composition of bridged metallocene catalyst with exchangeable hydrogen and comonomer effects

专利摘要:
METALOCHENE CATALYST SYSTEM CONNECTED TO BRIDGE WITH EXCHANGEABLE HYDROGEN AND COMONOMER EFFECTS. The present invention provides polymerization processes using a loop-metallocene catalyst system for the production of olefin polymers. Polymers produced from the polymerization processes have properties that vary based on the presence or absence of hydrogen and / or chromonomer in the polymerization process.
公开号:BR112013008476B1
申请号:R112013008476-6
申请日:2011-10-06
公开日:2020-11-03
发明作者:Richard M. Buck；Qing Yang；Albert P. Masino；Christopher E. Wittner
申请人:Chevron Phillips Chemical Company Lp.；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
The present invention generally relates to the field of olefin polymerization catalysis, metallocene catalyst compositions, methods for the polymerization and copolymerization of olefins, and polyolefins. SUMMARY OF THE INVENTION
Polymerization processes using bridged metallocene catalyst systems for the production of olefin polymers are described here. The olefin polymers produced from the described polymerization processes demonstrate properties based on the presence or absence of hydrogen and / or comonomer in the polymerization process.
According to an aspect of the present invention, a catalyst composition is provided, and that catalyst composition comprises a loop-metallocene compound and an activator or a support-activator. In another aspect, an olefin polymerization process is provided and, in that aspect, the process comprises contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, in which the The catalyst composition comprises a loop-metallocene compound and an activator or a support-activator.
In these catalyst compositions and polymerization processes, the loop-metallocene compound has formula (I): E (CpARAm) (CpBRBn) MXq; where: M is Ti, Zr, Hf, Cr, Sc, 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, hydrocarbilasilyl, hydrocarbilamino or hydrocarbyloxide group having up to 18 carbon atoms; E is a bridging chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium or tin atoms, where any substituents on atoms in the bridging chain independently are H or a hydrocarbyl group having up to 18 atoms of carbon; each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 OR SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbilamino group, or a hydrocarbilylyl group, any of which having 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; and q is 1 when M is Cr, Sc, Y, La or a lanthanide.
Polymers produced from the polymerization of olefins using these bridged metallocene catalyst systems, resulting in homopolymers, copolymers and the like, can be used to produce various articles of manufacture. BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 presents a graph of the molecular weight distributions of the polymers of Examples 3, 5 and 7.
FIG. 2 presents a graph of the molecular weight distributions of the polymers of Examples 2, 6 and 15.
FIG. 3 presents a graph of the molecular weight distributions of the polymers of Examples 2, 3 and 16.
FIG. 4 presents a graph of the molecular weight distributions of the polymers of Examples 6-7 and 44-45.
FIG. 5 presents a graph of the turning radius versus the logarithm of molecular weight for a linear pattern and the polymers of Examples 2-3 and 6-7.
FIG. 6 shows a graph of Delta versus the log G * (complex module) for the polymers of Examples 2-3 and 6-7.
FIG. 7 presents a graph of catalyst activity versus initial 1-hexene comonomer concentration for Examples 2-7 and 40-45.
FIG. 8 presents a graph of first-order catalyst activity models versus the initial 1-hexene comonomer concentration for Examples 2-7 and 40-45.
FIG. 9 presents a graph of the fusion index logarithm versus hydrogen feed concentration for the polymers of Examples 4-5, 7 and 17-24.
FIG. 10 presents a graph of the high charge melt index versus the melt index for the polymers of Examples 4 and 17-24.
FIG. 11 presents a graph of zero shear viscosity versus average weight molecular weight, specifically, log (7o) versus log (Mw), for the polymers of Examples 2-3, 5-7, 18, 44-45 and 66-67. DEFINITIONS
In order to define more clearly the terms used here, the following definitions are provided. To the extent that any definition or use provided by any document incorporated herein by reference conflicts with the definition or use provided here, the definition or use provided here prevails.
The term "polymer" is used generically here to include olefin homopolymers, copolymers, terpolymers, and so on. A copolymer is derived from an olefin monomer and an olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Accordingly, "polymer" encompasses copolymers, terpolymers, etc., derived from any olefin monomer and comonomer (s) described herein. Similarly, an ethylene polymer would 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 were ethylene and 1-hexene, respectively, the resulting polymer would be categorized as an ethylene / 1-hexene copolymer.
Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process would involve contacting an olefin monomer (for example, ethylene) and an olefin comonomer (for example, 1-hexene) to produce a copolymer.
Hydrogen in this description can refer to hydrogen (H2), which is used in a polymerization process, or a hydrogen atom (H), which can be present, for example, in a metallocene compound. When used to denote a hydrogen atom, hydrogen will be displayed as "H", whereas if the intention is to describe the use of hydrogen in a polymerization process, it will simply be referred to as "hydrogen".
The term "co-catalyst" is generally used here to refer to organoaluminium compounds that can form a component of a catalyst composition. In addition, "co-catalyst" can refer to other components of a catalyst composition including, but not limited to, aluminoxanes, organoboro or organoborate compounds and ionizing ion compounds, as described here, when used in addition to a support -activator. The term "co-catalyst" is used regardless of the compound's current function or any chemical mechanism through which the compound can function. In one aspect of this invention, the term "co-catalyst" is used to distinguish that component of the catalyst composition from the metallocene compound (s).
The terms "chemically treated solid oxide", "support-activator", "treated solid oxide compound" and the like, are used here to indicate a relatively high porosity solid inorganic oxide, which may exhibit Lewis acid or Bronsted acid behavior , which has been treated with an electron-withdrawing component, typically an anion, and which is calcined. The electron withdrawing component is typically an electron withdrawing anion source compound. Thus, the chemically treated solid oxide may comprise a calcined contact product of at least one solid oxide with at least one electron-withdrawing anion source compound. Typically, the chemically treated solid oxide comprises at least one acid solid oxide compound. The terms "support" and "support-activator" are not used to indicate that these components are inert, and such components should not be interpreted as an inert component of the catalyst composition. The support-activator of the present invention can be a chemically treated solid oxide. The term "activator", as used here, generally refers to a substance that is capable of converting a metallocene component into a catalyst that can polymerize olefins, or convert a contact product from a metallocene component and a component that provides an activable binder (for example, an alkyl, a hydride) to the metallocene, when the metallocene compound no longer comprises such a binder, for a catalyst that can polymerize olefins. This term is used regardless of the current activation mechanism. Illustrative activators include support-activators, aluminoxanes, organoboro or organoborate compounds, ionizing ion compounds and the like. Aluminoxanes, organoboro or organoborate compounds and ionizing ion compounds are generally referred to as activators if used in a catalyst composition in which a support-activator is not present. If the catalyst composition contains an activator support, then aluminoxane, organoboro or organoborate, and ionizing ionization materials are typically referred to as co-catalysts.
The term “fluoro-organoboro compound” is used here with its common meaning to refer to neutral compounds of the BY3 form. The term "fluorine-organoborate compound" also has its usual meaning to refer to the monoanionic salts of a fluorine-organoboro compound of the form [cation] + [BY4] ’, where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as "organoboro or organoborate compounds".
The term "metallocene", as used herein, describes a compound comprising at least a fraction of the type η3 to η5-cycloalkadienyl, wherein fractions η3 to η5-cycloalkadienyl include cyclopentadienyl binders, indenyl binders, fluorenil binders and the like, including substituted or partially saturated analogues or derivatives of any of these. Possible substituents on such binders may include H, so this invention comprises partially saturated binders, such as tetrahydroindenyl, tetrahydrofluorenyl, octahidrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl and the like. In some contexts, metallocene is referred to simply as the "catalyst", in the same way that the term "co-catalyst" is used here to refer to, for example, an organoaluminium compound. Metallocene is also used generically here to encompass dinuclear metallocene compounds, that is, compounds comprising two linked metallocene fractions or a connecting group, such as an alkenyl group resulting from an olefin metathesis reaction or a saturated version resulting from hydrogenation or derivatization.
The terms "catalyst composition", "catalyst mixture", "catalyst system" and the like, do not depend on the current product or composition resulting from the contact or reaction of the initial components of the claimed composition / system / catalyst mixture, the nature of the active catalytic site, or the destination of the co-catalyst, the metallocene compound (s), any olefin monomer used to prepare a pre-contacted mixture, or the activator (for example, 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 (any) product (s) that may result from the contact of these components initial starting points, and this is inclusive of both homogeneous and heterogeneous catalyst systems or compositions.
The term "contact product" is used here to describe compositions in which the components are contacted together in any order, in any way, and for any period of time. For example, components can be contacted by combining or mixing. In addition, the contactor of any component can occur in the presence or absence of any other component of the compositions described here. The combination of additional materials or components can be carried out using any suitable method. In addition, the term “contact product” includes mixtures, combinations, solutions, sludge, reaction products and the like, or combinations thereof. Although "contact product" may include reaction products, the respective components are not required to react with each other. Similarly, the term “contact” is used here to refer to materials that can be combined, mixed, made into sludge, dissolved, reacted, treated, or contacted in some other way.
The term "pre-contacted" mixture is used here to describe a first mixture of catalyst components that are contacted for a first period of time before the first mixture is used to form a "post-contacted" mixture or second mixture of catalyst components. catalyst that are contacted during a second period of time. Typically, the pre-contacted mixture describes a mixture of metallocene compound (one or more than one), olefin monomer (or monomers), and organoaluminum compound (or compounds), before that mixture is contacted with an activator support ( s) and optional additional organoaluminium compound. Thus, pre-contacted describes components that are used to contact each other, but before contacting the components in the second, post-contacted mixture. Consequently, this invention can occasionally distinguish between a component used to prepare the pre-contacted mixture and that component after the mixture has been prepared. For example, according to this description, it is possible that the pre-contacted organoaluminium compound, once it is contacted with the metallocene compound and the olefin monomer, has reacted to form at least one different chemical compound, formulation or structure from the distinct organoaluminium compound used to prepare the pre-contacted mixture. In that case, the pre-contacted organoaluminium component or compound is described as comprising an organoaluminium compound that was used to prepare the pre-contacted mixture.
In addition, the pre-contacted mixture may describe a mixture of metallocene compound (s) and organoaluminium compound (s), before contacting that mixture with an activator support (s). This pre-contacted mixture may also describe a mixture of metallocene compound (s), olefin monomer (s), and support-activator (s), before that mixture is contacted with an organoaluminium co-catalyst compound or compounds .
Similarly, the term "post-contacted" mixture is used here to describe a second mixture of catalyst components that are contacted during a second period of time, and a constituent of which is the "pre-contacted" mixture or first mixture of catalyst components that were contacted during a first period of time. Typically, the term “post-contacted” mixture is used here to describe the mixture of metallocene compound (s), olefin monomer (s), organoaluminium compound (s) and activator support (s) formed from the contact of the pre-contacted mixture of a portion of these components with any additional components added to make up the post-contacted mixture. Often, the support-activator comprises a chemically treated solid oxide. For example, the additional component added to make up the post-contacted mixture can be a chemically treated solid oxide (one or more than one), and optionally, it can include an organoaluminium compound that is the same or different from the organoaluminium compound used for prepare the pre-contacted mixture as described here. Consequently, this invention can also occasionally be distinguished between a component used to prepare the post-contacted mixture and that component after the mixture has been prepared.
While any 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 described here.
All publications and patents mentioned here are incorporated by reference for the purpose of describing, for example, the constructs and methodologies that are described in the publications, which can be used in connection with the invention described herein. The publications discussed throughout the text are provided for your description only prior to the filing date of this application. Nothing here should be construed as an admission that inventors are not entitled to precede such a description by virtue of a previous invention.
For any particular compound described herein, any general or specific structure shown here encompasses all conformational isomers, regioisomers and stereoisomers that may arise from a particular set of substituents, unless stated otherwise. Similarly, unless stated otherwise, the general or specific structure also encompasses all enantiomers, diastereoisomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by an artisan skilled in the art .
Applicants describe several types of variations in the present invention. These include, but are not limited to, a range of number of atoms, a range of weight ratios, a range of molar ratios, a range of surface areas, a range of pore volumes, a range of catalyst activities, a temperature range, a time range, and so on. When Claimants describe or claim a range of any kind, Claimants' intention is to individually describe or claim each possible number that a range could reasonably encompass, including end points of the range, as well as any sub-ranges and combinations of sub-ranges included in them. For example, when Claimants describe or claim a chemical fraction having a certain number of carbon atoms, Claimants' intention is to individually describe or claim each possible number that such a range could encompass, consistent with that described here. For example, the description that a fraction is a Ci to Ci8 hydrocarbyl group, or, alternatively, a hydrocarbyl group having up to 18 carbon atoms, as used here, refers to a fraction that can be selected independently of a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 carbon atoms, as well as any range between those two numbers (for example, a hydrocarbyl group C-] to C8), and also including any combination of bands between those two numbers (for example, a hydrocarbyl group C2 to C4 θ C12 to Ci6).
Similarly, another representative example follows the molar ratio of olefin comonomer to olefin monomer provided in one aspect of this invention. By a description that the ratio of the comonomer.olefin monomer can be in the range of about 0.001: 1 to about 0.06: 1, Applicants intend to recite that the comonomer: monomer ratio may be about 0.001: 1, about 0.002: 1, about 0.003: 1, about 0.004: 1, about 0.005: 1, about 0.006: 1, about 0.007: 1, about 0.008: 1, about 0.009: 1, about 0.01: 1, about 0.015: 1, about 0.02: 1, about 0.025: 1, about 0.03: 1, about 0.035: 1, about 0.04: 1, about 0.045: 1, about 0.05: 1, about 0.055: 1 or about 0.06: 1. In addition, the comonomer: monomer ratio can be within any range from about 0.001: 1 to about 0.06: 1 (for example, from about 0.01: 1 to about 0.05: 1), and this also includes any combination of ranges between about 0.001: 1 and about 0.06: 1 (for example, the comonomer: monomer ratio is in a range from about 0.001: 1 to about 0.01 : 1, or from about 0.04: 1 to about 0.06: 1). Similarly, all of the other tracks described here must be interpreted in a similar way to those two examples.
Claimants reserve the right to condition or exclude any individual members of any such group, including any sub-bands or combinations of sub-bands within the group, that may be claimed under a band or in any similar manner, if at all. for whatever reason, Claimants choose to claim less than the full measure of the description, for example, on account of a reference that Claimants may be unaware of when filing the application. In addition, Claimants reserve the right to condition or exclude any substituents, analogs, compounds, binders, structures or individual groups thereof, or any members of a claimed group, if, for any reason, Claimants choose to claim less than the full measure of the description, for example, on account of a reference that Claimants may be unaware of when filing the application.
The terms "one", "one", "the", etc., are intended to include plural alternatives, for example, at least one (a), unless otherwise specified. For example, the description of "a support-activator" or "an ansa-metallocene compound" is intended to encompass one, or mixtures or combinations of more than one, support-activator or ansa-metallocene compound, respectively.
