene having the formula (I) (for example, an ansa-metallocene compound having the formula (II), formula (III), formula (IV), formula (V), formula (VI), or formula (VII)); only a second metallocene compound (for example, a metallocene compound having the formula (C2), formula (D2), formula (E2), formula (F2)); at least one support activator; and at least one organoaluminum compound.

According to another aspect of the invention, the polymerization process can employ a catalyst composition comprising an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator, wherein the activator comprises a compound of aluminoxane, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.

The catalyst compositions of the present invention are proposed for any olefin polymerization method 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 than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of reactors include those which may be referred to as a batch reactor, suspension 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 reactor are well known to those skilled in the art. The gas phase reactors may comprise fluidized bed reactors or staggered horizontal reactors. The suspension reactors may comprise vertical or horizontal loops. High pressure reactors may comprise autoclave or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes could use intermittent or continuous product discharge. The processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, and / or diluent.

The polymerization reactor systems of the present invention may comprise a reactor type in a multiple system or reactors of the same or different type. The production of polymers in multiple reactors can include several stages in at least two separate reactors of polymerizations interconnected by a transfer device making it possible to transfer the resulting polymers from the first polymerization reactor in the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactor. Alternatively, polymerization in multiple reactors may include manual transfer of the polymer from a reactor to subsequent reactors for continued polymerization. Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of gas phase and loop reactors, multiple high pressure reactors, or a combination of high pressure with loop phase reactors and / or gas. Multiple reactors can be operated in series, in parallel, or both.

In accordance with one aspect of the invention, the polymerization reactor system may comprise at least one loop suspension reactor comprising vertical or horizontal loops. The monomer, diluent, catalyst, and comonomer can be continuously fed into a loop reactor where the polymerization occurs. In general, the continuous process may comprise the continuous introduction of monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising particles polymeric and the diluent. The reactor effluent can be reduced to remove the solid polymer from the liquids comprising the diluent, monomer and / or comonomer. Various technologies may be used for this separation step including, but not limited to, reduction which may include any combination of heat addition and pressure reduction; separation by cyclonic action in either a cyclone or hydrocyclone; or separation by centrifugation.

A typical suspension polymerization process (also known as the particle forming process) is described, for example, in U.S. 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 it is incorporated herein by reference in its entirety.

Suitable diluents used in the suspension polymerization include, but are not limited to, the monomer to be polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions may occur under volume conditions where diluent is not used. An example is the polymerization of propylene monomer as described in U.S. Patent Nos. 5,455,314, which are incorporated by reference herein in their entirety.

According to yet another aspect of this invention, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recycle stream containing one or more continuous cycle monomers through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream can be removed from the fluidized bed and recycled back into the reactor. Simultaneously, the polymeric product can be removed from the reactor and a new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors may comprise a process for multistage gas phase polymerization of olefins, in which the olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a polymer that contains catalyst formed in a first zone of polymerization zone to a second polymerization zone. One type of gas phase reactor is described in U.S. Patent Nos. 5,352,749, 4,588,790, and 5,436,304, each of which is incorporated herein by reference in its entirety.

In accordance with yet another aspect of the invention, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomer, initiators, or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into an area of the reactor. Initiators, catalysts, and / or catalyst components can be entrained in a gaseous stream and introduced into another area of the reactor. The gas streams can be intermixed for polymerization. The heat and pressure can be used appropriately to obtain the optimum polymerization reaction conditions.

In accordance with yet another aspect of the invention, the polymerization reactor may comprise a solution polymerization reactor wherein the monomer / comonomer is in contact with the catalyst composition by suitable agitation or other means. A carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer / comonomer can be brought into the vapor phase to be contacted with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures which will result in the formation of a solution of the polymer in a reaction medium. Agitation can be used to obtain better temperature control and keep the polymerization mixtures uniform throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of the polymerization.

Polymerization reactors suitable for the present invention may further comprise any combination of at least one feedstock feeding system, at least one feed system for the catalyst or catalyst components, and / or at least one polymer recovery system. Reactor systems suitable for the present invention may further comprise systems for purification of feed material, storage and catalyst preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis and control of process.

Polymerization conditions that are controlled for efficiency and to provide the desired polymer properties may include temperature, pressure, and the concentrations of various reagents. The polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. A suitable polymerization temperature can be any temperature below the depolymerization temperature in accordance with the equation of Gibbs Free energy. Typically, it includes from about 60 ° C to about 280 ° C, for example, or from about 60 ° C to about 110 ° C, depending on the type of polymerization reactor. In some reactor systems, the polymerization temperature is generally within a range of about 70 ° C to about 90 ° C, or about 75 ° C to about 85 ° C.

Suitable pressures will also vary in accordance with the reactor and type of polymerization. The pressure for liquid phase polymerizations in a loop reactor is typically less than 70.31 kgf / cm2 (1000 psig). The pressure for the gas phase polymerization is usually at about 14.06 to 35.15 kgf / cm2 (200 to 500 psig). High pressure polymerization in tubular reactors or autoclave is run in general at about 1406.14 to 5273.02 kgf / cm2 (20,000 to 75,000 psig). Polymerization reactors can also be operated in a supercritical region that occurs in general at higher temperatures and pressures. The operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.

Aspects of this invention are directed to an olefin polymerization process comprising contacting a catalyst composition with an olefin monomer and optionally an olefin monomer under polymerization conditions to produce an olefin polymer. The olefin polymer produced by the process can have a density greater than about 0.90 g / cm 3, or greater than about 0.91 g / cm 3, for example, in a range of from about 0.91 to about 0.96 g / cm 3. In addition, or alternatively, the olefin polymer may have an average of less than about 10 short chain branches (SCB's) per 1000 total carbon atoms, or less than about 5 SCB's per 1000 total carbon atoms, for example, from 0 up to about 4 SCB's per 1000 total carbon atoms. In addition, or alternatively, the olefin polymer may have less than about 0.005 long chain branches (LCB's) per 1000 total carbon atoms, eg, less than about 0.002, or less than about 0.001, LCB's per 1000 total carbon atoms .

In another aspect, the olefin polymer (e.g., copolymer) produced by the process may have a density greater than about 0.90 g / cm 3, or greater than about 0.91 g / cm 3, for example, in a range of about 0.91 to about 0.95 g / cm3. In addition, or alternatively, the olefin polymer can have an average of about 0.5 to about 10 short chain branches (SCB's) per 1000 total carbon atoms, for example, from about 0.5 to about 4 SCB's per 1000 total carbon atoms. In addition, or alternatively, the olefin polymer may have less than about 0.005 long chain branches (LCB's) per 1000 total carbon atoms, eg, less than about 0.002, or less than about 0.001, LCB's per 1000 total carbon atoms . In addition, or alternatively, the olefin polymer may have a bimodal molecular weight distribution. Additionally, or alternatively, the olefin comonomer may have a conventional comonomer distribution.

Aspects of this invention are also directed to an olefin polymerization process conducted in the absence of added hydrogen. In this description, "aggregate hydrogen" will be denoted as the ratio of hydrogen feed to olefin monomer entering the reactor (in units of ppm by weight). An olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin monomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises an ansa-metallocene compound. having the formula (I), a second metallocene compound, and an activator, wherein the polymerization process is conducted in the absence of hydrogen aggregate. As described above, the ansa-metallocene compound having the formula (I) may comprise an ansa-metallocene compound having the formula (II), formula (III), formula (IV), formula (V), formula (VI) ), formula (VII), formula (C), formula (D), formula (E), or combinations thereof; and the second metallocene compound may comprise a metallocene compound having the formula (C2), formula (D2), formula (E2), formula (F2), or combinations thereof. As one of ordinary skill in the art would recognize, hydrogen can be generated in situ by metallocene catalyst compositions in various olefin polymerization processes, and the amount generated can vary depending on the specific catalyst composition and metallocene compound (s). employees, the type of polymerization process used, the polymerization reaction conditions used, and so on.