While compositions and methods are described in terms of "comprising" various components or steps, compositions and methods can also "consist essentially of" or "consist of" various components or steps. For example, a catalyst composition of the present invention can comprise; alternatively, it may consist essentially of; or alternatively, it may consist of; (i) a loop-metallocene compound and (ii) an activator. DETAILED DESCRIPTION OF THE INVENTION
The present invention is generally directed to catalyst compositions, methods for preparing catalyst compositions, methods for using catalyst compositions to polymerize olefins, polymer resins produced using such catalyst compositions, and articles produced using such polymer resins. In one aspect, the present invention relates to a catalyst composition, such a catalyst composition comprising (or consisting essentially of, or consisting of) a loop-metallocene compound and a support-activator.
In another aspect, an olefin polymerization process is provided and, in that aspect, the process comprises (or consists essentially of, or consists of) contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises (or consists essentially of, or consists of) a loop-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. A / VSA-METALOCENE COMPOUND
A catalyst composition of the present invention can comprise an activator or support-activator and a loop-metallocene compound having formula (I). Formula (I) is:
E (CpARAm) (CpBRBn) MXq; on what:
M is Ti, Zr, Hf, Cr, Sc, 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, hydrocarbilasilyl, hydrocarbilamino or hydrocarbyloxide group having up to 18 carbon atoms;
E is a bridging chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium or tin atoms, where any substituents on atoms in the bridging chain independently are H or a hydrocarbyl group having up to 18 atoms of carbon; each X independently is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbilamino group, or a hydrocarbilylyl group, any of which having 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; and q is 1 when M is Cr, Sc, Y, La or a lanthanide.
Unless otherwise specified, formula (I) above, any other structural formulas described here, and any metallocene compounds or species described here are not designed to show stereochemistry or isomeric positioning of the different fractions (for example, these formulas are not intended to show cis or trans isomers, or R or S diastereoisomers, although such compounds are contemplated and encompassed by these formulas and / or structures.
Hydrocarbyl is used here to specify a hydrocarbon radical group that includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cyclocalkenyl, cycloalkylenyl, alkynyl, aralkyl, aralkenyl, aralquinyl and the like, and includes all linear derivatives, branched, substituted, and / or unsubstituted. Unless otherwise specified, the hydrocarbyl groups of this invention typically comprise up to about 18 carbon atoms. In another aspect, hydrocarbyl 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) -O- (alkyl or aryl), and these groups can comprise up to about 18 carbon atoms. Illustrative and non-limiting examples of alkoxide and aryloxide groups (i.e., hydrocarbyloxide groups) include methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy and the like. The term hydrocarbilamino group is used here to refer collectively to an alkylamino, arylamino, dialkylamino, diarylamino, and - (alkyl or aryl) -N- (alkyl or aryl) and the like groups. Unless otherwise specified, the hydrocarbilamino groups of this invention comprise up to about 18 carbon atoms. Hydrocarbilasilyl groups include, but are not limited to, alkylsilyl groups, alkenylsilyl groups, arylsilyl groups, arylalkylsilyl groups and the like, which have up to about 18 carbon atoms. For example, illustrative hydrocarbilasilyl groups can include trimethylsilyl and phenyloctylsilyl. These hydrocarbyloxy, hydrocarbilamino, and hydrocarbilasilyl 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, alkyl groups and alkenyl groups described herein are intended to include all structural, linear or branched isomers of a given fraction; for example, all enantiomers and all diastereoisomers are included within this definition. As an example, unless otherwise specified, the term propyl is intended to include n-propyl and iso-propyl, while the term butyl is intended 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 that can be employed in the present invention include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. Illustrative examples of alkenyl groups within the scope of the present invention include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl and the like. The alkenyl group may be a terminal alkenyl group, but this is not a requirement. For example, specific alkenyl group substituents may include, but are not limited to, 3-butenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, 7-octenyl, 3-methyl-3-butenyl, 4-methyl-3 -pentenyl, 1,1-dimethyl-3-butenyl, 1,1-dimethyl-4-pentenyl and the like.
In this description, aryl is intended to include aryl and arylalkyl groups, and these include, but are not limited to, alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl, phenyl-substituted alkyl, naphthyl-substituted alkyl and the like. Therefore, non-limiting examples of such "aryl" fractions 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 fraction of substituted aryl used here is intended to include all regioisomers; for example, the term tolyl is intended to include any possible substituent position, that is, ortho, meta or para.
In formula (I), M is Ti, Zr, Hf, Cr, Sc, Y, La or a lanthanide. In one aspect of this invention, M is Ti, Zr, Hf, or Cr. In another aspect, M is Sc, Y or La. In yet another aspect, M is a lanthanide. Yet, in some other aspects described here, 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, Sc, Y, La or a lanthanide, q is 1. CpA and CpB in formula (I) can independently be a cyclopentadienyl, indenyl group 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 are independently a cyclopentadienyl or indenyl group. For example, CpA can be a cyclopentadienyl group and CpB can be an indenyl group, or both CpA and CpB can be an indenyl group.
In formula (I), each RA and RB independently can be H or a hydrocarbyl, hydrocarbilasilyl, hydrocarbilamino or hydrocarbilaoxide group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. In some other respects, each RA and RB independently can be H or an alkyl group, an alkenyl group (for example, 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. Consequently, each RA and RB can independently be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decila, ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl , tolyl or benzyl.
Each RA and RB substituent, independently, can be different. For example, CpA can have both a methyl substituent and a propenyl substituent. As another example, CpB can have two t-butyl substituents. Accordingly, a CpARA2 group can be a group with both a methyl and a propenyl substituent, while a CpBRB2 group can be a fluorenyl group with two t-butyl substituents.
In formula (I), m can be 0, 1, 2, 3 or 4, while independently n can be 0, 1,2, 3 or 4. The integers men reflect the total number of substituents in CpA and CpB, respectively (excluding the bridging group E, to be further discussed 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, no substitution other than the bridging group E.
Each X can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 OR SO3R, where R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylasilyl group. The hydrocarbyloxide group, the hydrocarbilamino group, the hydrocarbilasilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. It is contemplated that each X independently can 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 may be benzyl, phenyl or methyl. In yet another aspect, each X can be Cl; alternatively, each X may be benzyl; alternatively, each X may 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 atoms of silicon, germanium or tin. For example, E can be a bridge 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 can be a bridging chain of 2 to 8 atoms of silicon, germanium or tin, of 2 to 6 atoms of silicon, germanium or tin, of 2 to 4 atoms of silicon, germanium or tin, of 2 to 4 silicon atoms, 2 silicon atoms, 3 silicon atoms or 4 silicon atoms.
Any substituents on atoms in the bridging chain independently 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, decila, ethylenyl, 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, ally, butenyl, pentenyl, hexenyl, phenyl or benzyl. In another aspect, the substituents independently can be methyl, ethyl, propyl, butyl, ally, butenyl, pentenyl or phenyl.
According to one aspect of this invention, E is a bridging chain having the formula - (CR1OAR1OB) U—, where u is an integer from 3 to 8 (for example, 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 R1OA and R10B may independently be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl or benzyl; alternatively, H, methyl, ethyl, propyl, butyl, ally, butenyl, pentenyl, phenyl or benzyl; or alternatively, H, methyl, ethyl, propyl or butyl. In some other respects, u is 3, 4, 5 or 6, and R10A and R10B are both H, or methyl, or ethyl, or propyl, or butyl, or ally, or butenyl, or pentenyl, or phenyl or benzyl.
According to another aspect of this invention, E is a bridging chain having the formula - (SiR11AR11B) v—, where 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 may independently be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decila, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl or benzyl; alternatively, H, methyl, ethyl, propyl, butyl, ally, butenyl, pentenyl, phenyl or benzyl; or alternatively, H, methyl, ethyl, propyl or butyl. In some other respects, v is 2, 3, 4, 5 or 6 (for example, v is 2), and R11A and R11B are both H, or methyl, or ethyl, or propyl, or butyl, or ally, or butenyl , or pentenyl, or phenyl or benzyl.
It is contemplated in aspects of the invention that M in formula (I) can 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 bridge of 3 to 6 carbon atoms or 2 to 4 silicon atoms, where any substituents on atoms in the bridge chain independently can be H or a hydrocarbyl group having up to 12 atoms of carbon. In addition, each X in formula (I) can independently be F, Cl, Br, I, methyl, benzyl or phenyl; m can be 0, 1 or 2; and n can be 0, 1 or 2.
In an additional aspect, M can be Zr or Hf; each RA and RB independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyla, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl or benzyl; And it can be a bridge of 3 to 4 carbon atoms or 2 to 3 silicon atoms, where any substituents on atoms in the bridge chain independently can be H or methyl; m can be 0 or 1; and n can be 0 or 1. Furthermore, CpA and CpB independently can be a cyclopentadienyl group or an indenyl group, E can be —SiMe2 — SiMe2—, and each X can be Cl, in other aspects of this invention.
Non-limiting examples of loop-metallocene compounds having formula (I) which are suitable for use in catalyst compositions and polymerization processes described herein, whether singly or in combination, include, but are not limited to, the following compounds:

and the like, including combinations thereof.
According to another aspect of this invention, the ansa-metallocene compound having formula (I) can comprise (or consist essentially of, 5 or consist of) an ansa-metallocene compound having formula (II), or formula (III), or formula (IV), or formula (V), or formula (VI), or formula (VII), or combinations thereof:
formula (VI) formula (VII).
In formulas (II), (III), (IV), (V), (VI) and (VII), X, RA, RB, men are as described above for formula (I). In some other respects, 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, decila, ethylene, 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 "= men' + n" = n. The substituents on silicon bridge chain atoms, RE, RF, RG and RH, independently can be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Consequently, RE, RF, RG and RH can independently be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyla, octyl, nonyl, decila, ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenila, decenyl, phenyl, tolyl or benzyl; alternatively, RE, RF, RG and RH can independently be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, ally, butenyl, pentenyl, hexenyl, phenyl or benzyl; alternatively, RE, RF, RG and RH can independently be methyl, ethyl, propyl, butyl, ally, 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 may 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. According to another aspect of this invention, the ansa-metallocene compound having formula (I) can comprise (or consist essentially of, or consist of) an ansa-metallocene compound having formula (C), formula (D), formula ( E), or combinations thereof.
Formula (C) is M3 is Zr or Hf; X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 OR SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbilamino group, or a hydrocarbilylyl group, any of which having up to 18 carbon atoms; E3 is a bridging group having the formula —SiR7DR8D— SiR7ER8E—, where R7D, R8D, R7E and R8E 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; and Cp1 is a cyclopentadienyl or indenyl group, any substituent on Cp1 is H or a hydrocarbyl or hydrocarbilasilyl group having up to 18 carbon atoms.
In formula (C), M3 can be Zr or Hf, while X4 and X5 independently can be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R can be an alkyl or aryl group; or a hydrocarbyloxide group, a hydrocarbilamino group or a hydrocarbilasilyl group. The hydrocarbyloxide group, the hydrocarbilamino group, the hydrocarbilasilyl 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 are independently benzyl, phenyl or methyl. In yet 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, an X4 and X5 can be methyl.
In formula (C), E3 can be a bridging group having the formula —SiR7DR8D — SiR7ER8E—, where 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. Consequently, in aspects of this invention, R7D, R8D, R7E and R8E independently can be H or an alkyl or alkenyl group having up to 6 carbon atoms; alternatively, R7D, R8D, R7E and R8E independently can be H, methyl, ethyl, propyl, butyl, ally, butenyl or pentenyl; alternatively, R7D, R8D, R7E and R8E independently can be H, methyl or ethyl; alternatively, R7D, R8D, R7E or R8E can be H; or alternatively, R7D, R8D, R7E and R8E may be methyl. R9 and R10 in the fluorenyl group in formula (C) independently can be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Consequently, 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 other respects, 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 can be H or, alternatively, both R9 and R10 can be t-butyl.
In formula (C), Cp1 is a cyclopentadienyl or indenyl group. Often, Cp1 is a cyclopentadienyl group. Any Cp1 substituent can be H or a hydrocarbyl or hydrocarbilasilyl group having up to 18 carbon atoms; or alternatively, any substituent can be H or a hydrocarbyl or hydrocarbilasilyl group having up to 12 carbon atoms. Possible substituents on Cp1 can 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 beyond those shown in formula (C), for example, no substituents other than the E3 bridge group. In another aspect, Cp1 can 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. In yet another aspect, Cp1 may have a single H substituent, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl or octenyl.
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 has no additional substituents or Cp1 it may have a single substituent selected from H or an alkyl, alkenyl, alkylsilyl or alkenylsilyl group having up to 8 carbon atoms. In these and other respects, E3 can be a bridging group having the formula —SiR7DR8D — SiR7ER8E—, where R7D, R8D, R7E and R8E are independently H or methyl.
The formula (D) is ^ == 5 / == /; where: M4 is Zr or Hf; X6 and X7 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbilamino group, or a hydrocarbilylyl group, any of which having up to 18 carbon atoms; E4 is a bridging group having the formula —SiR12DR13D— SiR12ER13E—, where R12D, R13D, R12E and R13E are independently H or a hydrocarbyl group having up to 10 carbon atoms; and R14, R15, R16 and R17 are independently H or a hydrocarbyl group having up to 18 carbon atoms.
In formula (D), M4 can be Zr or Hf, while X6 and X7 independently can be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbyloxide group, a hydrocarbilamino group or a hydrocarbilasilyl group. The hydrocarbyloxide group, the hydrocarbilamino group, the hydrocarbilasilyl 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 are independently benzyl, phenyl or methyl. In yet another aspect, both X6 and X7 can be Cl; alternatively, both X6 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—, where 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. Consequently, in aspects of this invention, R12D, R13D, R12E and R13E independently can be H or an alkyl or alkenyl group having up to 6 carbon atoms; alternatively, R12D, R13D, R12E and R13E independently can be H, methyl, ethyl, propyl, butyl, ally, butenyl or pentenyl; alternatively, R12D, R13D, R12E and R13E independently can be H, methyl, ethyl, propyl or butyl; alternatively, R12D, R13D, R12E and R13E independently can be H, methyl or ethyl; alternatively, R12D, R13D, R12E and R13E can be H; or alternatively, R12D, R13D, R12E and R13E can be methyl. R14, R15, R16 and R17 in the fluorenyl group in formula (D) can independently be H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Consequently, R14, R15, R16 and R17 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 other respects, 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 be F, Cl, Br, I, benzyl, phenyl or methyl in formula (D), and R14, R15, R16 and R17 can independently be H or t-butyl. In these and other respects, E4 can be a bridging group having the formula —SiR12DR13D — SiR12ER13E—, where R12D, R13D, R12E and R13Es are independently H or methyl.
M5 is Zr or Hf; X8 and X9 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbilamino group, or a hydrocarbilylyl group, any of which having up to 18 carbon atoms; and E5 is a jumper 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 — SÍR20CR21C—, in which R20B, R21B, R20C and R21C are independently H or a hydrocarbyl group having up to 10 carbon atoms.
In formula (E), M5 can be Zr or Hf, while X8 and X9 independently can be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbyloxy group, a hydrocarbylamino group, or a hydrocarbylasilyl group. The hydrocarbyloxy group, the hydrocarbylamino group, the hydrocarbylasilyl 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 are independently benzyl, phenyl or methyl. In yet 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 formula (E), E5 is a bridging group. According to 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 can be 3, 4, 5 or 6 in some other aspects of this invention. According to another aspect of this invention, E5 can be a bridging group having the formula —SiR20BR21B — SÍR20CR21C—, where R20B, R21B, R20C and R21C independently can be H or a hydrocarbyl group having up to 10 carbon atoms or alternatively, up to 6 carbon atoms. Consequently, in aspects of this invention, R20B, R21B, R20C and R21C independently can be H or an alkyl or alkenyl group having up to 6 carbon atoms; alternatively, R20B, R21B, R20C and R21C independently can be H, methyl, ethyl, propyl, butyl, ally, butenyl or pentenyl; alternatively, R20B, R21B, R20C and R21C independently can be H, methyl, ethyl, propyl or butyl; alternatively, R20B, R21B, R20C and R21C independently can 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) can independently be F, Cl, Br, I, benzyl, phenyl or methyl, and in some other aspects, E5 can 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 -SiR20BR21B-SiR20CR21c-, where R20B, R21B, R20C and R21C are independently H or methyl.
Non-limiting examples of loop-metallocene compounds having formula (E) that are suitable for use here 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 described here, and any metallocene species described here are not designed to show stereochemistry or isomeric positioning of the different fractions (for example, these formulas are not intended to show cis or trans, or R or S diastereoisomers), although such compounds are contemplated and encompassed by these formulas and / or structures. ACTIVATOR SUPPORT
The present invention encompasses several catalyst compositions containing an activator, which can be a support-activator. In one aspect, the support-activator comprises a chemically treated solid oxide. Alternatively, the activator support may comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, an aluminum mineral -layered silicate, a non-layered aluminum silicate mineral or any combination thereof.
Generally, chemically treated solid oxides exhibit improved acidity compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide also functions as a catalyst activator in comparison to the corresponding untreated solid oxide. While chemically treated solid oxide activates metallocene in the absence of co-catalysts, it is not necessary to eliminate co-catalysts from the catalyst composition. The activation function of the support-activator is evident for the improved activity of the catalyst composition as a whole, compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator, even in the absence of an organoaluminium compound, aluminoxanes, organoboro or organoborate compounds, ionizing ion compounds and the like. The chemically treated solid oxide may comprise a solid oxide treated with an electron withdrawing anion. While it is not intended to stick to the following statement, it is believed that the treatment of solid oxide with an electron-withdrawing component swells or increases the acidity of the oxide. Thus, the support-activator exhibits Lewis or Bronsted acidity that is typically greater than the strong Lewis or Bronsted acid of untreated solid oxide, or the support-activator has a greater number of acid sites than untreated solid oxide. , or both. One method to quantify the acidity of chemically treated or untreated solid oxide materials is by comparing the polymerization activities of treated and untreated oxides under acid catalyzed reactions.
The chemically treated solid oxides of this invention are generally formed from an inorganic solid oxide which exhibits Lewis acid or Bronsted acid behavior and has a relatively greater porosity. Solid oxide is chemically treated with an electron-withdrawing component, typically an electron-withdrawing anion, to form a support-activator.
According to one aspect of the present invention, the solid oxide used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc / g. According to another aspect of the present invention, the solid oxide has a pore volume greater than about 0.5 cc / g. In accordance with yet another aspect of the present invention, the solid oxide has a pore volume greater than about 1.0 cc / g.
In another aspect, the solid oxide has a surface area of about 100 to about 1000 m2 / g. In yet another aspect, the solid oxide has a surface area of about 200 to about 800 m2 / g. In yet another aspect of the present invention, the solid oxide has a surface area of about 250 to about 600 m2 / g.
The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and one or more of the 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 and actinide elements (See: Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley & Sons, 1995; Cotton, FA, Wilkinson, G., Murillo, CA, and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, inorganic oxide can 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 chemically treated solid oxide include, but are not limited to, AI2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O3, Sb2O3, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2 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, boron, zinc oxide, mixed oxides thereof or any combination thereof. .
The solid oxide of this invention encompasses oxide materials, such as alumina, compounds of "mixed oxide" thereof, such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds, such as silica-alumina can be 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 activator support of the present invention include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeotides, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boron, silica-boron, 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 description of which is incorporated herein by reference in its entirety.
The electron withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Bronsted acidity of the solid oxide being treated (compared to the solid oxide that is not treated with at least one electron withdrawing anion). According to one aspect of the present invention, the electron-withdrawing component is an electron-withdrawing anion derived from a salt, acid or other compound, such as a volatile organic compound, which serves as a source or precursor to that anion. Examples of electron-withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and similar phosphor-tungstates and combinations thereof. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions can also be employed in the present invention. It is contemplated that the electron withdrawing anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate or sulfate and the like or any combination thereof, in some other aspects of this invention. In other respects, the electron withdrawing 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 (for example, chemically treated solid oxide) used in the catalyst compositions of the present invention may be, or may comprise, fluoridated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluoridated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated silica, alumina-coated sulfated, phosphate-silica-coated alumina and the like, or combinations thereof. In one aspect, the support-activator may be, or may comprise, fluoridated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-silica-coated alumina and the like or any combination thereof. In another aspect, the support-activator comprises fluorinated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, it comprises fluorinated silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, it comprises fluoridated silica-zirconia; alternatively, it comprises chlorinated silica-zirconia; or alternatively, it comprises alumina coated with fluoridated silica.
When the electron-withdrawing component comprises a salt from an electron-withdrawing anion, the counterion or cation of that salt can be selected from any cation that allows the salt to reverse or decompose back to acid during calcination. Factors that determine the suitability of the particular salt to serve as a source for the electron withdrawing anion include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse cation reactivity, ion matching effects between the cation and anion, hygroscopic properties transmitted to the salt by the cation and the like, and thermal stability of the anion. Examples of suitable cations in the electron-withdrawing anion salt include, but are not limited to, ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H +, [H (OEt2) 2] + θ.
In addition, combinations of one or more different electron-withdrawing anions, in varying proportions, can be used to obtain the specific acidity of the activator support at the desired level. Combinations of electron-withdrawing components can be contacted with the oxide material simultaneously or individually, and in any order that yields the desired acidity of the chemically treated solid oxide. For example, one aspect of this invention is the use of two or more electron-withdrawing anion source compounds in two or more separate contact steps.
Thus, an example of a process such that a chemically treated solid oxide is prepared is as follows: a selected solid oxide, or combination of solid oxides, is contacted with a first electron-withdrawing anion source compound to form a first mixture; this first mixture is calcined and then a second electron-withdrawing anion source compound is contacted to form a second mixture; the second mixture is then calcined to form a treated solid oxide. In such a process, the first and second electron-withdrawing anion source compounds can be both the same and different compounds.
According to 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-withdrawing 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 oxides that contain a metal or metal ion include, but are not limited to, alumina impregnated with chlorinated zinc, alumina impregnated with fluorinated titanium, alumina impregnated with fluorinated zinc, silica-alumina impregnated with chlorinated zinc, silica-alumina impregnated with fluorinated zinc, alumina impregnated with fluorinated zinc, chlorinated zinc aluminate, fluorinated zinc aluminate, sulfated zinc aluminate, silica coated alumina treated with hexafluorotitanic acid, silica coated alumina treated with zinc and then floured and the like or any combination thereof of the same.
Any method of impregnating the solid oxide material with a metal can be used. The method by which the oxide is contacted with a metal source, typically a metal-containing salt or compound, can include, but is not limited to, gelation, co-gelation, 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 supported metal with calcination. Consequently, the solid inorganic oxide can additionally 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 as the solid oxide is treated with the electron-withdrawing anion. Following any contact method, the contacted mixture of solid compound, electron-withdrawing anion, and the metal ion is typically calcined. Alternatively, a solid oxide material, an electron-withdrawing anion source, and the metal salt or metal-containing compound are contacted 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 oxides with one or more electron withdrawing anion sources. It is not required that the solid oxide be calcined before contacting the electron-withdrawing anion source. The contact product is typically calcined during or after the solid oxide is contacted with the electron-withdrawing anion source. The solid oxide can be calcined or not. Various processes for preparing solid oxide support-activators that can be employed in this invention have been reported. For example, such 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 and 6,632,894.
According to one aspect of the present invention, the solid oxide material is chemically treated by contacting it with an electron-withdrawing component, typically an electron-withdrawing anion source. In addition, the solid oxide material is optionally chemically treated with a metal ion, and then calcined to form a chemically treated solid oxide containing metal or impregnated with metal. According to another aspect of the present invention, the solid oxide material and the electron withdrawing anion source are contacted and calcined simultaneously.
The method by which the oxide is contacted with the electron-withdrawing component, typically an electron-withdrawing anion salt or acid, may include, but is not limited to, gelation, co-gelation, impregnation of one compound with another and the like. Thus, following any contact method, the contacted mixture of solid oxide, electron-withdrawing anion and optional metal ion, is calcined.
The solid oxide support-activator (i.e. chemically treated solid oxide) can thus be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with an electron-withdrawing anion source compound (or compounds) to form a first mixture; and 2) calcining the first mixture to form the solid oxide activator support.
According to 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 of withdrawal anion source electron to form a first mixture; 2) calcining the first mixture to produce a first calcined mixture; 3) contacting a first calcined mixture with a second electron-withdrawing anion source compound to form a second mixture; and 4) calcining the second mixture to form the solid oxide support-activator.
According to yet another aspect of the present invention, chemically treated solid oxide is produced or formed by contacting the solid oxide with the electron-withdrawing anion source compound, where the solid oxide compound is calcined before, during or after contact from the electron-withdrawing anion source, and where there is a substantial absence of aluminoxanes, organoboro or organoborate compounds, and ionizing ion compounds.
The calcination of the treated solid oxide is generally conducted in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature of about 200 ° C to about 900 ° C, and for a time of about 1 minute to about 100 ° C. hours. The calcination can be conducted at a temperature of about 300 ° C to about 800 ° C, or alternatively, at a temperature of about 400 ° C to about 700 ° C. The calcination can be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350 ° C to about 550 ° C. Any suitable ambient atmosphere can be used during calcination. Calcination is generally conducted in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.
According to one aspect of the present invention, the solid oxide material is treated with a source of halide ion, sulfate ion or a combination of anions, optionally treated with a metal ion, and then calcined to provide chemically treated solid oxide in the in the form of a particulate solid. For example, the solid oxide material can be treated with a sulfate source (called a "sulfating agent"), a chloride ion source (called a "chlorinating agent"), a fluoride ion source (called a of a “fluoridating agent”), or a combination thereof, and calcined to provide a solid oxide activator. Useful acid support-activators include, but are not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, brominated silica-zirconia, chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, hexafluorotitanic acid-treated alumina, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorzironic acid, silica-alumina treated , fluoridated boron-alumina, silica treated with tetrafluorbic acid, alumina treated with tetrafluorbic acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pillared montmorillonite, optionally treated with fluoride, chloride or sulfate; phosphate alumina or other aluminophosphates optionally treated with sulfate, fluoride or chloride; or any combination of the above. In addition, any of these support 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. Fluoridated solid oxide can be formed by contacting a solid oxide with a fluoridating agent. The fluoride ion can be added to the oxide by forming an oxide slurry in a suitable solvent, such as alcohol or water including, but not limited to, alcohols with one to three carbons due to their volatility and low surface tension . Examples of suitable fluoridating agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosylate) (( 2SiF6), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TiF6), hexafluorotitanic ammonium ((NH4) 2TiF6), hexafluorzironic acid (H2ZrF6), AIF3, NH4AIF4, combinations of the same, and the same. Triflic acid and ammonium triflate can also be used.
For example, ammonium bifluoride (NH4HF2) can be used as the fluoridating agent, due to its ease of use and availability.
If desired, the solid oxide is treated with a fluoridating agent during the calcination step. Any fluoridating agent capable of meticulously contacting the solid oxide during the calcination step can be used. For example, in addition to those fluoridating agents described above, volatile organic fluoridating agents can be used. Examples of volatile organic fluoridating 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. Calcination temperatures should generally be high enough to decompose the compound and release fluoride. Hydrogen gas fluoride (HF) or fluorine itself (F2) can also be used with solid oxide if fluoridated while calcining. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4 ') can also be used. A convenient method of contacting the solid oxide with the fluoridating agent is to vaporize a fluoridating 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 solid chloride oxide in the form of a particulate solid. Solid chloride oxide is formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide by forming an oxide slurry in a suitable solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a chloride source and meticulously contacting the oxide during the calcination step can be used, such as SiCI4, SiMe2CI2, TiCI4, BCI3 and the like, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol and the like or any combination thereof. Gaseous hydrogen chloride or chlorine itself can also be used with solid oxide during calcination. A convenient method for contacting the oxide with the chlorinating agent is to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.
The amount of fluoride or chloride ion present before calcination of the solid oxide is generally about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, for example, silica-alumina, before calcination. According to another aspect of this invention, the amount of fluoride or chloride ion present before calcination of the solid oxide is from about 1 to about 25% by weight, and according to another aspect of this invention, from about 2 to about 20% by weight. According to yet another aspect of this invention, the amount of fluoride or chloride ion present before calcination of the solid oxide is from about 4 to about 10% by weight. Once impregnated with halide, halet 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 drying step. calcination immediately without drying the impregnated solid oxide.
The silica-alumina used to prepare the treated silica-alumina typically has a pore volume greater than about 0.5 cc / g. According to one aspect of the present invention, the pore volume is greater than about 0.8 cc / g, and according to another aspect of the present invention, greater than about 1.0 cc / g. In addition, silica-alumina generally has a surface area greater than about 100 m2 / g. According to another aspect of this invention, the surface area is greater than about 250 m2 / g. In yet 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. According to one aspect of this invention, the alumina content of silica-alumina is about 5 to about 50%, or 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 range from about 60% to about 90%, or about 65% at about 80%, alumina by weight. According to yet another aspect of this invention, the solid oxide component comprises alumina without silica, and according to 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 so that the calcined sulfated oxide comprises a metal. According to one aspect of the present invention, the sulfated solid oxide comprises sulfate and alumina. In some cases, sulfated alumina is formed through a process in which the alumina is filtered with a sulfate source, for example, sulfuric acid or a sulfate salt, such as ammonium sulfate. This process is usually performed by forming an alumina slurry in a suitable solvent, such as alcohol or water, to which the desired concentration of the sulfating agent has been added. Suitable organic solvents include, but are not limited to, alcohols with one to three carbons due to their volatility or low surface tension.