In other aspects, it may be desirable to conduct the polymerization process in the presence of a certain amount of added hydrogen. Therefore, an olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin monomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator, and wherein the polymerization process is conducted in the presence of added hydrogen. For example, the ratio of hydrogen to the olefin monomer in the polymerization process can be controlled, often by the ratio of hydrogen feed to the olefin monomer entering the reactor. The ratio of hydrogen added to the olefin monomer in the process can be controlled at a weight ratio which often fails within a range of from about 10 to about 2000 ppm, from about 25 ppm to about 1500 ppm, from about 50 to about about 1000 ppm, from about 75 ppm to about 750 ppm, or from about 100 to about 500 ppm (by weight).

Figure 1 graphically represents the impact of hydrogen addition on the molecular weight in a representative double standard catalyst system, for the molecular weight distribution curves as a function to increase the logarithm of the molecular weight. In this conventional dual catalyst system, the addition of hydrogen broadens the molecular weight distribution of the total polymer. On the contrary, Figure 2 graphically represents the impact of hydrogen addition on the molecular weight in a representative double catalyst system in accordance with aspects of the present invention, for the molecular weight distribution curves as a function to increase the logarithm of the molecular weight. In Figure 2, the hydrogen addition unexpectedly narrows the molecular weight distribution of the total polymer. For example, the ansa-metallocene compound having the formula (I) with an activator (eg, a chemically treated solid oxide) can produce a low molecular weight component of the polymer and be relatively unaffected by the addition of hydrogen. Therefore, a component of the higher molecular weight polymer produced by the second metallocene can be independently controlled with the addition of hydrogen.

In a particular aspect, the polymerization process is conducted in the presence of aggregate hydrogen, and the ratio of Pm / Nm of the olefin polymer produced by the process may decrease as the amount of added hydrogen increases from about 100 to about 1000 ppm. , for example, from about 100 to about 500 ppm, or from about 100 to about 400 ppm. The decrease in the Pm / Nm ratio can be up to 10%, up to 15%, or up to 20%, or more; non-limiting examples of ranges of percentage decrease in the Pm / Nm ratio include from about 0.1% to about 20%, from about 0.5% to about 15%, of about 0.5% to about 10%, from about 1% to about 10%, or from about 1% to about 8%, and the like. Unexpectedly, the molecular weight distribution of the olefin polymer can be narrowed as the addition of hydrogen increases. For example, the ratio of Pm / Nm of the polymer produced by the process in the presence of approximately 350 ppm of added hydrogen (or approximately 300 ppm, or approximately 400 ppm) may be less than the Pm / Nm of a polymer produced by the process in the presence of about 150 ppm of added hydrogen (or about 100 ppm, or about 200 ppm), when it is produced under the same polymerization conditions. In one aspect, the ratio of Pm / Nm can be up to 10% less, up to 15% less, or up to 20% less, etc., while in another aspect, the Pm / Nm can be less by a percentage in a range of about 0.1% to about 20%, from about 0.5% to about 15%, from about 0.5% to about 10%, from about 1% to about 10%, or from about 1% to about 8%. In a further aspect, the ratio of Pm / Nm of a polymer produced by the process in the presence of aggregate hydrogen can be reduced from a Pm / Nm higher than 6 up to a Pm / Nm of less than 5.5, reduced from a Pm / Nm greater than 5.5 up to a Pm / Nm less than 5, reduced from a Pm / Nm higher than 5 to a Pm / Nm less than 5, or reduced from a Pm / Nm higher than 4.5 to a Pm / Nm less than 4.5. Additionally, although not required, these processes may be conducted in the presence of a comonomer (one or more), such as, for example, at a molar ratio of comonomer: monomer in a range of about 0.01 to about 0.25: 1, about 0.02: 1 to about 0.20: 1, or about 0.01 to about 0.10: 1.

Applicants also contemplate a method for lowering the Pm / Nm ratio of an olefin polymer, and this method comprises contacting a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce the olefin polymer.; contacting the catalyst composition with the olefin monomer and the optional olefin comonomer in the presence of added hydrogen; and increasing the amount of hydrogen added within the range of from about 100 to about 1000 ppm, or from about 100 to about 500 ppm, or from about 100 to about 400 ppm; wherein the catalyst composition comprises an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator (eg, a support activator). For example, the amount of added hydrogen can be increased from about 150 ppm to about 350 ppm, unexpectedly resulting in a decrease in the Pm / Nm of the polymer. In this method, the ratio of Pm / Nm can be decreased up to 10%, up to 15%, or up to 20%, etc., for example, the Pm / Nm can be decreased by a percentage in a range of approximately 0.1% up to about 20%, from about 0.5% to about 15%, from about 0.5% to about 10%, from about 1% to about 10%, or from about 1% to about 8%. Furthermore, in some aspects, the ratio of Pm / Nm can be decreased from a Pm / Nm higher than 6 to a Pm / Nm less than 5.5, decreased from a Pm / Nm higher than 5.5 to a Pm / Nm less than 5, decreased from a Pm / Nm greater than 5 to a Pm / Nm less than 5, or decreased from a Pm / Nm greater than 4.5 to a Pm / Nm less than 4.5.

According to another aspect, an olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin monomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition it comprises an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator, and wherein the polymerization process is conducted in the presence of added hydrogen. In this aspect, the Pm of the high molecular weight component of the olefin polymer can be independently controlled. For example, the Mw of the high molecular weight component of the olefin polymer can be reduced by the addition of hydrogen, while the Mw of the low molecular weight molecular component of the olefin polymer is not reduced by the addition of hydrogen. Such may be the case over a range of aggregate hydrogen that generally falls between about 100 and about 1000 ppm, between about 100 and about 500 ppm, or between about 100 and about 400 ppm.

Consistent with other aspects of the invention described herein, an olefin polymerization process may comprise contacting a catalyst composition with an olefin monomer and an olefin monomer under polymerization conditions to produce an olefin polymer, and in this aspect, the olefin polymer (e.g., an olefin copolymer) has a conventional comonomer distribution. The catalyst composition employed may comprise an amphalo-metallocene compound having the formula (I), a second metallocene compound (eg, a metallocene containing hafnium or, alternatively, zirconium), and an activator (eg, a support activator comprising a solid oxide treated with an electron attractant anion). Often, this polymerization process can be conducted in the presence of added hydrogen. Typical levels of aggregate hydrogen may include, but are not limited to, from about 50 ppm to about 2000 ppm, from about 75 ppm to about 1500 ppm, from about 75 ppm to about 1250 ppm, from about 100 ppm to about 1000 ppm, or from about 100 ppm to about 750 ppm, and the like.

Applicants also contemplate a method for producing an olefin polymer (e.g., an olefin copolymer) having a conventional comonomer distribution, and this method comprises contacting a catalyst composition with an olefin monomer and a low olefin monomer. polymerization conditions to produce the olefin polymer; contacting the catalyst composition with the olefin monomer and the olefin comonomer in the presence of added hydrogen; wherein the catalyst composition comprises an ansa-metallocene compound having the formula (I), a second metallocene compound, and an activator (eg, a support activator). For example, the ansa-metallocene compound having the formula (I) and the second metallocene in the catalyst composition can be selected from so that the arysa-metallocene compound having the formula (I) can produce the higher molecular weight component of the polymer, and the second metallocene can promote the incorporation of the comonomer and produce the low molecular weight component of the polymer.

In some aspects of this invention, the feed or reagent ratio of hydrogen to olefin monomer can be maintained substantially constant during the polymerization run for a particular polymer grade. That is, the ratio of hydrogen: olefin monomer can be selected at a particular ratio within a range of about 5 ppm to about 1500 ppm or so in succession, and maintained in the ratio within about +/- 25% during the run. of polymerization. For example, if the target ratio is 100 ppm, then maintaining the hydrogen: substantially constant olefin monomer ratio could link maintaining the feed ratio between about 75 ppm and about 125 ppm. In addition, the addition of comonomer (or comonomers) can be, and in general is, substantially constant through the polymerization run for a particular polymer grade.