According to one aspect of this invention, the amount of sulfate ion present before calcination is about 0.5 to about 100 parts by weight 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 according to yet another aspect of 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 sulfated 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 drying step. calcination immediately.
According to another aspect of the present invention, the support-activator used in the preparation of the catalyst compositions of this invention comprises an exchangeable ion support-activator, including, but not limited to, silicate and aluminum-silicate compounds or minerals, structures with or without layers, and combinations thereof. In another aspect of this invention, aluminum silicates with an exchangeable ion layer, such as pillared clays, are used as support-activators. When the acid activating support comprises an exchangeable ion activating support, it can optionally be treated with at least one electron withdrawing anion, such as those described here, although typically the exchangeable ion activating support is not treated with a withdrawing anion electron.
According to another aspect of the present invention, the support-activator of this invention comprises clay minerals having interchangeable cations and layers capable of expansion. Typical clay mineral support-activators include, but are not limited to, exchangeable ion-layer aluminum silicates 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, on the contrary, it should be considered as an active part of the catalyst composition, due to its intimate association with the component of metallocene.
In accordance with another aspect of the present invention, the clay materials of this invention encompass materials in their natural state or which have been treated with various ions through wetting, ion exchange, or pillaring. Typically, the clay material support-activator of this invention comprises clays that have been ion-exchanged with large cations, including complex cations of highly charged polynuclear metal. However, the clay material support-activators of this invention also encompass clays that have been ion-exchanged with simple salts, including, but not limited to, Al (lll), Fe (ll), Fe (lll) salts, and Zn (ll) with binders, such as halide, acetate, sulfate, nitrate or nitrite.
According to another aspect of the present invention, the support-activator comprises a pillared clay. The term “pillared clay” is used to refer to clay materials that have been ion-exchanged with complex cations of highly charged metal typically large polynuclear. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometalates, and other large ions. Thus, the term pillarization refers to a simple permutation reaction in which the exchangeable cations in a clay material are replaced by large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the clay interlayer and, when calcined, are converted into metal oxide “pillars”, effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the pillars supporting between the clay layers, the expanded truss structure is maintained and the porosity is increased. The resulting pores can vary in shape and size as a function of the pillar material and the clay base material used. Examples of pillarization and pillarized clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent No. 4,060,480; descriptions of which are incorporated herein by reference in their entirety.
The pillarization process uses clay minerals having interchangeable cations and layers capable of expansion. Any pillarized clay that can increase the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, clay minerals suitable for pillaring include, but are not limited to, allophanes; smectites, both dioctaedral (Al) and trioctaedral (Mg) and derivatives thereof, such as montmorillonites (bentonites), nontronites, hectorites or Laponites; haloisites; vermiculites; micas; fluoromics; chlorites; mixed layer clays; fibrous clays including, but not limited to, sepiolites, atapulgites and paligorschites; serpentine clay; illita; laponite; saponite; and any combination thereof. In one aspect, the pillar-clay support-activator comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
Pillarized 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 a pre-treatment is described here, it should be understood that pre-heating can be performed at many other temperatures and times, including any combination of temperature and time steps, 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, zeotides, inorganic oxides, phosphate inorganic oxides and the like. In one aspect, typical support materials that are used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boron, thorium, aluminophosphate, aluminum phosphate, silica-titania, silica / titania coprecitipated, mixtures thereof or any combination thereof.
According to another aspect of the present invention, one or more of the metallocene compounds can be pre-contacted with an olefin monomer and an organoaluminium compound for a first period of time before contacting this mixture with the activator support. Since the pre-contacted mixture of the metallocene compound (s), olefin monomer and organoaluminium compound is counted on the support-activator, the composition additionally comprising the support-activator is called a mixture “Post-contacted”. The post-contacted mixture can be allowed to remain in additional contact for a second period of time before being loaded into the reactor in which the polymerization process was carried out.
In accordance with yet another aspect of the present invention, one or more of the metallocene compounds can be pre-contacted with an olefin monomer and a support-activator for a first period of time before contacting that mixture with the organoaluminium compound. Once the pre-contacted mixture of the metallocene compound (s), olefin monomer and activator support is contacted with the organoaluminium compound, the composition additionally comprising the organoaluminium is called a “powders mixture. -contacted ”. The post-contacted mixture can be allowed to remain in additional contact for a second period of time before being introduced into the polymerization reactor. ORGANOALUMINUM COMPOUNDS
In some other aspects, the catalyst compositions of the present invention can comprise one or more organoaluminium compounds. Such compounds may include, but are not limited to, compounds having the formula:
where Rc is an aliphatic group having 1 to 10 carbon atoms. For example, Rc can be without methyl, ethyl, propyl, butyl, hexyl or isobutyl.
Other organoaluminium compounds that can be used in catalyst compositions described here may include, but are not limited to, compounds having the formula:

where XA is a hydrocarbyl; XB is an alkoxide or an aryloxide, a halide or a hydride; and p is 1 to 3, inclusive. Hydrocarbyl is used here to specify a hydrocarbon radical group and includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cyclocalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkyl and the like, and includes all substituted derivatives, unsubstituted, branched, linear and / or substituted by heteroatoms thereof.
In one aspect, XA is a hydrocarbyl having from 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.
According to one aspect of the present invention, XB is an alkoxide or an aryloxide, any of which has from 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. Yet, in another aspect, XB is chlorine.
In the formula, AI (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 an integer; therefore, this formula includes sesquihalide compounds or other organoaluminium atomic aggregate compounds.
Examples of organoaluminium compounds suitable for use in accordance with the present invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminium halide compounds, dialkylaluminium alkoxide compounds, dialkylaluminium hydride compounds and combinations thereof. Specific non-limiting examples of suitable organoalumin compounds include trimethyl aluminum (TMA), triethyl aluminum (TEA), tri-n-propyl aluminum (TNPA), tri-n-butylalumin (TNBA), triisobutylaluminum (TIBA), tri-n-hexylalumin, tri -n-octyl aluminum, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum chloride and the like, or combinations thereof.
The present invention contemplates a method of pre-contacting a metallocene compound with an organoaluminium compound and an olefin monomer to form a pre-contacted mixture, before contacting that pre-contacted mixture with an activator support to form a composition of catalyst. When the catalyst composition is prepared in this way, typically, although not necessarily, a portion of the organoaluminium compound is added to the pre-contacted mixture and another portion of the organoaluminium compound is added to the post-contacted mixture prepared when the pre-contacted mixture is contacted with the solid oxide support-activator. However, the entire organoaluminium compound can be used to prepare the catalyst composition in the pre-contact or post-contact stage. Alternatively, all catalyst components are contacted in one step.
In addition, more than one organoaluminium compound can be used in the pre-contact or post-contact stage. When an organo-aluminum compound is added in multiple steps, the amounts of organo-aluminum compound described here include the total amount of organo-aluminum compound used in both pre-contacted and post-contacted mixtures, and any additional organo-aluminum compound added to the reactor. polymerization. Therefore, total amounts of organoaluminium compounds are discussed regardless of whether a single organoaluminium compound or more than one organoaluminium compound is used. ALUMINOXAN COMPOUNDS
The present invention further provides a catalyst composition that can comprise an aluminoxane compound. As used herein, the term "aluminoxane" refers to discrete aluminoxane compounds, compositions, mixtures, or species, regardless of how such aluminoxanes are prepared, formed or otherwise provided. For example, a catalyst composition comprising an aluminoxane compound can be prepared, in which the aluminoxane is provided as the poly (hydrocarbyl aluminum oxide), or in which the aluminoxane is provided as the combination of an alkyl aluminum compound. and a source of active protons, such as water. Aluminoxanes are also referred to as poly (hydrocarbyl aluminum oxides) or organoaluminoxanes.
The other catalyst components are typically contacted with the aluminoxane in a saturated hydrocarbon compound solvent, although any solvent that is substantially inert to the reactants, intermediates and products of the activation step can be used. The catalyst composition formed in this way is collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition is introduced into the polymerization reactor without being isolated.
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. Cyclic aluminoxane compounds having the formula:
where R in that formula is straight or branched alkyl having 1 to 10 carbon atoms, and p in that formula is an integer from 3 to 20, are encompassed by this invention. The AIRO fraction shown here also constitutes the repeating unit in a linear aluminoxane. Thus, linear aluminoxane having the formula:
where R in that formula is straight or branched alkyl having 1 to 10 carbon atoms, and q in that formula is an integer from 1 to 50, are also encompassed by that invention.
In addition, aluminoxanes may have the cage structures of the formula R ^ r + αR ^ -αAUrOsr, where Rf is a terminal linear or branched alkyl group having from 1 to 10 carbon atoms; Rb is a straight or branched bridging alkyl group having 1 to 10 carbon atoms; aft 3 or 4; and α is equal to / 7AI (3) - r o <2) + now, where nAi (3) θ the number of three coordinated aluminum atoms, n0 (2) θ the number of two coordinated oxygen atoms, and now θ the number of 4 coordinated oxygen atoms.
Thus, the aluminoxanes that can be employed in the catalyst compositions of the present invention are generally represented by formulas such as (R-AI-O) P, R (R-AI-O) qAIR2 and the like. In these formulas, the group R is typically a straight or branched C 1 -C 6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples of aluminoxane compounds that can be used according to the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane isane , 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane and the like or any combination thereof. Methylaluminoxane, ethylaluminoxane and iso-butylaluminoxane are prepared from trimethylaluminum, triethylalumin or triisobutylalumin, respectively, and are sometimes referred to as poly (methyl aluminum oxide), poly (ethyl aluminum oxide) and poly (butyl oxide) aluminum), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminium, such as that described in U.S. Patent No. 4,794,096, incorporated herein by reference in its entirety.
The present invention contemplates many p and q values in the aluminoxane (R-AI-O) P and R (R-AI-O) qAIR2 formulas, respectively. In some other respects, p and q are at least 3. However, depending on how organoaluminoxane is prepared, stored and used, the value of p and q can vary within a single sample of aluminoxane, and such combinations of organoaluminoxanes are contemplated here.
In preparing 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 compound (s) in the composition is generally between about 1:10 and about 100,000 :1. In another aspect, the molar ratio is in the range of about 5: 1 to about 15,000: 1. Optionally, aluminoxane can be added to a polymerization zone in the range of about 0.01 mg / L to about 1000 mg / L, from about 0.1 mg / L to about 100 mg / L or about 1 mg / L to about 50 mg / L.
Organoaluminoxanes can be prepared through various procedures. Examples of organoaluminoxane preparations are described in U.S. Patent Nos. 3,242,099 and 4,808,561, the descriptions of which are incorporated herein by reference in their entirety. For example, water in an inert organic solvent can be reacted with an alkyl aluminum compound, such as (RC) 3AI, to form the desired organoaluminoxane compound. While this statement is not intended, it is believed that this synthetic method can yield a mixture of both linear and cyclic R-AI-0 aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes are prepared by reacting an alkyl aluminum compound, such as (RC) 3AI, with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent. ORGANOBORO / ORGANOBORATE COMPOUNDS
According to another aspect of the present invention, the catalyst composition can comprise an organoboro or organoborate compound. Such compounds include neutral boron compounds, borate salts and the like, or combinations thereof. For example, fluorine-organoboro compounds and fluorine-organoborate compounds are contemplated.
Any fluorine-organoboro or fluorine-organoborate compound can be used with the present invention. Examples of fluoroorganoborate compounds that can be used in the present invention include, but are not limited to, fluorinated aryl borates, such as N, N-dimethylaniline tretraquis- (pentafluorophenyl) borate, trichloro (pentafluorophenyl) triphenylcarbene borate, tretraquis (pentafluorophenyl) lithium borate, N, N-dimethylaniline traces [3,5-bis (trifluoromethyl) phenyl] borate, traces [3,5-bis (trifluoromethyl) phenyl] triphenylcarbene borate and the like, or mixtures thereof. Examples of fluoro-organoboro 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 of the same. While not intended to stick to the following theory, these examples of fluoroorgan borate and fluorine-organoboro compounds, and related compounds, are taught to form “poorly coordinated” anions when combined with organometal or metallocene compounds, as described in the U.S. Patent 5,919,983, the description of which is incorporated herein by reference in its entirety. Applicants also contemplate the use of diboro, or bis-boron, 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.
Generally, any amount of organoboro compound can be used. According to one aspect of this invention, the molar ratio of the total moles of organoboro or organoborate compound (or compounds) to the total moles of metallocene compound (or compounds) in the catalyst composition is in a range of about 0.1 : 1 to about 15: 1. Typically, the amount of fluorine-organoboro or fluorine-organoborate compound used is about 0.5 moles to about 10 moles of boron / borate compound per mole of metallocene compound (s). According to another aspect of this invention, the amount of fluorine-organoboro or fluorine-organoborate compound is from about 0.8 moles to about 5 moles of boron / borate compound per mole of metallocene compound (s). IONIZING IONIZING COMPOUNDS
The present invention further provides a catalyst composition that can comprise an ionizing ion compound. An ionic ionization compound is an ionic compound that can function as a co-catalyst for
increase the activity of the catalyst composition. While it is not intended to stick to the theory, it is believed that the ionizing compound is capable of reacting with a metallocene compound and converting the metallocene into one or more cationic metallocene compounds, or incipient cationic metallocene compounds. Again, while it is not intended to stick to the theory, it is believed that the ionizing compound can function as an ionizing compound by completely or partially extracting an anionic binder, possibly a non-alkadienyl binder, from the metallocene. However, the ionizing compound is an activator or co-catalyst regardless of whether it ionizes the metallocene, abstracts a ligand in a way that forms an ionic pair, weakens the metal ligand bond in the metallocene, simply coordinates with a ligand, or activates the metallocene by some other mechanism.
Furthermore, it is not necessary for the ionizing compound to activate the metallocene compound (s) only. The activation function of the ionization compound may be evident in the increased activity of the catalyst composition as a whole, compared to a catalyst composition that does not contain an ionization compound.