However, in other aspects, it is contemplated that the monomer, comonomer (or comonomers), and / or hydrogen may be periodically pulsed to the reactor, for example, in a similar to that used in U.S. Patent No. 5,739,220 and U.S. Patent Application No. 2004/0059070, the descriptions of which are hereby incorporated by reference in their entirety.

The concentration of reagents entering the polymerization reactor can be controlled to produce resins with certain physical and mechanical properties. The proposed end-use product that will be formed by the polymer resin and the method of forming such a product can finally determine the desired properties and attributes of the polymer. The mechanical properties include stress, bending, impact, drag, stress relaxation and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, vitreous transition temperature, crystallization melting temperature, density, stereoregularity, crack growth, long chain branching, and rheological measurements.

This invention is also directed to, and encompasses, the polymers produced by any of the polymerization processes described herein. The articles of manufacture may be formed from, and / or may comprise, polymers produced in accordance with this invention.

POLYMERS and ARTICLES If the resulting produced polymer according to the present invention is, for example, an ethylene polymer or copolymer, its properties can be characterized by various known analytical techniques and are used in the polyolefin industry. The articles of manufacture may be formed from, and / or may comprise, the ethylene polymers of this invention, whose typical properties are provided below.

The ethylene polymers (copolymers, terpolymers, etc.) produced in accordance with this invention generally have a melt index of from 0 to about 100 g / 10 min. Melt indices in the range from 0 to about 75 g / 10 min, from 0 to about 50 g / 10 min, or from 0 to about 25 g / 10 min, are contemplated in some aspects of this invention. For example, a polymer of the present invention can have a melt index (MI) in a range from 0 to about 5 g / 10 min, from 0 to about 1 g / 10 min, or from 0 to about 0.5 g / 10 min.

The ethylene polymers produced in accordance with this invention may have an HLMI / MI ratio of greater than about 5, such as, for example, greater than about 10, greater than about 15, or greater than approximately 20. Intervals contemplated for HLMI / MI include, but are not limited to, from about 5 to about 150, from about 10 to about 125, from about 10 to about 100, from about 15 to about 90, from about 15 to about 80, from about 15 to about 70, or from about 15 to about 65.

The densities of ethylene-based polymers produced using the catalyst systems and processes described herein are often greater than about 0.90 g / cm 3. In one aspect of this invention, the density of an ethylene polymer can be greater than about 0.91, greater than about 0.92, or greater than about 0.93 g / cm3. Still, in another aspect, the density may be in a range of from about 0.90 to about 0.97 g / cm 3, such as, for example, from about 0.91 to about 0.96 g / cm 3, from about 0.92 to about 0.96 g / cm 3, or from about 0.91 to about 0.95 g / cm3.

The ethylene polymers of this invention can generally average from 0 to about 10 short chain branches (SCB's) per 1000 total carbon atoms. For example, the contents of SCB average in a range from 0.5 to about 10, from 0 to about 8, from 0 to about 5, or from about 0.5 to about 5, SCB's per 1000 total carbon atoms are contemplated herein.

Ethylene polymers, such as copolymers and terpolymers, within the scope of the present invention generally have a polydispersity index - a ratio of average molecular weight (Pm) to number average molecular weight (Nm) - in a range In some aspects described herein, the ratio of Pm / Nm is in a range of from about 3 to about 9, from about 3 to about 8, or from about 4 to about 7. The ratio of Mz. / Pm for the polymers of this invention is often in a range of about 1.6 to about 12. Mz is the z-average molecular weight. According to one aspect, the Mz / Pm of the ethylene polymers of this invention may be in a range of from about 1.6 to about 10, from about 1.7 to about 5, from about 1.7 to about 3, or from about 1.7 to about 2.5.

In general, the olefin polymers of the present invention have low levels of chain branching long, with typically less than 0.05 long chain branches (LCB's) per 1000 total carbon atoms. In some aspects, the number of LCB's per 1000 total carbon atoms is less than about 0.02, less than about 0.01, or less than about 0.008. In addition, the olefin polymers of the present invention (e.g., ethylene polymers) can have less than about 0.005, less than about 0.004, less than about 0.003, less than about 0.002, or less than about 0.001 LCB's per 1000 atoms carbon totals, in other aspects of this invention.

Certain ethylene polymers (e.g., certain copolymers) produced using the polymerization process and catalyst systems described above may have a conventional comonomer distribution, i.e., a short chain branch content that decreases as the molecular weight increases, e.g. , the higher molecular weight components of the polymer in general have lower comonomer incorporation than the lower molecular weight components. In general, there is a decrease in incorporation of the comonomer as the molecular weight increases. Often, the amount of comonomer incorporation into higher molecular weights may be about 20% lower, or about 30% lower, or about 50% lower, or about 70%. lower, or approximately 90% lower, than at lower molecular weights. For example, the number of SCB 's per 1000 total carbon atoms may be greater in Nm than in Pm. The ethylene polymers of this invention may have a SCBD (short chain branching distribution) which is similar to the SCBD found in ethylene polymers produced using traditional Ziegler-Natta catalyst systems (ie, a conventional comonomer distribution).

Furthermore, the SCBDs of certain polymers of the present invention can be characterized by the ratio of the number of SCB's per 1000 total carbon atoms of the polymer in DI to the number of SCB's per 1000 total carbon atoms of the polymer in D90, ie , (SCB's in DIO) / (SCB's in D90). D90 is the molecular weight at which 90% of the polymer by weight has higher molecular weight, and DIO is the molecular weight at which 10% of the polymer by weight has higher molecular weight. D90 and DIO are plotted in Figure 3 for a molecular weight distribution curve as a function to increase the logarithm of the molecular weight. In accordance with one aspect of the present invention, a ratio of the number of SCB 's per 1000 total carbon atoms of the polymer in DI to the number of SCB' s per 1000 total carbon atoms of the polymer in D90 is less than about 0.9. For example, the ratio of (SCB's in DIO) / (SCB's in D90) can be in a range of approximately 0.1 to approximately 0.9. In another aspect, the ratio is less than about 0.8, or less than about 0.7. Still, in another aspect, the ratio of the number of SCB's per 1000 total carbon atoms of the polymer in Di to the number of SCB's per 1000 total carbon atoms of the polymer in D90 is in a range of from about 0.2 to about 0.8, such as, for example, from about 0.3 to about 0.7.

An illustrative and non-limiting example of an ethylene polymer of the present invention may be characterized by a density greater than about 0.90 g / cm 3, or greater than about 0.91 g / cm 3 (e.g., in a range of about 0.91 to about 0.96. g / cm3); and / or an average of less than about 10 short chain branches (SCB's) per 1000 total carbon atoms, or less than about 5 SCB's per 1000 total carbon atoms (e.g., in a range from 0 to about 4 SCB's per 1000 total carbon atoms); and / or less than about 0.005 long chain branches (LCB's) per 1000 total carbon atoms (eg, less than about 0.002, or less than about 0.001, LCB's per 1000 total carbon atoms); and / or a melt index in a range from 0 to about 5 g / 10 min (e.g., from 0 to approximately 0.5 g / 10 min); and / or a ratio of Pm / Nm in a range from about 2 to about 10 (e.g., from about 3 to about 7); and / or a ratio of Mz / Pm in a range of about 1.6 to about 10 (e.g., from about 1.7 to about 3).

Another illustrative and non-limiting example of an ethylene polymer (e.g., copolymer) of the present invention can be characterized by a density greater than about 0.90 g / cm3, or greater than about 0.91 g / cm3 (e.g., in a range from about 0.91 to about 0.95 g / cm 3); and / or an average of about 0.5 to about 10 short chain branches (SCB's) per 1000 total carbon atoms (eg, in a range of about 0.5 to about 4 SCB's per 1000 total carbon atoms); and / or less than about 0.005 long-chain branches (LCB's) per 1000 total carbon atoms (eg, less than about 0.002, or less than about 0.001, LCB's per 1000 total carbon atoms, and / or a weight distribution) bimodal molecular and / or a conventional comonomer distribution (eg, a number of SCB's per 1000 total carbon atoms being greater in Nm than in Pm) and / or a ratio of (SCB's in DIO) / (SCB's in D90) ) in a range of about 0.1 to about 0. 9; and / or melt index in a range from 0 to about 100 g / 10 min (eg, from 0 to about 25 g / 10 min); and / or a ratio of Pm / Nm in a range from about 2 to about 10 (e.g., from about 3 to about 7); and / or a ratio of Mz / Pm in a range of about 1.6 to about 10 (e.g., from about 1.7 to about 3).

Ethylene polymers, be they homopolymers, copolymers, terpolymers, and so on, can be formed into various articles of manufacture. The articles which may comprise polymers of this invention include, but are not limited to, an agricultural film, an automotive part, a bottle, a drum, a fiber or cloth, a film or container for packaging food, an article for service of food, a fuel tank, a geomembrane, a domestic container, a liner, a molded product, a medical device or material, a pipe, a sheet or tape, a toy, and the like. Several processes can be used to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. Additionally, additives and modifiers are often added to these polymers with the In order to provide beneficial polymer processing or end-use product attributes. Such processes and materials are described in Modern Plastics Encyclopedia, Mid-November 1995 Issue, Vol. 72, No. 12; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992; the descriptions of which are incorporated herein by reference in their entirety.

Applicants also contemplate a method for forming or preparing an article of manufacture comprising a polymer produced by any of the polymerization processes described herein. For example, a method may comprise (i) contacting a catalyst composition with an olefin monomer and optionally an olefin monomer (one or more) under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise an ansa-raetalocene compound having the formula (I), a second metallocene compound, an activator (e.g., a support activator), and an optional co-catalyst (e.g., an organoaluminum compound); and (ii) forming an article of manufacture comprising the olefin polymer. The forming step may comprise mixing, melt processing, extrusion, molding, or thermoforming, and the like, including combinations thereof.

EXAMPLES The invention is further illustrated by the following examples, which are not being constructed in any way as imposing limitations on the scope of this invention. Various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest the same for one of ordinary skill in the art without departing from the spirit of the present invention or within the scope of attached claims.

The melt index (MI, g / 10 min) was determined in accordance with ASTM D1238 at 190 ° C with a weight of 2,160 grams.

The high load melt index (HLMI g / 10 min) was determined in accordance with ASTM D1238 at 190 ° C with a weight of 21,600 grams.

The density of the polymer in grams per cubic centimeter (g / cm3) was determined in a compression molded sample, cooled to approximately 15 ° C per hour, and conditioned for approximately 40 hours at room temperature in accordance with ASTM D1505 and ASTM D1928, procedure C.

Molecular weights and molecular weight distributions were obtained using a high temperature chromatography unit PL 220 SEC (Polymer Laboratories) with trichlorobenzene (TCB) as the solvent, with 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 stabilizer in the TCB. An injection volume of 200 μL was used with a nominal polymer concentration of 1.5 mg / mL. Dissolution of the sample in the stabilized TCB was carried out by heating at 150 ° C for 5 hours with gentle, occasional shaking. The columns used were three columns PLgel Mixed A LS (7.8x300mm) and were calibrated with a wide linear polyethylene standard (Phillips Marlex® BHB 5003) for which the molecular weight was determined.

SEC-MALS combines the methods of size exclusion chromatography (SEC) with multiple angle light scattering detection (MALS). A DAWN EOS-18 angle light scattering photometer (Wyatt Technology, Santa Barbara, CA) joined a PL-210 SEC system (Polymer Labs, UK) or a 150 HP Plus system (Milford, MA) through of a heat transfer line, thermally controlled at the same temperature as the SEC columns and its differential refractive index (DRI) detector (145 ° C). At a flow rate adjustment of 0.7 mL / min, the mobile phase, 1,2,4-trichlorobenzene (TCB), was eluted through three columns, 7.5 mm x 300 mm, 20 μ? Mixed A-LS (Polymer Labs). Polyethylene (PE) solutions with concentrations of -1.2 mg / mL, depending on the samples, were prepared at 150 ° C for 4 h before being transferred to the SEC injection vials seated in a carrousel heated to 145 ° C. For polymers of higher molecular weight, prolonged heating times were necessary in order to obtain true homogenous solutions. In addition to acquiring a concentration chromatogram, seventeen light scattering chromatograms at different angles were also acquired for each injection using Wyatt 's Astra ® software. In each chromatographic slice, both absolute molecular weight (M) and root mean square radius (RMS), also known as radius of gyration (Rg) were obtained from an intercept and slope of the Debye line, respectively. The methods for this process are detailed in Wyatt, P.J., Anal. Chim. Acta, 272, 1 (1993), which is incorporated herein by reference in its entirety.

The Zimm-Stockmayer procedure was used to determine the amount of LCB. Since SEC-MALS measures M and Rg in each slice of a chromatogram simultaneously, the branching indices, gM, as a function of M could be determined in each slice directly by determining the ratio of the average square Rg of branched molecules to those of the linear ones, in the same M, as shown in the following equation (the subscripts br and lin represent branched and linear polymers, respectively).

In a given gM, the average number by weight of LCB per molecule was computed using the Zimm-Stockmayer equation, shown in the following equation, where the branches were assumed to be trifunctional, or in the form of Y.

The LCB frequency (LCBMi), the LCB number per 1000 C, of the ith slice was then computed directly using the following equation (Mi is the PM of the slice Ith): LCBUi = 1 000 * 14 * B3"/ Mi The LCB distribution (LCBD) through the molecular weight distribution (DPM) was thus established for a complete polymer.

The short chain branching distribution (SCBD) data was obtained using a high temperature heated flow cell SEC-FTIR (Polymer Laboratories) as described by P.J. DesLauriers, D.C. Rohlfing, and E.T. Hsieh, Polymer, 43, 159 (2002).

The rheological characterizations of fusion are performed as follows. Small strain oscillatory cutoff measurements (10%) were performed on an ARES rheometer from Rheometrics Scientific, Inc. using parallel plate geometry. All the rheological tests were carried out at 190 ° C. The complex viscosity \? * \ Against the frequency data (co) were then adjusted in the curve using the three-parameter Carreau-Yasuda (CY) empirical model to obtain the zero-0 viscosity, characteristic viscous relaxation time - t ?, and the amplitude parameter - a. The simplified Carreau-Yasuda (CY) empirical model is as follows.

I? (fi I ~ r1i, a-i (l-n) fa 5 [+ (T) J} Where: \? * (?) \ = Magnitude of the complex cutting viscosity; • o = zero shear viscosity; t? = viscous relaxation time; a = "amplitude" parameter; n = sets the last slope energy law, set to 2/11; Y ? = angular frequency of the oscillatory cut deformation.

Details of the meaning and interpretation of the CY model and derived parameters can be found in: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); AC Hieber and H.H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety.

Nuclear Magnetic Resonance (NMR) spectra were obtained on an NMR Varian Mercury Plus 300 spectrometer. CDC13 and C6D6 were purchased from Cambridge Isotope Laboratories, degassed and stored on 13X molecular sieves activated under nitrogen. NMR spectra were recorded using NMR J. Young tubes or capped at ambient probe conditions. Chemical changes of 1H are reported against SiMe4 and were determined with reference to residual 1H and solvent peaks. Coupling constants are reported in Hz.

Gas chromatography was performed using a Varian 3800 GC analyzer fitted with four capillary columns for all purpose Dual Factor (30 mx 0.25 mm), flame ionization detector, and Varian 8400 autosampler unit. The mass spectral analysis was performed at set with an instrument Varies 320 MS using electron ionization at 70 eV.

The sulfated alumina support activator (abbreviated ACTl) used in some of the examples was prepared according to the following procedure. The bohemite was obtained from W.R. Grace Company under the designation "Alumina A" and having a surface area of approximately 300 m2 / g and a pore volume of approximately 1.3 mL / g. This material was obtained as a powder having an average particle size of about 100 microns. This material was impregnated to incipient humidity with an aqueous solution of ammonium sulfate to equal approximately 15% sulfate. This mixture was then placed in a plant tray and allowed to dry under vacuum at about 110 ° C for about 16 hours.