Examples of ionizing ionization compounds include, but are not limited to, the following compounds: tri (n-butyl) ammonium trichlor (p-tolyl) borate, tri (n-butyl) ammonium trichlor (m-tolyl) borate, tri ( n-butyl) ammonium traces (2,4-dimethylphenyl) - borate, tri (n-butyl) ammonium traces (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium traces [3,5-bis (trifluoromethyl) phenyl] borate, tri (n-butyl) ammonium traces (pentafluorophenyl) borate, N, N-dimethylaniline traces (p-tolyl) borate, N, N-dimethylaniline traces (m-tolyl) borate, N, N-dimethylaniline traces ( 2,4-dimethylphenyl) borate, N, N-dimethylaniline traces (3,5-dimethylphenyl) borate, N, N-dimethylaniline traces [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethyl aniline traces (pentafluorophenyl) ) borate, triphenylcarbenium (p-tolyl) borate, triphenylcarbenium (m-tolyl) borate, triphenylcarbenium (2,4-dimethylphenyl) triphenylcarbene borate, triphenylcarbene borate, 3,5-dimethylphenyl [3] , 5-bis (trifluoromethyl) phenyl] b triphenylcarbene orate, trichlor (pentafluorophenyl) triphenylcarbene borate, tretish (p-tolyl) tropilium borate, tretish (m-tolyl) tropilium borate, tretish (2,4-dimethylphenyl) trillium borate, trichloride (3,5- dimethylphenyl) tropilium borate, tretrakis [3,5-bis (trifluoromethyl) phenyl] tropilium borate, tretrakis (pentafluorophenyl) tropilium borate, tretrakis (pentafluorophenyl) lithium borate, lithium tetrafenylborate, tretraquis (p-tolyl) borethat lithium, lithium tretrakis (m-tolyl) borate, lithium tretrakis (2,4-dimethylphenyl) borate, lithium tretrakis (3,5-dimethylphenyl), lithium tetrafluoroborate, trichloride (pentafluorophenyl) sodium borate, sodium tetrafenylborate, sodium tretrakis (p-tolyl) borate, sodium tretrakis (m-tolyl) borate, sodium tretrakis (2,4-dimethylphenyl) borate, sodium tretrakis (3,5-dimethylphenyl) sodium borate, tetrafluoroborate sodium, tretrakis- (pentafluorophenyl) potassium borate, potassium tetrafenylborate, tretrakis (p-tolyl) bora potassium tetra, potassium tretrakis (m-tolyl) borate, potassium tretrakis (2,4-dimethylphenyl) borate, potassium tretrakis (3,5-dimethylphenyl) borate, potassium tetrafluoroborate, tretrakis (pentafluorophenyl) aluminate lithium, lithium tetrafenylaluminate, lithium tretrakis (p-tolyl) lithium, tretrakis (m-tolyl) lithium tretrakis (2,4-dimethylphenyl) lithium aluminate, lithium tretrakis (3,5-dimethylphenyl) lithium, lithium tetrafluoroaluminate, sodium tretrakis (pentafluoro-phenyl) aluminate, sodium tetrafenylaluminate, sodium tretrakis (p-tolyl) aluminate, sodium tretrakis (m-tolyl) aluminate, sodium tretrakis (2,4-dimethylphenyl) aluminate, tretrakis (3,5-dimethylphenyl) sodium aluminate, sodium tetrafluoroaluminate, tretrakis (pentafluorophenyl) potassium aluminate, potassium tetrafenylaluminate, tretrakis (p-tolyl) potassium aluminate, tretachis (m-tolyl) potassium aluminate 2,4-dimethylphenyl) potassium aluminate, tretachis (3,5-dimethylphenyl) l) potassium aluminate, potassium tetrafluoroaluminate and the like, or combinations thereof. Ionization compounds useful in this invention are not limited to these; other examples of ionizing ionization compounds are described in U.S. Patent Nos. 5,576,259 and 5,807,938, the descriptions of which are incorporated herein by reference in their entirety. OLEFINE MONOMERS
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 a single olefin, 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 major amount of ethylene (> 50 mole percent) and a minor amount of comonomer (<50 mole percent), although this is not a requirement. Comonomers that can be copolymerized with ethylene often have 3 to 20 carbon atoms in their molecular chain.
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-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3 - heptene, the four normal octenes (for example, 1-octene), the four normal nonenes, the five normal and similar decines, 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 used as a monomer in the present invention. In one aspect, the olefin monomer is a C2-C10 olefin; alternatively, the olefin monomer is ethylene; or alternatively, the olefin monomer is propylene.
When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer can comprise, for example, ethylene or propylene, which is copolymerized with at least one comonomer. According to one aspect of this invention, the olefin monomer in the polymerization process comprises ethylene. In that 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-1 -pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene and the like , or combinations thereof. According to one aspect of the present invention, the comonomer can comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene or any combination thereof.
Generally, the amount of comonomer introduced into a 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. According to another aspect of the present invention, the amount of comonomer introduced into a 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 a reactor zone is about 0.1 to about 35 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 a reactor zone is 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 stick to this theory, where branched, substituted or functionalized olefins are used as reagents, it is believed that a steric resistance can prevent and / or delay the polymerization process. Thus, branched and / or cyclic portion (s) of the olefin removed in some way from the carbon-carbon double bond would not be expected to withstand the reaction in the same way that the same olefin substituents located closest to the bond double carbon-carbon would do. According to one aspect of the present invention, at least one monomer / reagent is ethylene, so that the polymerizations are a homopolymerization involving only ethylene, or copolymerizations with an acyclic, cyclic, terminal, linear, branched, substituted or unsubstituted olefin. 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 COMPOSITION
In some other respects, the present invention employs catalyst compositions containing a loop-metallocene compound having formula (I) and an activator, while in other aspects, the present invention employs catalyst compositions containing a loop-metallocene compound having formula (I) and a support-activator. These catalyst compositions can be used to produce polyolefins - homopolymers, copolymers and the like - for a variety of end-use applications. Metallocene compounds having formula (I) were discussed above. For example, in one aspect, the loop-metallocene compound having formula (I) may comprise (or essentially consist of, or consist of) a loop-metallocene compound having formula (II), formula (III), formula (IV ), formula (V), formula (VI), formula (VII) or combinations thereof. In yet another aspect, the ansa-metallocene compound having formula (I) can comprise (or essentially consist of, or consist of) an ansa-metallocene compound having formula (C), formula (D), formula (E) or combinations thereof.
In aspects of the present invention, it is contemplated that the catalyst composition may contain more than one metallocene compound having formula (I). In addition, additional metallocene compounds - other than those having formula (I) - can be used in the catalyst composition and / or the polymerization process, provided that the additional metallocene compound (s) do not reduce the advantages described here. In addition, more than one activator and / or more than one support-activator can also be used.
Generally, the catalyst compositions of the present invention comprise a loop-metallocene compound having formula (I) and an activator. In aspects of the invention, the activator may comprise a support-activator. Support-activators useful in the present invention have been described above. Such catalyst compositions may additionally comprise one or more of an organoaluminium compound or compounds (suitable organoaluminium compounds have also been discussed above). Thus, a catalyst composition of this invention may comprise a loop-metallocene compound having formula (I), a support-activator and an organoaluminium 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 , fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-silica-coated alumina and the like, or combinations thereof . In addition, the organoaluminium compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, hydride diisobutylaluminum, diethylaluminium ethoxide, diethylaluminium chloride and the like, or combinations thereof.
In another aspect of the present invention, a catalyst composition is provided that comprises a loop-metallocene compound having formula (I), a support-activator, and an organoaluminium compound, wherein that catalyst composition is substantially free of aluminoxanes, organoboro or organoborate compounds, ionizing ion compounds and / or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, substantially free or compounds of organoboro or organoborate; or alternatively, substantially free of ionizing ion compounds. In these respects, the catalyst composition has catalyst activity, to be discussed below, in the absence of these additional materials. For example, a catalyst composition of the present invention can essentially consist of a loop-metallocene compound having formula (I), a support-activator and an organoaluminium compound, where no other material is present in the catalyst composition that would increase / would decrease the activity of the catalyst composition by more than about 10% from the catalyst activity of the catalyst composition in the absence of said materials.
However, in other aspects of this invention, such activators / co-catalysts can be employed. For example, a catalyst composition comprising a loop-metallocene compound having formula (I) and a support-activator can additionally comprise an optional co-catalyst. Suitable co-catalysts in this regard include, but are not limited to, aluminoxane compounds, organoboro or organoborate compounds, ionizing ion compounds and the like or any combination thereof. More than one co-catalyst can 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 a loop-metallocene compound having formula (I) and an activator, wherein the activator comprises an aluminoxane compound, an organoboro or organoborate compound, an ionizing compound or combinations thereof.
This invention further encompasses methods of making such catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
The loop-metallocene compound having formula (I) can be pre-contacted with an olefinic monomer if desired, not necessarily the olefin monomer to be polymerized, and an organoaluminium compound for a first period of time before contacting this pre-mixture. -contacted with a support-activator. The first time period for contact, the pre-contact time, between the metallocene compound, the olefinic monomer and the organoaluminium compound typically ranges over a period of time from about 1 minute to about 24 hours, for example, from about 3 minutes to about 1 hour. Pre-contact times of about 10 minutes to about 30 minutes are also employed. Alternatively, the pre-contact process is carried out in multiple steps, instead of a single step, in which multiple mixtures are prepared, each comprising a set of different catalyst components. For example, at least two catalyst components are contacted forming a first mixture, followed by contacting the first mixture with at least another catalyst component forming a second mixture, and so on.
Multiple pre-contact steps can be performed in a single container or in multiple containers. In addition, multiple pre-contact steps can be performed in series (sequentially), in parallel or a combination of them. For example, the first mixture of two catalyst components can be formed in a first container, a second mixture comprising the first mixture plus an additional catalyst component can be formed in the first container or a second container, which is typically positioned downstream of the first container.
In another aspect, one or more of the catalyst components can be separated and used in different pre-contact treatments. For example, part of a catalyst component is fed into a first pre-contact container for pre-contact with at least one other catalyst component, while the remainder of that same catalyst component is fed to a second pre-contact container for pre-contact with at least one other catalyst component, either it is fed directly to the reactor, or a combination thereof. Pre-contact can be performed on any suitable equipment, such as tanks, stirring mixing tanks, various static mixing devices, a flask, a container of any kind, or combinations of these devices.
In another aspect of this invention, the various catalyst components (for example, a loop-metallocene compound having formula (I), activator support, organoalumin co-catalyst, and optionally an unsaturated hydrocarbon) are contacted in the polymerization reactor simultaneously while the polymerization reaction is proceeding. Alternatively, any two or more of these catalyst components can be pre-contacted in a container before entering the reaction zone. This pre-contact step can be continuous, in which the pre-contacted product is fed continuously to the reactor, or it can be a stepped or batch process in which a batch of pre-contacted product is added to make a catalyst composition. . This pre-contact step can be performed over a period of time that can be in the range of a few seconds to as long as several days, or more. In this respect, the continuous pre-contact step generally lasts from about 1 second to about 1 hour. In another aspect, the continuous pre-contact step lasts from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.
Once the pre-contacted mixture of the loop-metallocene compound having formula (I), the olefin monomer and the organoaluminium co-catalyst is contacted with the activator support, this composition (with the addition of the activator support) it is called a “post-contacted mixture”. The post-contacted mixture optionally remains in contact for a second period of time, the post-contact time, before starting the polymerization process. The post-contact times between the pre-contacted mixture and the activator support are generally in the range of about 1 minute to about 24 hours. In an additional aspect, the post-contact time is in the range of about 3 minutes to about 1 hour. The pre-contact step, the post-contact step, or both, can increase the productivity of the polymer compared to the same catalyst composition that is prepared without pre-contact or post-contact. However, neither a pre-contact step nor a post-contact step is required.
The post-contacted mixture can be heated to a temperature and for a period of time sufficient to allow the adsorption, impregnation or interaction of the pre-contacted mixture and the support-activator, so that a portion of the components of the pre-contacted mixture is immobilized, adsorbed or deposited in it. Where preheating is employed, the post-contacted mixture is usually heated to a temperature of between about -18 ° C to about 66 ° C, or from about 4 ° C to about 35 ° C.
When a pre-contact step is used, the molar ratio of total moles of olefin monomer to total moles of metallocene (s) in the pre-contacted mixture is typically in the range of about 1:10 to about 100,000: 1 .
Total moles of each component are used in this ratio taking into account the aspects of this invention where more than one olefin monomer and / or more than one metallocene compound is used in a pre-contact step. Furthermore, this molar ratio can be in the range of about 10: 1 to about 1,000: 1 in another aspect of the invention.
Generally, the weight ratio of organoaluminium compound to support-activator is in the range of about 10: 1 to about 1: 1000. If more than one organoaluminium compound and / or more than one activator support is used, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminium compound to the support-activator is in the range of about 3: 1 to about 1: 100, or about 1: 1 to about 1:50.
In some other aspects of this invention, the weight ratio of metallocene compound (s) to support-activator is in the range of about 1: 1 to about 1: 1,000,000. If more than one support-activator is employed, this ratio is based on the total weight of the support-activator. In another aspect, this weight ratio is in the range of about 1: 5 to about 1: 100,000, or about 1:10 to about 1: 10,000. In yet another aspect, the weight ratio of the metallocene compound (s) to the support-activator is in the 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 / h). In another aspect, the catalyst activity is greater than about 150, greater than about 250 or greater than about 500 g / g / h. In yet another aspect, catalyst compositions of this invention can be characterized by having a catalyst activity greater than about 550, greater than about 650 or greater than about 750 g / g / h. In yet another aspect, the catalyst activity can be greater than about 1000 g / g / h. This activity is measured under sludge polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90 ° C and a reactor pressure of about 390 psig.
According to another aspect of the present invention, catalyst compositions described herein can have a catalyst activity greater than about 10 grams of polyethylene (homopolymer, copolymer, etc., as required by the context) per pmol of metallocene per hour (abbreviated g / pmol / h). An activity of 10 g / pmol / h is equivalent to an activity of 10,000 kg / mol / h. In another aspect, the catalyst activity of the catalyst composition can be greater than about 15, greater than about 20 or greater than about 25 g / pmol / h. In yet another aspect, catalyst compositions of this invention can be characterized by having a catalyst activity greater than about 30, greater than about 40 or greater than about 50 g / pmol / h. In yet another aspect, the catalyst activity can be greater than about 100 g / pmol / h. This activity is measured under sludge polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90 ° C and a reactor pressure of about 390 psig.
As discussed above, any combination of the ansa-metallocene compound having formula (I), the support-activator, the organoaluminium compound, and the olefin monomer, can be pre-contacted in some other aspects of this invention. When any pre-contact occurs with an olefinic monomer, it is not necessary for the olefin monomer used in the pre-contact step to be the same as the olefin to be polymerized. In addition, when a pre-contact step between any combination of the catalyst components is employed for a first period of time, that pre-contacted mixture can be used in a subsequent post-contact step between any other combination of catalyst components during a second period of time. For example, the metallocene compound, the organoaluminium compound and 1-hexene can be used in a pre-contact step for a first period of time, and this pre-contacted mixture can then be contacted with the activator support to form a post-contacted mixture that is contacted for a second period of time before the polymerization reaction starts. For example, the first contact time, the pre-contact time, between any combination of the metallocene compound, the olefinic monomer, the support-activator, and the organoaluminium compound can be from about 1 minute to about 24 hours, about 3 minutes to about 1 hour, or about 10 minutes to about 30 minutes. The post-contacted mixture is optionally allowed to remain in contact for a second period of time, the post-contact time, before the polymerization process begins. According to one aspect of this invention, post-contact times between the pre-contacted mixture and any remaining catalyst components are about 1 minute to about 24 hours or about 5 minutes to about 1 hour. POLYMERIZATION PROCESS
Catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers and the like. Such a 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 comonomer (one or more) under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a loop-metallocene compound having formula (I) and an activator. Metallocene compounds having formula (I):
were discussed above. For example, in one aspect, the ansa-metallocene compound having formula (I) can comprise (or essentially consist of, or consist of) an ansa-metallocene compound having formula (II), formula (III), formula (IV ), formula (V), formula (VI), formula (VII), or combinations thereof. In yet another aspect, the loop-metallocene compound having formula (I) can comprise (or essentially consist of, or consist of) a loop-metallocene compound having formula (C), formula (D), formula (E) , or combinations thereof.