To calcinate the support, approximately 10 grams of this powder mixture were placed in a 4.44 cm (1.75 inch) quartz tube fitted with a sintered quartz disc in the bottom. While the powder was supported on the disk, the air (nitrogen can be replaced) was dried by passing through a 13X molecular sieve column, it was blown upwardly through the disk at the linear velocity of about 0.045 to 0.05 m3 (1.6 up to 1.8 ft3) standard per hour. An electric burner around the quartz tube was then ignited and the temperature was raised at the rate of about 400 ° C per hour to the desired calcination temperature of about 600 ° C. At this temperature, the powder was allowed to fluidize for about three hours in the dry air. Later, the sulfated alumina support activator (ACT1) was collected and stored under dry nitrogen, and used without exposure to the atmosphere.

The fluorinated silica-alumina support activator (abbreviated ACT2) used in some of the examples was prepared according to the following procedure. A silica-alumina was obtained from W.R. Grace Company containing approximately 13% alumina by weight and having a surface area of approximately 400 m2 / g and a pore volume of approximately 1.2 mL / g. This material was obtained as a powder having an average particle size of about 70 microns. Approximately 100 grams of this material was impregnated with a solution containing approximately 200 mL of water and approximately 10 grams of hydrogen fluoride and aluminum, resulting in a wet powder having the consistency of wet sand. This mixture was then placed on a flat tray and allowed to dry under vacuum at about 110 ° C for about 16 hours.

To calcinate the support, approximately 10 grams of this powder mixture were placed in a 4.44 cm (1.75 inch) quartz tube fitted with a sintered quartz disc in the bottom. While the powder was supported on the disc, the air (nitrogen can be replaced) was dried by passing through a 13X molecular sieve column, it puffed up through the disk at the linear velocity of approximately 0.045 to 0.05 m3 (1.6 to 1.8 ft3) standard per hour. An electric burner around the quartz tube was then ignited and the temperature was raised at the rate of about 400 ° C per hour to the desired calcination temperature of about 450 ° C. At this temperature, the powder was allowed to fluidize for about three hours in the dry air. Subsequently, the fluorinated alumina support activator (ACT2) was collected and stored under dry nitrogen, and used without exposure to the atmosphere.

The fluorinated silica-alumina support activator (abbreviated ACT4) employed in some of the examples was prepared in accordance with the following procedure. A silica-coated alumina was obtained from Sasol Company under the designation "Siral 28M" containing about 72% alumina by weight and having a surface area of about 340 m2 / g and a pore volume of about 1.6 mL / g, and an average particle size of approximately 90 microns. Approximately 20 grams of Siral 28 was first calcined at approximately 600 ° C for about 8 hours, then impregnated to incipient wetness with 60 mL of a methanol solution containing 2 g of ammonium bifluoride. This mixture was then placed on a flat tray and allowed to dry under vacuum to approximately 110 ° C for approximately 12 hours.

To calcinate the support, the powder mixture was placed in a 5.08 cm (2 inch) fluidized bed per dry nitrogen. The temperature was raised to 600 ° C for a period of 1.5 hours, and then maintained at 600 ° C for three hours. Subsequently, fluorided silica-coated alumina (ACT4) was collected and stored under dry nitrogen, and used without exposure to the atmosphere.

The titanium fluorinated silica-alumina support activator (abbreviated ACT3) used in some of the examples was prepared according to the following procedure. A silica-coated alumina was obtained from Sasol Company under the designation "Siral 28M" containing approximately 72% alumina by weight, and having a surface area of approximately 340 m2 / g, a pore volume of approximately 1.6. mL / g, and an average particle size of approximately 90 microns. Approximately 682 g of 28M Siral was first calcined at about 600 ° C for about 8 hours, then impregnated to incipient wetness with 2200 mL of a methanol solution containing 147 g of a solution containing 60% of H2TiF6. This mixture, with the consistency of wet sand, was then placed on a flat tray and allowed to dry under vacuum at about 110 ° C for about 12 hours.

To calcinate the support, the powder mixture is placed in a 5.08 cm (2 inch) fluidized bed per dry nitrogen. The temperature was raised to 600 ° C for a period of 1.5 hours, and then maintained at 600 ° C for three hours. Subsequently, titanated fluorinated silica coated alumina (ACT3) was collected and stored under dry nitrogen, and used without exposure to the atmosphere.

The polymerization runs were conducted in a 3.8 liter (one gallon) stainless steel reactor as follows. First, the reactor was purged with nitrogen and then with isobutane vapor. Approximately 0.5 mL of a 1M solution in heptane of either triisobutylaluminum (TIBA) or triethylaluminum (TEA), the support activator (ACT1, ACT2, ACT3, or ACT4), and the metallocene (s) (METI, MET2 , MET3, MET A, structures provided below) were added through a loading port while isobutane vapor is vented. The loading port was closed and approximately 2 L of isobutane were added. The resulting mixture was stirred for 5 min., and then heated to the desired polymerization temperature. After reaching the temperature of the polymerization reactor, the ethylene was charged to the reactor to achieve the desired total reactor pressure, together with a desired amount of 1-hexene comonomer (if used). The ethylene was fed on demand as the polymerization reaction proceeds to keep the reactor pressure constant. If used, nitrogen is added to a fixed mass ratio with regarding the ethylene flow. The reactor is maintained and controlled at the desired temperature and the reactor pressure through the run time of 60 minutes of the polymerization. After completion the isobutane and ethylene were vented from the reactor, the reactor was opened and cooled, and the polymer product was collected and dried.

EXAMPLES 1-99 Polymers produced using an ansa-metallocene having the formula (I) The metallocene compounds used in these examples have the following structures and abbreviations: METI MET2 MET3 Synthesis of METI: A solution of 1,2-dichloro-1,2,12-tetramethyldisilane (2.29 g, 12.3 mmol) in Et20 (25 mL) was prepared. A solution of Li (allyl indenyl) (1.00 g, 6.17 mmol) in Et20 (25 mL) was prepared and added by drip by cannula to the stirred silane solution at approximately 22 ° C for 1 hr. The mixture was stirred overnight and evaporated under vacuum. The residue was suspended in toluene (20 mL), filtered through a pad of Celite and an aliquot of the filtrate was removed. The NMR analysis showed the presence of Me4Si2 (allyl-indenyl) Cl and starting disilane. XH NMR data for Me4Si2 (allyl-indenyl) Cl (C6D6): d 7.31 (d, J = 8, 2H, C6-Ind), 7.19 (t, J = 8, 1H, C6-Ind), 7.08 (t , J = 8, 1H, C6-Ind), 6.22 (m, 1H, C5-Ind), 5.96 (m, 1H, CH = CH2), 5.14 (m, 1H, CH = CH2), 5.06 (m, 1H , CH = CH2), 3.30 (m, C5-Ind), 3.20 (m, 2H, CH2), 0.21 (s, 3H, SiMe), 0.15 (s, 3H, SiMe), 0.12 (s, 3H, SiMe) , -0.09 (s, 3H, SiMe). The filtrate was evaporated and dried under vacuum overnight to obtain a yellow oil (1.9 g). THF (20 mL) was added per cannula, and a solution of cyclopentadienyl-MgCl (7.0 mL, 1.0 M in THF, 7.0 mmol) was added dropwise by syringe to the stirred solution at approximately 22 ° C for 15 min. The mixture was stirred for 2 hr and an aliquot was removed by syringe. The GC-MS analysis showed approximately 95% conversion to the expected ligand Me4Si2 (allyl-indenyl) (cyclopentadienyl). { m / z, 337 { M +} ), with the included balance of products derived from the starting materials. The mixture was stirred an additional 1 hr and evaporated under vacuum. The residue was dried under vacuum at 35 ° C for 1 hr and toluene (20 mL) was added. The suspension was filtered through a pad of Celite and the Celite was washed with toluene (2 x 20 mL). The toluene solutions were combined and evaporated under vacuum to obtain an oil yellow (2.05 g). Et20 (50 mL) was added and the resulting solution was cooled in an ice water bath. A solution of n-BuLi (5.1 mL, 2.5 M in hexanes, 13 mmol) was added via syringe for 3 min and the stirred mixture was warmed to room temperature for 30 min. A suspension of ZrCl4 (1.49 g, 6.39 mmol) in heptane (50 mL) was prepared and cooled in an ice water bath. The lithium solution was added by drip by cannula to the stirred zirconium suspension for 30 min, and the mixture was stirred in the bath overnight. The bright yellow suspension was evaporated under vacuum and CH2Cl2 (50 mL) was added by cannula. The suspension was filtered through a pad of Celite and the Celite was washed with CH2Cl2 (2 x 20 mL). The resulting solutions were combined and evaporated under vacuum to obtain a dark yellow solid (2.76 g). The residue was recrystallized from toluene (10 mL) at -30 ° C to obtain METI as a yellow crystalline solid, which was dried under vacuum (900 mg, 29% recrystallized yield based on Li (allyl-indenyl). NMR (CDCl 3): d 7.73 (d, J = 8, 1H, C6-Ind), 7.63 (d, J = 8, 1H, Ce-Ind), 7.32 (t, J = 8, 1H, C6-Ind) , 7.24 (t, J = 8, 1H, C6-Ind), 6.73 (m, 1H, Cp), 6.72 (s, 1H, C5-Ind), 6.41 (m, 1H, Cp), 6.18 (m, 1H , Cp), 6.13 (m, 1H, Cp), 6.01 (m, 1H, CH = CH2), 5.16 (m, 1H, CH = CH2), 5.11 (m, 1H, CH = CH2), 3.72 (d, J = 1, 2H, CH2), 0.62 (s, 3H, SiMe), 0.58 (s, 3H, SiMe), 0.55 (s, 3H, SiMe), 0.52 (s, 3H, SiMe).

Synthesis of MET2: A solution of indene (10.0 mL, 86.1 mmol) in Et20 (200 mL) was prepared and cooled in acetone / dry ice. A solution of n-BuLi (34.5 mL, 2.5 M, 86 mmol) was added by syringe for 3 min. The bath was stirred and the mixture was stirred for 4 hr, and then cooled again on dry ice / acetone, pure l-bromo-3-phenylpropane (13.1 mL, 86.1 mmol) was added by syringe for 1 min and the mixture stirred it was slowly heated from the bath at about 22 ° C overnight. The mixture was quenched slowly with water (5 mL) and then additional water (50 mL) was added. The biphasic mixture was shaken, the organic layer was separated, dried over MgSO 4, filtered and evaporated under vacuum to obtain (3-phenylpropyl) -β-indene as a yellow oil (18.61 g, 95 mol% pure with base in the GC analysis). GC-MS: miz, 234 (M +). A solution of (3-phenylpropyl) -lH-indene (3.00 g, 12.8 mmol) in Et20 (50 mL) was prepared and cooled in an ice water bath. A solution of n-BuLi (5.1 mL, 2.5 M, 13 mmol) was added by syringe for 30 sec, the bath was removed and the mixture was stirred for 1.5 hr. A solution of Me4Si2Cl2 (4.92 g, 26.2 mmol) in Et20 (25 mL) was prepared and the Li (indenyl) solution was added by drip by cannula to the stirred silane solution at approximately 22 ° C for 1 hr. The mixture was stirred overnight, and then evaporated and dried under vacuum for 4 hr to obtain a yellow oil. THF (50 mL) was added per cannula and a solution of Cyclopentadienyl-MgCl (14.0 mL, 1.0 M in THF, 14 mmol) was added to the stirred solution by syringe for 5 min. The mixture was stirred overnight, evaporated under vacuum, triturated with toluene (20 mL), allowed to settle, and the supernatant was decanted. The trituration procedure was repeated and the toluene solutions were combined and evaporated under vacuum to obtain an orange oil (4.11 g). Et20 (75 mL) was added per cannula, and the resulting mixture was cooled in an ice bath. A solution of n-BuLi (8.1 mL, 2.5 M in hexanes, 20 mmol) was added by syringe for 1 min to obtain a fine suspension. The bath was removed and the stirred suspension was heated to about 22 ° C for 2 hr. THF (1.6 mL) was added per syringe. A suspension of ZrCl4 (2.37 g, 10.2 mmol) in heptane (75 mL) was prepared and cooled in an ice water bath. The lithium solution was added by drip by cannula to the stirred zirconium suspension for 20 min, and the mixture was heated to about 22 ° C overnight. The volatiles were removed under vacuum and CH2Cl2 (100 mL) was added per cannula. The suspension was filtered through a pad of Celite and the Celite was washed with CH2C12 (2 x 20 mL). The filtrate and the washings were combined and evaporated under vacuum to obtain a dark yellow solid (5.79 g). The residue was triturated in 1/1 toluene / heptane (20 mL) in storage at -30 ° C to precipitate the impurities. The supernatant was decanted and it was evaporated under vacuum, and the grinding procedure was repeated. The supernatant was decanted and evaporated to obtain MET2 as an orange oil (3.03 g).

Synthesis of MET3: Portions of the following synthesis procedure were based on a method described in the Journal of Organometallic Chemistry, 1999, 585, 18-25, the disclosure of which is hereby incorporated by reference in its entirety. A solution of indene (95 mole percent purity, 10 mL, 81.8 mmol) in Et20 (200 mL) was prepared, cooled in acetone / dry ice, and charged with a solution of n-BuLi (33 mL, 2.5 M in hexanes, 83 mmol) per syringe for 1 min. The solution was stirred and allowed to slowly warm to about 22 ° C for 16 hr. A separate solution of 1,2-dichloro-1,2,2-tetramethyldisilane (7.54 g, 40.3 mmol) in Et20 (100 mL) was prepared and cooled in ice water. The prepared solution of Li-Ind was added by drip by cannula to the disilane solution for 1 hr. The resulting yellow-pale suspension was stirred and heated slowly to about 22 ° C for 16 hr. The solution was evaporated under vacuum resulting in a beige solid. Toluene (75 mL) was added per cannula and the resulting suspension was centrifuged. The supernatant solution was removed by cannula, and this toluene extraction procedure was repeated to produce two toluene extracts. The two extracts were combined and evaporated to a volume of approximately 75 mL. The resulting suspension was heated to 40 ° C in a hot water bath, and stirred to dissolve the precipitated solid. Agitation was stopped after complete dissolution of the solid, and then the solution was allowed to cool slowly to about 22 ° C for about 16 hours. The solution of the supernatant was decanted by cannula and the resulting precipitate was dried under vacuum to obtain rac / meso-1 r 2-bis (inden-l-yl) -1, 1,2, 2-tetramethyldisilane as a crystalline solid, amber (5.55 g). The supernatant solution was concentrated and a recrystallization procedure analogous to the previous one was repeated twice to obtain two additional amounts of the bridged ligand rae / meso (2.83 g and 1.52 g, respectively) exhibiting NMR purity comparable to that of the former. The total yield isolated from rac / meso-1,2-bis (inden-1-yl) -1,1,2,2-tetramethyldisilane was 9.90 g, 71%. The 1H NMR data indicate the presence of a 2/1 mixture of diastereomers, none of which could be unambiguously characterized as rae or meso due to the presence of elements of symmetry in both cases. Key data of "" "H NMR for the major isomer (CDC13): d 6.28 (dd, J = 5, 2; 2H, C5-Ind), 3.16 (s, 2H, C5-Ind), -0.18 (s, 6H, SiMe2), -0.30 (s, 6H, SiMe2) .Key data of 1H NMR for the minor isomer (CDCI3): d 6.42 (dd, J = 5, 2; 2H, C5-Ind), 3.27 (s, 2H, C5-Ind), -0.10 (s, 6H, SiMe2), -0.45 (s, 6H, SiMe2). A solution of rac / meso-1,2-bis (inden-1-yl) -1,1,2,2-tetramethyldisilane (2.82 g, 8.14 mmol) in Et20 (75 mL) was prepared, cooled to -5 ° C, and loaded with a solution of n-BuLi (6.7 mL, 2.5 M in hexanes, 17 mmol) per syringe for 30 sec. The mixture was stirred for 10 min, and then allowed to warm to about 22 ° C for 16 hr while stirring. A suspension of ZrCl4 (1.90 g, 8.14 mmol) in toluene (50 mL) was prepared and cooled to -5 ° C. The lithiated solution of bis (indenido) obtained from the bridged ligand rae / meso was added to the stirred suspension of zirconium by cannula for 30 sec. The cooling bath was removed and the resulting yellow suspension was stirred and heated to about 22 ° C for 16 hr. The yellow suspension was evaporated under vacuum and toluene (50 mL) was added by cannula. The suspension was centrifuged, and the supernatant solution was removed by cannula and evaporated under vacuum at 40 ° C to obtain rac / meso-MET3 (1: 1 rae / meso) as a yellow solid. The solid was recrystallized twice from toluene to obtain pure meso-MET3. The NMR data for these samples in the CDC13 solution matched those reported in the Journal of Organometallic Chemistry, 1999, 585, 18-25, for the MET3 compound.