According to one aspect of the invention, the polymerization process employs a catalyst composition comprising an ansa-metallocene compound having formula (I) and an activator, wherein the activator comprises a support-activator. Support-activators useful in the polymerization processes of the present invention have been described above. The catalyst composition may additionally comprise one or more of an organoaluminium compound or compounds (suitable organoaluminium compounds have also been discussed above). Thus, a process for polymerizing olefins in the presence of a catalyst composition can employ a catalyst composition comprising a loop-metallocene compound having formula (I), a support-activator, and an organoaluminium compound. In some other respects, the activator support may comprise (or essentially consist of, or consist of) fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica-alumina sulfated alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-silica-coated alumina and the like, or combinations of the same. In some other respects, the organoaluminium compound may comprise r (or consist essentially of, or consist of) trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n- octyl aluminum, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum chloride and the like, or combinations thereof.
According to another aspect of the invention, the polymerization process can employ a catalyst composition comprising a loop-metallocene compound having formula (I) and an activator, wherein the activator comprises an aluminoxane compound, an organoboro or organoborate compound , an ionic ionization compound, or combinations thereof.
The catalyst compositions of the present invention are intended for any method of olefin polymerization using various types of polymerization reactors. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers and the like. The various types of reactors include those that can be referred to as a batch reactor, mud reactor, gas phase reactor, solution reactor, high pressure reactor, autoclave reactor, tubular reactor and the like, or combinations thereof. The polymerization conditions for the various types of reactors are well known to those skilled in the art. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Mud reactors can comprise horizontal and vertical circuits. High pressure reactors can comprise autoclave or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes could use continuous or intermittent product discharge. The processes may also include direct total or partial recycling of unreacted monomer, unreacted comonomer, and / or diluent.
Polymerization reactor systems of the present invention may comprise one type of reactor in a system or multiple reactors of the same or different types. The production of polymers in multiple reactors can include several stages in at least two separate polymerization reactors interconnected via a transfer device making it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may differ from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization. Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of circuit and gas phase reactors, multiple high pressure reactors, or a combination of high pressure with circuit and / or gas phase. The multiple reactors can be operated in series, in parallel, or both.
According to one aspect of the invention, the polymerization reactor system can comprise at least one looped sludge reactor comprising vertical or horizontal circuits. The monomer, diluent, catalyst and comonomer can be continuously fed to a loop reactor where polymerization takes place. Generally, continuous processes can comprise the continuous introduction of monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of that reactor from a suspension comprising polymer particles and the diluent. The effluent from the reactor can be evaporated in flash to remove the solid polymer from the liquids that comprise the diluent, monomer and / or comonomer. Various technologies can be used for the separation step, including, but not limited to, flash evaporation which can include any combination of heat addition and pressure reduction; separation by cyclonic action in a cyclone or hydrocyclone; or separation by centrifugation.
A sludge polymerization process (also known as the particulate form 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 is incorporated herein by reference in its entirety.
Suitable diluents used in sludge polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some circuit polymerization reactions can occur under volume conditions where no diluent is used. An example is the polymerization of propylene monomer, as described in U.S. Patent No. 5,455,314, which is incorporated herein by reference in its entirety.
According to yet another aspect of this invention, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycling stream containing one or more monomers continuously cycled along a fluidized bed in the presence of the catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back to the reactor. At the same time, the polymer product can be removed from the reactor and the new, fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for polymerizing multi-stage gas phase olefins, wherein the olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a polymer containing catalyst formed in a first polymerization zone for 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.
According to yet another aspect of the invention, a high pressure polymerization reactor can comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomer, initiators or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a reactor zone. The initiators, catalysts and / or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. Gas streams can be intermixed for polymerization. Heat and pressure can be used appropriately to obtain optimal polymerization reaction conditions.
According to yet another aspect of the invention, the polymerization reactor can comprise a solution polymerization reactor in which the monomer / comonomer is contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer / comonomer can be placed in the vapor phase in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Oscillation can be used to obtain the best temperature control and to keep the polymerization mixes uniform throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
Polymerization reactors suitable for the present invention can additionally comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components, and / or at least one polymer recovery system. Reactor systems suitable for the present invention may further comprise systems for the purification of raw material, storage and preparation of catalyst, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis and process control .
Polymerization conditions that are controlled for efficiency and to provide the desired polymer properties can include temperature, pressure and the concentrations of various reagents. The polymerization temperature can affect the productivity of the catalyst, the molecular weight of the polymer and the molecular weight distribution. A suitable polymerization temperature can be any temperature below the depolymerization temperature according to the Gibbs Free energy equation. Typically, this includes from about 60 ° C to about 280 ° C, for example, or from about 60 ° C to about 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 according to the type of reactor and polymerization. The pressure for liquid phase polymerizations in a loop reactor is typically less than 1000 psig. The pressure for the gas phase polymerization is generally around 200 to 500 psig. High pressure polymerization in a tubular or autoclave reactor generally works at about 20,000 to 75,000 psig. Polymerization reactors can also work in a supercritical region occurring at generally higher temperatures and pressures. Operating above the critical point of a pressure / temperature diagram (supercritical phase) can offer disadvantages.
Aspects of this invention are directed to olefin polymerization processes comprising contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer. The olefin polymer produced by the process can have a density greater than about 0.92 g / cm3, for example, in a range of about 0.935 to about 0.97 g / cm3. In addition, or alternatively, the olefin polymer may have an average of less than about 5 short chain branches (SCB’s) per 1000 total carbon atoms, for example, from 0 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, for example, less than about 0.002, or less than about 0.001, LCB's per 1000 atoms total carbon.
Aspects of this invention are also addressed to olefin polymerization processes conducted in the absence of added hydrogen. In this description, “added hydrogen” will be denoted as the hydrogen feed ratio to the olefin monomer entering the reactor (in units of ppm). An olefin polymerization process of this invention may comprise a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises an ansa-metallocene compound having formula (I) and an activator, in which the polymerization process is conducted in the absence of added hydrogen. As described above, the loop-metallocene compound having formula (I) can comprise a loop-metallocene compound having formula (II), formula (III), formula (IV), formula (V), formula (VI), formula (VII), formula (C), formula (D), formula (E), or combinations thereof. As one of ordinary skill in the art would recognize, hydrogen can be hydrogenated in-situ by metallocene catalyst compositions in various olefin polymerization processes, and the amount generated can vary depending on the specific catalyst composition and the compound (s) ) of metallocene employed, the type of
polymerization process used, the polymerization reaction conditions, and so on.
In one aspect, the polymerization process is conducted in the absence of added hydrogen, and the Mw / Mn ratio of the olefin polymer produced by the process can increase as the molar ratio of olefin comonomer to olefin monomer increases from about 0.001: 1 at about 0.06: 1. For example, the Mw / Mn of the polymer produced by the process in a 0.06: 1 comonomer: monomer molar ratio may be greater than the Mw / Mn of the polymer produced by the process in a 0.005: comonomer: monomer molar ratio: 1, when produced under the same polymerization conditions. Additionally, the Mw / Mn of the polymer produced by the process in a 0.05: 1 comonomer: monomer molar ratio may be greater than the Mw / Mn of the polymer produced by the process in a 0.01 comonomer: monomer molar ratio : 1, when produced under the same polymerization conditions. Applicants also contemplate a method of increasing an Mw / Mn ratio of an olefin polymer, and that method comprises contacting a catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce the olefin polymer ; contacting the catalyst composition with the olefin monomer and the olefin comonomer in the absence of added hydrogen; and increasing the molar ratio of olefin comonomer to olefin monomer within the range of about 0.001: 1 to about 0.2: 1, wherein the catalyst composition comprises a loop-metallocene compound having formula (I) and an activator (for example, a support-activator). For example, the molar ratio can be increased from a smaller ratio (for example, 0.001: 1, 0.005: 1, etc.) to a larger ratio (for example, 0.01: 1, 0.05: 1).
In other respects, it may be desirable to conduct the polymerization process in the presence of a certain amount of added hydrogen. Accordingly, an olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a compound loop-metallocene having formula (I) and an activator, in which 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 olefin monomer in the process can be controlled in a weight ratio that falls in a range of about 25 ppm to about 1500 ppm, about 50 to about 1000 ppm, or about 100 ppm at about 750 ppm.
In another aspect, the polymerization process is conducted in the presence of added hydrogen and the olefin comonomer, and the Mw of the olefin polymer is substantially constant over a range of about 50 ppm to about 1000 ppm of added hydrogen; alternatively, from about 75 ppm to about 750 ppm of added hydrogen; alternatively, from about 75 ppm to about 500 ppm of added hydrogen; or alternatively, from about 100 ppm to about 500 ppm of added hydrogen. As far as the Mw of the olefin polymer is concerned, substantially constant means +/- 25%. In some other respects, however, the Mw may be within a range of +/- 15%. Applicants also contemplate an olefin production method having an Mw that is substantially independent of the hydrogen content, and that method comprises contacting a catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce the olefin polymer; and contacting the catalyst composition with the olefin monomer and the olefin comonomer in the presence of hydrogen added in the range of about 50 ppm to about 1000 ppm (alternatively, from about 75 ppm to about 750 ppm; alternatively, from about 75 ppm to about 500 ppm; or alternatively, from about 100 ppm to about 500 ppm), wherein the catalyst composition comprises a loop-metallocene compound having formula (I) and an activator (for example , a support-activator). Similarly to the above, the olefin polymer having an Mw that is substantially independent of the hydrogen content means that the Mw remains within a range of +/- 25% in the target range of ppm of added hydrogen (for example, of 100 to 500 ppm). Often, Mw will fall in a range of +/- 15% over certain ranges of hydrogen content.
In another aspect, an olefin polymerization process may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a compound loop-metallocene having formula (I) and an activator, in which the polymerization process is conducted in the presence of hydrogen added in a range of about 50 ppm to about 1000 ppm hydrogen, or from about 75 ppm to about 750 ppm, or from about 75 ppm to about 500 ppm, or from about 100 ppm to about 500 ppm. In the presence of these ppm hydrogen contents, an Mw of an olefin polymer produced by the process in the presence of an olefin comonomer can be at least 25% greater than an Mw of an olefin polymer produced by the process under the same polymerization conditions. without the olefin comonomer (for example, 25% to 200% higher, 30% to 100% higher, etc.). For example, the Mw of the olefin polymer produced by the process in the presence of the olefin comonomer can be at least 30% greater, 40% greater, 50% greater, or 60% greater than an Mw of an olefin polymer produced by the process under the same polymerization conditions without the olefin comonomer. Similarly, in the presence of these contents of hydrogen added in ppm, an Mw / Mn ratio of an olefin polymer produced by the process in the presence of an olefin comonomer can be at least 15% greater than an Mw / Mn ratio of a polymer of olefin produced by the process under the same polymerization conditions without the olefin comonomer (for example, 15% to 200% higher, 15% to 100% higher, etc.). According to additional examples, the Mw / Mn ratio of the olefin polymer produced by the process in the presence of the olefin comonomer can be at least 20% greater, 25% greater, 30% greater, 40% greater, or 50% greater than an Mw / Mn of an olefin polymer produced by the process under the same polymerization conditions without the olefin comonomer. Applicants also contemplate a method of increasing the Mw (or Mw / Mn ratio) of an olefin polymer, and that method comprises introducing an olefin comonomer to a contact product of a catalyst composition, an olefin monomer under polymerization conditions to produce the olefin polymer; and the introduction of the olefin comonomer to the contact product of the catalyst composition and the olefin monomer in the presence of hydrogen added in the range of about 50 ppm to about 1000 ppm (alternatively, from about 75 ppm to about 750 ppm ; alternatively, from about 75 ppm to about 500 ppm; or alternatively, from about 100 ppm to about 500 ppm), wherein the catalyst composition comprises a loop-metallocene compound having formula (I) and an activator (for example, a support-activator). The Mw (or Mw / Mn ratio) can be increased by introducing the olefin comonomer by at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50%, compared to the Mw (or Mw / Mn ratio) of the olefin polymer produced in the absence of the olefin comonomer (for example, 15% to 200% greater, 20% 150% higher, etc.). Typically, the amount of comonomer introduced is in a molar ratio of olefin comonomer to olefin monomer in a range of about 0.001: 1 to about 0.2: 1, or from about 0.005: 1 to about 0, 1: 1, or from about 0.01: 1 to about 0.05: 1.
In another aspect, the catalyst activity of the catalyst composition can vary with the comonomer content and / or can be substantially constant with added hydrogen content. For example, an olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the activity of the catalyst composition may decrease as the molar ratio of olefin comonomer to olefin monomer increases from about 0.001: 1 to about 0.06: 1. Consequently, the activity of the catalyst composition in a 0.06: 1 comonomer: monomer molar ratio may be less than the activity of the catalyst composition in a 0.005: 1 comonomer: monomer molar ratio, when determined under the same. polymerization conditions. In addition, the activity of the catalyst composition at a 0.05: 1 comonomer: monomer molar ratio may be less than the activity of the catalyst composition at a 0.01: 1 comonomer: monomer molar ratio, when determined under the same polymerization conditions. Applicants also contemplate a method of increasing the activity of a catalyst composition, and that method comprises contacting the catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce the olefin polymer; and decreasing the molar ratio of the olefin comonomer to the olefin monomer within the range of about 0.2: 1 to about 0.001: 1, wherein the catalyst composition comprises an ansa-metallocene compound having formula (I ) and an activator (for example, a support-activator).
For example, a molar ratio can be decreased from a larger ratio (for example, 0.01: 1, 0.05: 1) to a smaller ratio (for example, 0.001: 1, 0.005: 1, etc.) .