Polymerization Experiments: The polymerization conditions and resultant polymeric properties for Examples 1-99 are summarized in Table I. Any listing of MET3 in Table I means to indicate the meso isomer of MET3, that is, meso-MET3. The H2 fed in Ethylene is listed in ppm on a weight basis (pppm). Applicants believe that a quality problem with the co-catalyst batch used in Examples 91-93 may have adversely affected the catalyst activity and the polymeric properties of these examples.

Figure 4 illustrates the molecular weight distributions of the polymers of Examples 3, 5, and 7. For the copolymers of these examples, Figure 4 demonstrates that the Pm was substantially constant over a range of amounts of added hydrogen.

Figure 5 illustrates the molecular weight distributions of the polymers of Examples 2, 6, and 15. For the homopolymers of these examples, Figure 5 demonstrates that the Pm decreased as the amount of added hydrogen is increased.

Figure 6 illustrates the molecular weight distributions of the polymers of Examples 2-3 and 16. For the polymers of these examples, Figure 6 demonstrates that the Pm / Nm increases as the comonomer content increases, in the absence of added hydrogen.

Figure 7 illustrates the molecular weight distributions of the polymers of Examples 6-7 and 44-45 to 250 ppm of added hydrogen. Figure 7 shows that the Pm and the Pm / Nm of the copolymers were significantly higher than those of the homopolymer.

Figure 8 illustrates the radius of gyration against the logarithm of the molecular weight for a linear standard and the polymers of Examples 2-3 and 6-7, with data from SEC-MALS. Figure 8 demonstrates that these polymers were substantially linear polymers with minimal amounts of LCB (long chain branches).

Figure 9 illustrates the Delta versus log G * (complex module) for the polymers of Examples 2-3 and 6-7. Similar to Figure 8, the rheology data in Figure 9 demonstrate that these polymers were substantially linear.

Figure 10 illustrates the catalytic activity against the initial concentration of 1-hexene comonomer for Examples 2-7 and 40-45 at varying amounts of added hydrogen. Figure 10 demonstrates that the catalyst activities for these examples were substantially constant at a given comonomer concentration, even when the hydrogen is added. Additionally, Figure 10 demonstrates that the catalyst activity in general decreases as the comonomer content increases.

Figure 11 illustrates traces of first-order models of catalytic activity against concentration Initial Hexene Comonomer for Examples 2-7 and 40-45. Figure 11 demonstrates that the catalytic activities (abbreviated A) of these examples varied uniformly with the concentration of comonomer (1-hexene) at a given hydrogen content, following the exponential profile of first order below (ec.l), where k is the inclination.

Figure 12 illustrates plots of the logarithm of the melt index against the logarithm of the hydrogen feed concentration (hydrogen / ethylene) for the polymers of Examples 4-5, 7, and 17-24. Figure 12 demonstrates the difference in hydrogen response when a copolymer is being produced compared to when a homopolymer is being produced.

Figure 13 illustrates a trace of the high load melt index against the melt index for the polymers of Examples 4 and 17-24. Figure 13 demonstrates that the cut-off ratio (HLMI / MI) was substantially constant across a range of hydrogen concentrations under homopolymer conditions.

Figure 14 illustrates a plot of zero shear viscosity versus weight average molecular weight, specifically, loq. { ? o) against the log (Pm), for polymers of Examples 2-3, 5-7, 18, 44-45, and 66-67. Figure 14 demonstrates the low levels of long chain branches (LCB) attributable to this invention. Linear polyethylene polymers are observed to follow an energy law relationship between their zero shear viscosity,,, and their weight average molecular weight, Pm, with an energy very close to 3.4. This relationship is shown by a straight line with an inclination of 3.4 when the logarithm of ?? it is plotted against the logarithm of the Pm (linear PE labeled in Figure 14). Deviations from this linear polymer line are generally accepted to be caused by the presence of LCB. Janzen and Colby present a model that predicts the expected deviation from the linear trace of log (o) against log (Pm) for given quantities of LCB content as a function of the polymer's Pm. See "Diagnosing long-chain branching in polyethylenes," J. Mol. Struct. 485-486, 569-584 (1999), which is incorporated by reference in its entirety. The polymers of Examples 2-3, 5-7, 18, 44-45, and 66-67 deviate only slightly from the 3.4 well-known energy laws "Arnett line" which are used as an indication of a linear polymer (J. Phys. Chem. 1980, 84, 649). All these polymers have LCB levels at or below the line representing 1 x 10"° LCB per carbon atom, which is equivalent to 0.001 LCB per 1000 total carbon atoms.

Table I. Polymerization Conditions and Polymeric Properties for Examples 1-99.

Table I. Polymerization Conditions and Polymeric Properties for Examples 1-99. 5 10 Table I. Polymerization Conditions and Polymeric Properties for Examples 1-99. 5 10 Table I. Polymerization Conditions and Polymeric Properties for Examples 1-99.

Table I Polymerization Conditions and Polymeric Properties for Examples 1-99 (continued). 5 10 Table I. Polymerization Conditions and Polymeric Properties for Examples 1-99 (continuation) .

Table I Polymerization Conditions and Polymeric Properties for Examples 1-9 (continuation) .

Table I Polymerization Conditions and Polymeric Properties for Examples 1-99 (continued).

EXAMPLES 100-102 Polymers produced using a dual catalyst system containing an ansa-metallocene having a formula (I) and a second metallocene The ansa-metallocene having the formula (I) used in these examples was METI, and the second metallocene was MET; following their respective structures and abbreviations: METI MET A The polymerization conditions and the properties of the resulting polymer for Examples 100-102 are summarized in Table II. The ¾ fed in Ethylene is listed in ppm on a weight basis (pppm). The catalyst components were previously contacted for 5 min prior to polymerization. The catalyst activity listed in Table II is based on either the weight of ACT1 or the total moles of METI and MET A.

Figure 15 illustrates the molecular weight distributions of the polymers of Examples 100-102. For the copolymers of these examples, Table II and Figure 15 demonstrate, unexpectedly, that the molecular weight distribution narrows (e.g., the Pm / Nm ratio decreases) as the amount of added hydrogen increases.

Table II. Polymerization Conditions and Polymeric Properties for the Examples 5 Table II. (continuation) 10 fifteen CONSTRUCTION EXAMPLES 103-105 Constructive polymerization process for producing a polymer having a conventional comonomer distribution using a dual catalyst system containing an ansa-metallocene having the formula (I) and a second metallocene Constructive Example 103 uses the following metallocene compounds in a dual catalyst system: MET2 MET B Constructive Example 105 uses the following metallocene compounds in a catalyst system du MET3 MET C A stirred stainless steel polymerization reactor of 3.78 liters (one gallon) can be used for Construction Examples 103-105. The catalyst composition may contain about 3 mg of the disilyl metallocene (METI, MET2, or MET3); about 1 mg of the second metallocene (MET A, MET B, or MET C) which can incorporate comonomer more effectively than the disilyl metallocene; about 150 mg of a support activator such as ACT1 (alternatively, it can be ACT2 or ACT3); and about 0.5 mL of a 1M heptane solution of a trialkylaluminium, for example, TIBA. The catalyst components are fed into the reactor via a charging port against a slow flow of isobutane vapor. The reactor is sealed, followed by the addition of 2L of liquid isobutane. The contents of the reactor are stirred and heated to a polymerization temperature of about 90 ° C. Prior to reaching the temperature of polymerization, ethylene is charged to the reactor to achieve the desired reactor pressure of 390 psig, along with 30 g of 1-hexene comonomer. The ethylene can be fed on demand as the polymerization reaction proceeds in order to keep the reactor pressure constant. Hydrogen is introduced into the reactor by dilution in the ethylene feed stream at a feed concentration of about 1000 pppm (alternatively, it may be in another dilution level in the range of 750 pppm to 1250 pppm). The polymerization reaction can be conducted for 60 min. After completion of the polymerization experiment, the reactor is vented, then the reactor is opened and cooled, and the polymer product is collected and dried.