In another aspect, an olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a loop-metallocene compound having formula (I) and an activator, in which the polymerization process is conducted in the presence of added hydrogen, and in which the activity of the catalyst composition is substantially constant over a range of about 50 ppm about 1000 ppm of hydrogen added; alternatively, from about 75 ppm to about 750 ppm of added hydrogen; alternatively, from about 75 ppm to about 500 ppm of added hydrogen; or alternatively, from about 100 ppm to about 500 ppm of added hydrogen. As far as the activity of the catalyst composition is concerned, substantially constant means +/- 25%. In some other respects, however, the activity of the catalyst composition can be within a range of +/- 15%. This catalyst activity can be substantially constant at a given comonomer concentration. Applicants also contemplate a method of producing an olefin polymer in a catalyst activity that is substantially independent of the hydrogen content, and that method comprises contacting a catalyst composition with an olefin monomer and an olefin comonomer under conditions polymerization to produce the olefin polymer; and contacting the catalyst composition with the olefin monomer and the olefin comonomer in the presence of hydrogen added in the range of about 50 ppm to about 1000 ppm (alternatively, from about 75 ppm to about 750 ppm; alternatively, from about 75 ppm to about 500 ppm; or alternatively, from about 100 ppm to about 500 ppm), wherein the catalyst composition comprises a loop-metallocene compound having formula (I) and an activator (for example , a support-activator). Similarly to the above, the catalyst composition having an activity that is substantially independent of the hydrogen content means that the catalyst activity remains within a range of +/- 25% in the target range of ppm of added hydrogen (e.g. , from 100 to 500 ppm). Often, catalyst activity will fall within a range of +/- 15% over certain ranges of hydrogen content.
In some other aspects of this invention, the ratio of feed or hydrogen reagent to olefin monomer can be kept substantially constant during the polymerization operation for a particular polymer classification. That is, a hydrogen: olefin monomer ratio can be selected at a particular ratio within a range of about 5 ppm to about 1000 ppm approximately, and maintained at about +/- 25% during the polymerization operation. For example, if the target ratio is 100 ppm, then maintaining the hydrogen: olefin monomer substantially constant would bind by maintaining the feed ratio between about 75 ppm and about 125 ppm. In addition, the addition of a comonomer (or comonomers) can be, and generally is, substantially constant throughout the polymerization operation for a particular polymer classification.
However, in other respects, it is contemplated that monomer, comonomer (or comonomers), and / or hydrogen can be periodically pulsed into the reactor, for example, in a similar manner to that employed in U.S. Patent No. 5,739,220 and in the Publication U.S. Patent No. 2004/0059070, the descriptions of which are incorporated herein 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 formation that the product will ultimately determine the desired polymer properties and attributes. Mechanical properties include tests of stress, curvature, impact, slip, stress relaxation and stiffness. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, fracture growth, long chain branching and rheological measurements.
This invention is also directed to, and encompasses, the polymers produced by any polymerization processes described herein. Manufacturing articles can be formed from, and / or can comprise, the polymers produced according to that invention. POLYMERS AND ARTICLES
If the resulting polymer produced according to the present invention is, for example, an ethylene polymer or copolymer, its properties can be characterized by several analytical techniques known and used in the polyolefin industry. Manufacturing articles can be formed of, and / or can comprise, the ethylene polymers of this invention, whose typical properties are provided below.
Ethylene polymers (copolymers, terpolymers, etc.) produced according to this invention generally have a melt index of 0 to about 100 g / 10 min. melting indices in the range of 0 to about 75 g / 10 min, from 0 to about 50 g / 10 min, or from 0 to about 30 g / 10 min, are contemplated in some other aspects of this invention. For example, a polymer of the present invention can have a melt index (Ml) in the range of 0 to about 25, or from 0 to about 10 g / 10 min.
Ethylene polymers produced in accordance with this invention can 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 about 20. Ranges contemplated for HLMI / MI include, but are not limited to, about 5 to about 150, about 10 to about 125, about 10 to about 100, about 15 to about 90, about 15 to about 80, about 15 to about 70, or about 15 to about 65.
In some other aspects of this invention, the catalyst systems described herein can be referred to as comonomer rejectors, that is, the comonomer is not as readily incorporated into an olefin polymer when compared to other bridge-linked metallocene catalyst systems. Consequently, the densities of ethylene-based polymers produced using the catalyst systems and processes described herein are often greater than about 0.92 g / cm3. In one aspect of this invention, the density of an ethylene polymer can be greater than about 0.925, greater than about 0.93, or greater than about 0.935 g / cm3. In yet another aspect, the density can be in the range of about 0.92 to about 0.97 g / cm3, such as, for example, from about 0.925 to about 0.97 g / cm3, of about 0.93 to about 0.965 g / cm3, or about 0.935 to about 0.965 g / cm3.
Ethylene polymers of this invention can generally have an average of 0 to about 5 short chain branches (SCB’s) per 1000 total carbon atoms. For example, average SCB contents in a range of 0 to about 4.5, from 0 to about 4, from 0 to about 3.5, or from 0 to about 3, SCB's per 1000 total carbon atoms are contemplated here.
Ethylene polymers, such as copolymers and terpolymers, within the scope of the present invention generally have a polydispersity index - a ratio of the average molecular weight (Mw) to the average numerical molecular weight (Mn) - in a range of about 2 to about of 10. In some other aspects described here, the Mw / Mn ratio is in the range of about 2.1 to about 9, about 2.1 to about 8, or about 2.2 to about 7. The Mz / Mw ratio for the polymers of this invention is often in the range of about 1.6 to about 12. Mz is the average molecular weight z. According to one aspect, the Mz / Mw of the ethylene polymers of this invention can be in the range of about 1.6 to about 10, about 1.7 to about 6, about 1.7 to about 4, or about 1.7 to about 3.5.
Generally, the olefin polymers of the present invention have low levels of long chain branching, with typically less than 0.05 long chain branching (LCB's) per 1000 total carbon atoms. In some other respects, 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 (for example, 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 total carbon atoms, in other aspects of this invention.
Ethylene polymers, whether homopolymers, copolymers, terpolymers, and so on, can be formed into various articles of manufacture. Articles that may comprise polymers of this invention include, but are not limited to, an agricultural film, an automobile part, a bottle, a drum, a fiber or fabric, a food packaging film or container, a food service article , a fuel tank, a geomembrane, a domestic container, a liner, a molded product, a medical device or material, a pipe, a blade or tape, a toy and the like. Various processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, blade extrusion, profile extrusion, thermoforming and the like. In addition, additives and modifiers are often added to these polymers in order to provide processing of beneficial polymer or end-use product attributes. EXAMPLES
The invention is further illustrated by following the examples below, which should not be construed in any way as imposing limitations on the scope of this invention. Various other aspects, modalities, modifications and equivalents thereof, which, after reading the description here, may suggest on their own to someone commonly skilled in the art without departing from the spirit of the present invention or the scope of the appended claims.
The melt index (Ml, g / 10 min) was determined according to ASTM D1238 at 190 ° C with 2,160 grams in weight.
The high charge melting index (HLMI, g / 10 min) was determined according to ASTM D1238 at 190 ° C with 21,600 grams of weight.
The polymer density was determined in grams per cubic centimeter (g / cm3) in a compression molded sample, cooled at about 15 ° C per hour, and conditioned for about 40 hours at room temperature according to ASTM D1505 and ASTM D1928, procedure C.
Molecular weights and molecular weight distribution were obtained using a PL 220 SEC high temperature chromatography unit (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 pL was used with a nominal polymer concentration of 1.5 mg / ml. The dissolution of the sample in stabilized TCB was performed by heating at 150 ° C for 5 hours with additional gentle oscillation. The columns used were three PLgel Mixed A LS columns (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 size exclusion chromatography (SEC) methods with multi-angle light scattering (MALS) detection. A DAWN EOS 18-angle light scattering photometer (Wyatt Technology, Santa Barbara, CA) was attached to a PL-210 SEC system (Polymer Labs, UK) or a Waters 150 CV Plus system (Milford, MA) via a hot transfer line, thermally controlled at the same temperature according to the SEC columns and its differential refractive index (DRI) detector (145 ° C). in a flow rate setting of 0.7 mL / min, the mobile phase, 1,2,4-trichlorobenzene (TCB), was eluted through three 7.5 mm x 300 mm Mixed A-LS columns, 20 pm (Polymer Labs). Polyethylene (PE) solutions with concentrations of ~ 1.2 mg / mL, depending on the samples, were prepared at 150 ° C for 4h before being transferred to SEC injection vials sitting on a carousel heated to 145 ° C. For higher molecular weight polymers, longer heating periods were necessary in order to obtain true homogeneous solutions. In addition to the acquisition of a concentration chromatogram, seventeen light scattering chromatograms at different angles were also suitable for each injection using the Wyatt’s Astra® software. In each chromatographic slice, both the absolute molecular weight (M) and the mean square value radius (RMS), also known as the turning radius (Rg), were obtained from an intercept and slope of the Debye graph, respectively. 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 approach was used to determine the amount of LCB. Since the SEC-MALS M and Rg measurements on each slice of a chromatogram simultaneously, branching indices, gM, as a function of M could be determined on each slice directly by determining the ratio of the mean square Rg of branched molecules for that of linear, in the same M, as shown in the following equation (subscripts br and lin represent branched and linear polymers, respectively).

In a given gM, the average number of LCB weight per molecule (B3w) was computed using the Zimm-Stockmayer equation, shown in the equation below, in which the branches were assumed to be trifunctional or Y-shaped.

The LCB frequency (LCBMÍ), the number of LCB per 1000 C, of the / slice was then computed directly using the following equation (Mt is the Mw of the / * slice):

The LCB distribution (LCBD) over the molecular weight distribution (MWD) was then established for a complete polymer.
Short chain branch distribution (SCBD) data were obtained using a SEC-FTIR high temperature heated flow cell (Polymer Laboratories) as described by PJ DesLauriers, DC Rohlfing and ET Hsieh, Polymer, 43, 159 (2002) .
Rheological fusion characterizations were performed as follows. Small strain oscillatory shear measurements (10%) were performed on a Rheometrics Scientific, Inc. ARES rheometer using parallel plate geometry. All rheological tests were performed at 190 ° C. The complex viscosity data | 7 * | versus frequency (ω) were then fitted to the curve using the empirical model of three modified Carreau-Yasuda parameters (CY) to obtain the zero shear viscosity - η0, characteristic viscosity relaxation time - vη, and the width parameter - The. the Carreau-Yasuda (CY) empirical model is as follows.
where: | η ω) | = magnitude of complex shear viscosity; 770 = zero shear viscosity; zη = viscosity relaxation time; a = “width” parameter; n = sets the final energy law slope, set at 2/11; and ω = angular frequency of oscillatory shear deformation.
Details of the significance and interpretation of the CY model and derived parameters can be found at: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polym. Eng. Scí., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2a. Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety.
The Nuclear Magnetic Resonance (NMR) spectra were obtained on a Varian Mercury Plus 300 NMR spectrometer. CDCI3 and C6D6 were acquired from Cambridge Isotope Laboratories, degassed and stored on 13X molecular sieves under nitrogen. NMR spectra were recorded using J. Young NMR tubes or covered under ambient test conditions. The 1H chemical shifts are reported versus SiMe4 and were determined by 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 capillary columns for all purposes Dual Factor Four (30 mx 0.25 mm), flame ionization detector, and Varian 8400 self-sampling unit. Mass spectral analysis was performed in conjunction with a Varian 320 MS instrument using 70 eV electron ionization.
The sulfated alumina activator support (abbreviated as ACT1) employed in some of the examples was prepared according to the following procedure. Bohemite was obtained from W.R. Grace Company under the design of “Alumina A” and having a surface area of about 300 m2 / g and a pore volume of about 1.3 ml / g. This material was obtained as a powder having an average particle size of about 100 microns. This material was impregnated in incipient moisture with an aqueous solution of ammonium sulfate to equal about 15% sulfate. This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 110 ° C for about 16 hours.
To calcinate the support, about 10 grams of this powder mixture were placed in a 4 cm quartz tube adjusted with a sintered quartz disk at the bottom. While the powder was supported on the disk, air (nitrogen can be replaced) dried by passing through a 13X molecular sieve column, was blown upward through the disk at the standard rate of about 1.6 to 1.8 cubic feet per hour. An electric oven around the quartz tube was then switched on and the temperature was increased at the rate of about 400 ° C per hour to the desired calcination temperature of about 600 ° C. At that temperature, the powder was allowed to fluidize for about three hours in dry air. Then, the sulfated alumina activator support (ACT1) was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
The fluoridated silica-alumina activator support (abbreviated as 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 about 13% alumina by weight and having a surface area of about 400 m2 / g and a pore volume of about 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 were impregnated with a solution containing about 200 mL of water and about 10 grams of ammonium hydrogen fluoride, resulting in a wet powder having the consistency of wet sand. This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 110 ° C for about 16 hours.
To calcinate the support, about 10 grams of this powder mixture were placed in a 4 cm quartz tube adjusted with a sintered quartz disk at the bottom. While the powder was supported on the disk, the air (nitrogen can be replaced) dried as it passed through the 13X molecular sieve column, was blown upward through the disk at a linear rate of about 1.6 to 1.8 cubic feet hourly pattern. An electric oven around the quartz tube was then switched on and the temperature was increased at a rate of about 400 ° C per hour to the desired calcination temperature of about 450 ° C. At that temperature, it was allowed to fluidize for about three hours in dry air. Then, the support-activator of fluoridated silica-alumina (ACT2) was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
The fluoridated silica-alumina activator support (abbreviated as ACT4) used in some of the examples was prepared according to the following procedure. A silica-coated alumina was obtained from Sasol Company under the design of “Siral 28M” containing about 72% alumina by weight, and having a surface area of about 340 m2 / g, a pore volume of about 1.6 mL / g, and an average particle size of about 90 microns. About 20g of Siral 28M was then calcined at around 600 ° C for approximately 8 hours, then soaked in incipient moisture with 60 mL of a methanol solution containing 2g of ammonium bifluoride.
This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 110 ° C for about 12 hours.
To calcinate the support, the powder mixture was placed in a 5 cm fluidized bed using dry nitrogen. The temperature was raised to 600 ° C over a period of 1.5 hours, and then maintained at 600 ° C for three hours. Then, alumina coated with fluoridated silica (ACT4) was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
The titanate fluoridated silica-alumina activator support (abbreviated as 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 design of “Siral 28M" containing about 72% alumina by weight, and having a surface area of about 340 m2 / g, a pore volume of about 1.6 ml / g, and an average particle size of about 90 microns. About 682 g of Siral 28M was first calcined at about 600 ° C for approximately 8 hours, then impregnated to incipient moisture with 2200 ml_ of a methanol solution containing 147 g of a solution containing 60% H2TiF6. This mixture, with the consistency of wet sand, was then placed in a flat pan and allowed to dry under vacuum at approximately 110 ° C for about 12 hours.