Measurement of the comonomer or SCBD distribution of the polymer product of Constructive Examples 103-105 by SEC-FTIR will reveal that the total short chain branching content decreases with increasing molecular weight, for example, the number of SCB per 1000 atoms Total carbon is greater than Nm than Pm.

Claims (20)

CLAIMS Having described the invention as above, the content of the following is claimed as property.

1. An olefin polymerization process, characterized in that the process comprises: contacting a catalyst composition with an olefin monomer and optionally an olefin monomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises: (i) an ansa-metallocene compound having the formula (I): E (CpARAm) (CpBRBn) MXq (I), where: M is Ti, Zr, Hf, Cr, Se, Y, La, or a lanthanide; CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group; each RA and RB independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxy group having up to 18 carbon atoms; E is a bridged chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium or tin atoms, wherein any substituent on independently bridged chain atoms is H or a hydrocarbyl group having up to 18 carbon atoms; each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; m is 0, 1, 2, 3, or 4; n is 0, 1, 2, 3, or 4; q is 2 when M is Ti, Zr, or Hf; Y q is 1 when M is Cr, Se, Y, La, or a lanthanide; (ii) a second metallocene compound; Y (iii) an activator.

2. The process according to claim 1, characterized in that the process is conducted in the presence of added hydrogen, and a ratio of Pm / Nm of the olefin polymer decreases as the amount of added hydrogen is increased from about 100 to about 500 ppm.

3. The process according to claim 2, characterized in that the process is conducted in the presence of an olefin monomer at a molar ratio of olefin comonomer to olefin monomer in a range of about 0.01: 1 to about 0.25: 1.

4. The process in accordance with the claim 1, characterized in that the process is conducted in the presence of added hydrogen, and a ratio of Pm / Nm of an olefin polymer produced by the process in the presence of 350 ppm of added hydrogen is less than a ratio of Pm / Nm of an olefin polymer produced by the process under the same polymerization conditions in the presence of 150 ppm of added hydrogen.

5. The process according to claim 1, characterized in that: a Pm of a high molecular weight component of the olefin polymer is reduced by the addition of hydrogen; or a Pm of a low molecular weight component of the olefin polymer is not reduced by the addition of hydrogen; or the olefin polymer has less than about 0.002 long chain branches per 1000 total carbon atoms; or the olefin polymer has an average from 0 to about 5 short chain branches per 1000 total carbon atoms; or the olefin polymer has a density greater than about 0.91 g / cm 3; or any combination of them.

6. The process in accordance with the Claim 1, characterized in that: M is Ti, Zr, or Hf; each RA and RB independently is H or a hydrocarbyl group having up to 12 carbon atoms; E is a bridged chain of 3 to 6 carbon atoms or 2 to 4 silicon atoms, wherein any substituent on independently bridged chain atoms is H or a hydrocarbyl group having up to 12 carbon atoms; each X independently is F, Cl, Br, I, methyl, benzyl, or phenyl; m is 0, 1, or 2; n is 0, 1, or 2; Y What is 2?

7. The process according to claim 6, characterized in that: M is Zr or Hf; CpA and CpB independently are a cyclopentadienyl or indenyl group; each RA and RB independently is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl; Y E is -SiMe2-SiMe2-.

8. The process according to claim 1, characterized in that the ansametallocene compound having the formula (I) comprises: or a combination thereof.

9. The process according to claim 1, characterized in that the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

10. The process according to claim 1, characterized in that the activator comprises an activator of support, and wherein the support activator comprises a solid oxide treated with an electron attractant anion.

11. The process according to claim 10, characterized in that the support activator comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, silica-brominated alumina, silica-sulfated alumina, silica- fluorinated zirconia, silica-chlorinated zirconia, silica-brominated zirconia, silica-sulfated zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, coated silica-sulfated alumina, phosphatized silica-coated alumina, or any combination thereof.

12. The process according to claim 11, characterized in that the catalyst composition further comprises an organoaluminum compound, and wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n -hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.

13. The process according to claim 1, characterized in that the second metallocene compound comprises a non-bridged metallocene compound, a bridged metallocene compound, a compound of dinuclear metallocene, or a combination thereof.

14. The process according to claim 1, characterized in that the process is conducted in a batch reactor, suspension reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, or a combination thereof.

15. The process according to claim 1, characterized in that the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

16. An olefin polymerization process, characterized in that the process comprises: contacting a catalyst composition with an olefin monomer and an olefin monomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises: (i) an ansa-metallocene compound having the formula (I): E (CpARAm) (CpBRBn) MXq (I), where: M is Ti, Zr, Hf, Cr, Se, Y, La, or a lanthanide; CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group; each RA and RB independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxy group having up to 18 carbon atoms; E is a bridged chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium or tin atoms, wherein any substituent on independently bridged chain atoms is H or a hydrocarbyl group having up to 18 carbon atoms; each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; m is 0, 1, 2, 3, or 4; n is 0, 1, 2, 3, or 4; q is 2 when M is Ti, Zr, or Hf; Y q is 1 when M is Cr, Se, Y, La, or a lanthanide; (ii) a second metallocene compound; Y (i) an activator; wherein the olefin polymer has a conventional comonomer distribution.

17. The process according to claim 16, characterized in that: M is Zr or Hf; CpA and CpB independently are a cyclopentadienyl or indenyl group; each RA and RB independently is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl; E is -SiMe2-SiMe2-; each X independently is F, Cl, Br, I, methyl, benzyl, or phenyl; m is O, 1, or 2; n is 0, 1, or 2; q is 2; the activator comprises a support activator comprising a solid oxide treated with an electron attractant anion; the process is conducted in the presence of added hydrogen; Y The olefin polymer has: a bimodal molecular weight distribution; or less than about 0.002 long chain branches per 1000 total carbon atoms; or an average of about 0.5 to about 5 short chain branches per 1000 total carbon atoms; or a density greater than about 0.91 g / cm 3; or any combination thereof.

18. The process according to claim 17, characterized in that the catalyst composition further comprises an organoaluminum compound, and wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n -hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof; Y the support activator comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica-sulfated alumina, silica-fluorinated zirconia, silica-chlorinated zirconia, silica-zirconia brominated, silica-sulfated zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, coated silica-sulfated alumina, phosphatized silica-coated alumina, or any combination thereof.

19. The process according to claim 18, characterized in that the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

20. A catalyst composition characterized in that it comprises: (i) an ansa-metallocene compound having the formula (I): E (CpAR) (CpBRBn) MXq (I), where: M is Ti, Zr, Hf, Cr, Se, Y, La, or a lanthanide; CpA and CpB independently are a cyclopentadienyl, indenyl, or fluorenyl group; each RA and RB independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxy group having up to 18 carbon atoms; E is a bridged chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium or tin atoms, wherein any substituent on independently bridged chain atoms is H or a hydrocarbyl group having up to 18 carbon atoms; each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or S03R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which has up to 18 carbon atoms; m is 0, 1, 2, 3, or 4; q is 2 when M is Ti, Zr, or Hf; Y q is 1 when M is Cr, Se, Y, La, or a lanthanide; (ii) a second metallocene compound; Y (iii) an activator.