To calcinate the support, the powder mixture was placed in a 5 cm fluidized bed using dry nitrogen. The temperature was raised to 600 ° C over a period of 1.5 hours, and then maintained at 600 ° C for three hours. Then, alumina coated with titanium fluoridated silica (ACT3) was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
The polymerization operations were carried out in a one-gallon (3.8 liter) 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 triisobutylaluminum heptane (TIBA) or triethylaluminium (TEA), the support activator (ACT1, ACT2, ACT3 or ACT4), and the metallocene (MET1, MET2 or MET3; structures provided below ) were added through a loading port while venting isobutane vapor. The loading door was closed and about 2L of isobutane was added. The resulting mixture was stirred for 5 min, and then heated to the desired polymerization temperature. With the polymerization temperature reactor approach, ethylene was charged to the reactor to obtain 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 proceeded to keep the reactor pressure constant. If used, hydrogen was added in a fixed mass ratio to the ethylene flow. The reactor was maintained and controlled at the desired reactor temperature and pressure over the 60 min polymerization run time. When complete, 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 a metallocene loop having formula (I) Metallocene compounds used in these examples had the following structures and abbreviations:

Synthesis of MET1: A solution of 1,2-dichloro-1,1,2,2-tetramethyldisilane (2.29 g, 12.3 mmol) in Et2O (25 mL) was prepared. A solution of Li (allyl-indenyl) (1.00 g, 6.17 mmol) in Et2O (25 mL) was prepared and added in drops per cannula to the disyllane solution stirred at approximately 22 ° C over 1h. The mixture was stirred overnight and evaporated in vacuo. The residue was suspended in toluene (20 ml), filtered through a Celite disc and an aliquot of the filtrate was removed. NMR analysis showed the presence of Me4Si2 (allyl-indenyl) CI and initial disilane. 1H NMR data for Me4Si2 (allyldenenyl) CI (C6D6): δ 7.31 (d, J = 8, 2H, C6-lnd), 7.19 (t, J = 8, 1H, C6-lnd), 7.08 (t , J = 8, 1H, Ce-lnd), 6.22 (m, 1H, C5-lnd), 5.96 (m, 1H, CH = CH2), 5.14 (m, 1H, CH = CH2), 5.06 (m, 1H , CH = CH2), 3.30 (m, C5-lnd), 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 in vacuo overnight to obtain a yellow oil (1.9 g). THF (20 mL) was added by 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 2h and an aliquot was removed by syringe. The GC-MS analysis showed about 95% conversion to the expected ligand Me4Si2 (allyldenenyl) (cyclopentadienyl) (m / z, 337 {M +}), with the balance comprised of products derived from the starting materials. The mixture was stirred an additional 1h and evaporated in vacuo. The residue was dried in vacuo at 35 ° C for 1h and toluene (20 ml) was added. The suspension was filtered through a Celite disc and Celite was washed with toluene (2 x 20 ml). The toluene solutions were combined evaporated in vacuo to obtain a yellow oil (2.05 g). Et2O (50 ml) was added and the resulting solution was cooled in a water and ice bath. A solution of n-BuLi (5.1 ml, 2.5 M in hexanes, 13 mmol) was added by syringe over 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 in drops by cannula to the stirred zirconium suspension for 30 min, and the mixture was stirred in the bath overnight. The bright yellow sludge was evaporated in vacuo and CH2 Cl2 (50 ml) was added by cannula. The suspension was filtered through a Celite disc and Celite was washed with CH2 Cl2 (2 x 20 ml). The resulting solutions were combined and evaporated in vacuo to obtain a dark yellow solid (2.76 g). The residue was recrystallized from toluene (10 mL) at -30 ° C to obtain MET1 as a yellow crystalline solid, which was dried under vacuum (900 mg, 29% yield crystallized from Li (allyl-indenyl)) . 1H NMR (CDCI3): δ 7.73 (d, J = 8, 1H, CΘ-Ind), 7.63 (d, J = 8, 1H, C6-lnd), 7.32 (t, J = 8, 1H, C6-lnd ), 7.24 (t, J = 8, 1H, C6-lnd), 6.73 (m, 1H, Cp), 6.72 (s, 1H, C5-lnd), 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 = 7, 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: The solution of indene (10.0 mL, 86.1 mmol) in Et2O (200 mL) was prepared and cooled in dry ice / acetone. A solution of n-BuLi (34.5 mL, 2.5 M, 86 mmol) was added by syringe over 3 min. The bath was removed and the mixture was stirred for 4h, and then cooled again in dry ice / acetone. Clean 1-Bromo-3-phenylpropane (13.1 mL, 86.1 mmol) was added by syringe over 1 min and the stirred mixture was slowly heated out of the bath to approximately 22 ° C overnight. The mixture was slowly quenched with water (5 ml) and then additional water (50 ml) was added. The biphasic mixture was stirred, the organic layer was separated, dried over MgSO4, filtered and evaporated in vacuo to obtain (3-phenylpropyl) -1 / - / - indene as a yellow oil (18.61 g, 95% in mol purity based on GC analysis). GC-MS: m / z, 234 (M +). The solution of (3-phenylpropyl) - 1 / - / - indene (3.00 g, 12.8 mmol) in Et2O (50 mL) was prepared and cooled in a water and ice bath. A solution of n-BuLi (5.1 ml, 2.5 M, 13 mmol) was added by syringe over 30 sec, the bath was removed and the mixture was stirred for 1.5 h. A solution of Me4Si2Cl2 (4.92 g, 26.2 mmol) in Et2O (25 mL) was prepared and the Li (indenyl) solution was added in drops per cannula to the disyllane solution stirred at approximately 22 ° C for 1h. The mixture was stirred overnight, then evaporated and dried in vacuo for 4h to obtain a yellow oil. THF (50 ml) was added by cannula and a solution of cyclopentadienyl-MgCl (14.0 ml, 1.0 M in THF, 14 mmol) was added to the syringe solution for 5 min. The mixture was stirred overnight, evaporated in vacuo, triturated with toluene (20 ml), allowed to settle, and the supernatant was decanted. The grinding procedure was repeated and the toluene solutions were combined and evaporated in vacuo to obtain an orange oil (4.11 g). Et2O (75 ml) was added by 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 over 1 min to obtain a fine suspension. The bath was removed and the stirred suspension was heated to approximately 22 ° C for 2h. THF (1.6 mL) was added by syringe. A suspension of ZrCL (2.37 g, 10.2 mmol) in heptane (75 mL) was prepared and cooled in an ice-water bath. The lithium solution was added in drops by cannula to the stirred zirconium suspension for 20 min, and the mixture was heated to approximately 22 ° C overnight. The volatiles were removed in vacuo and CH2 Cl2 (100 mL) was added by cannula. The suspension was filtered through a Celite disc and Celite was washed with CH2 Cl2 (2 x 20 ml). The filtrate and washes were combined and evaporated in vacuo 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 impurities. The supernatant was decanted and 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 description of which is incorporated herein by reference in its entirety. A solution of indene (95 mole percent purity, 10 mL, 81.8 mmol) in Et2O (200 mL) was prepared, cooled in dry ice / acetone, and charged with a n-BuLi solution (33 mL, 2.5 M in hexanes, 83 mmol) per syringe for 1 min. The solution was stirred and allowed to slowly warm to approximately 22 ° C over 16h. A separate solution of 1,2-dichloro-1,1,2,2-tetramethyldisilane (7.54 g, 40.3 mmol) in Et2O (100 mL) was prepared and cooled in water and ice. The prepared Li-lnd solution was added in drops per cannula to the disilane solution over 1h. The resulting pale yellow suspension was stirred and heated slowly to approximately 22 ° C over 16h. The solution was evaporated in vacuo resulting in a beige solid. Toluene (75 mL) was added by 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. Stirring was stopped with complete dissolution of the solid, and then the solution was allowed to cool slowly to approximately 22 ° C over about 16 hours. The supernatant solution was cannulated and the resulting precipitate was dried under vacuum to obtain rac / n7eso-1,2-bis (inden-1-yl) -1,1,2,2-tetramethyldisilane as an amber crystalline solid ( 5.55 g). The supernatant solution was concentrated and a recrystallization procedure analogous to the aforementioned was repeated twice to obtain two additional amounts of the rac / meso bridged ligand (2.83 g and 1.52 g, respectively) exhibiting NMR purity comparable to that of first. The total isolated yield of rac / meso-1,2-bis (inden-1-yl) -1,1,2,2-tetramethyldisilane was 9.90 g, 71%. 1H NMR data indicated the presence of a mixture of 2/1 diastereoisomers, neither of which could be characterized unambiguously as rac or meso due to the presence of elements of symmetry in both cases. Key data from 1H NMR for the main isomer (CDCI3): δ 6.28 (dd, J = 5, 2; 2H, C5-lnd), 3.16 (s, 2H, C5-Ind), -0.18 (s, 6H, SiMe2), -0.30 (s, 6H, SiMe2). Key data from 1H NMR for the minority isomer (CDCI3): δ 6.42 (dd, J = 5, 2; 2H, Cβ-lnd), 3.27 (s, 2H, Cs-lnd), - 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 Et2O (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) by syringe for 30 sec. the mixture was stirred for 10 min, and then allowed to warm to approximately 22 ° C for 16h while stirring. A suspension of ZrCl4 (1.90 g, 8.14 mmol) in toluene (50 mL) was prepared and cooled to -5 ° C. The lit (bis) solution obtained from the rac / meso bridge ligand was added to the cannula stirred zirconium suspension for 30 sec. The cooling bath was removed and the orange-yellow suspension was stirred to approximately 22 ° C for 16h. The yellow suspension was evaporated in vacuo and toluene (50 ml) was added by cannula. The suspension was centrifuged, and the supernatant solution was cannulated and evaporated in vacuo at 40 ° C to obtain rac / meso-MET3 (1: 1 rac / mesó) as a yellow solid. The solid was recrystallized twice from toluene to obtain pure meso-MET3. The NMR data for these samples in CDCI3 solution were equivalent to those reported in the “Journal of Organometallic Chemistry”, 1999, 585, 18-25, for the MET3 compound.
Polymerization Experiments: The resulting polymerization conditions and polymer properties for Examples 1-99 are summarized in Table I. Any listing of MET3 in Table I is intended to indicate the meso isomer of MET3, i.e., / -MET3. The H2 feed in Ethylene is listed in ppm on a weight basis (ppmw). Applicants believe that a quality problem with the batch of co-catalyst used in Examples 91-93 may have adversely affected the catalyst activity and the polymer properties of these examples. FIG. 1 illustrates the molecular weight distribution of the polymers of Examples 3, 5 and 7. For the copolymers of these examples, FIG. 1 demonstrates that Mw was substantially constant over a range of added hydrogen quantities. FIG. 2 illustrates the molecular weight distribution of the polymers of Examples 2, 6 and 15. For the homopolymers of these examples, FIG. 2 shows that Mw decreased as the amount of hydrogen added increased. FIG. 3 illustrates the molecular weight distribution of the polymers of Examples 2-3 and 16. For the polymers of these examples, FIG. 3 shows that Mw / Mn increased as the comonomer content increased, in the absence of added hydrogen. FIG. 4 illustrates the molecular weight distribution of the polymers of Examples 6-7 and 44-45 in 250 ppm of added hydrogen. FIG. 4 shows that the Mw and Mw / Mn of the copolymers were significantly higher than those of the homopolymer. FIG. 5 illustrates the turning radius versus the logarithm of the molecular weight for a linear pattern and the polymers of Examples 2-3 and 6-7, with data from SEC-MALS. FIG. 5 demonstrates that these polymers were substantially linear polymers with minimal amounts of LCB's (long chain branches). FIG. 6 illustrates Delta versus log G * (complex module) for the polymers of Examples 2-3 and 6-7. Similar to FIG. 5, the rheology data in FIG. 6 demonstrate that these polymers were substantially linear. FIG. 7 illustrates the catalyst activity versus the initial 1-hexene comonomer concentration for Examples 2-7 and 40-45 in varying amounts of added hydrogen. FIG. 7 demonstrates that the catalyst activities for these examples were substantially constant at a given comonomer concentration, even when hydrogen was added. Additionally, FIG. 7 shows that the catalyst activity generally decreased as the comonomer content increased. FIG. 8 illustrates graphs of first-order models of catalyst activity versus initial 1-hexene comonomer concentration for Examples 2-7 and 40-45. FIG. 8 demonstrates that the catalyst activities (abbreviated as A) of these examples varied uniformly with the concentration of comonomer (1-hexene) in a given hydrogen content, following the first exponential order profile of (eq.1) below, where k is is the slope.
FIG. 9 illustrates graphs of the fusion index logarithm versus the logarithm of the hydrogen feed concentration (hydrogen / ethylene) for the polymers of Examples 4-5, 7, and 17-24. FIG. 9 demonstrates the difference in the hydrogen response when a copolymer was being produced compared to when a homopolymer was being produced. FIG. 10 illustrates a graph of the high charge melt index versus the melt index for the polymers of Examples 4 and 17-24. FIG. 10 demonstrates that the shear rate ratio (HLMI / MI) was substantially constant over concentrations of a hydrogen band under homopolymer conditions. FIG. 11 illustrates a graph of zero shear viscosity versus average molecular weight, specifically log (770) versus log (Mw), for the polymers of Examples 2-3, 5-7, 18, 44-45, and 66- 67. FIG. 11 demonstrates that the low levels of long chain branches (LCB's) related to this invention. Linear ethylene polypolymers are observed to follow an energy law relationship between their zero shear viscosity, ηQ, and their average weight molecular weight, Mw, with an energy very close to 3.4. This relationship is shown by a straight line with a slope of 3.4 when the logarithm of 770 θ is shown in a graph versus the logarithm of Mw (labeled Linear PE in FIG. 11). Deviations from this linear polymer line are generally accepted to be caused by the presence of LCB's. Janzen and Colby presented a model that predicts the expected deviation from the log linear graph (7/0) vs. log (Mw) for given amounts of LCB content as a function of the polymer's Mw. See "Diagnosing long-chain branching in polyethylenes", J. Mol. Struct. 485-486, 569-584 (1999), which is incorporated here by reference in its entirety. The polymers of Examples 2-3, 5-7, 18, 44-45, and 66-67 deviated only slightly from the well-known “Arnett line” of energy law 3.4, which is used as an indication of a linear polymer (J. Phys. Chem. 1980, 84, 649 All of these polymers had LCB levels at or below the line representing 1 x 10'6 LCB's per carbon atom, which is equivalent to 0.001 LCB's per 1000 total carbon atoms.
Example Catalyst Catalyst Ativator Ativator Co-catalyst Temp Reactor Pressure H2 Feed in Ethylene 1- Hexene 1- Hexene / Ethylene PE Performance Catalyst Activity Activator Activity

权利要求:
Claims (10)
[0001]
1. Catalyst composition characterized by the fact that it comprises: (i) a support-activator comprising a solid oxide treated with an electron-withdrawing anion; and (ii) a loop-metallocene compound having formula (I): E (CpARAm) (CpBRBn) MXq
[0002]
2. Composition according to claim 1, characterized in that the support-activator comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica- sulfated alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-silica-coated alumina or any combination thereof .
[0003]
3. Composition according to claim 1, characterized in that the catalyst composition additionally comprises an organoaluminium compound, and in which the organoaluminium compound comprises trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylaluminium , triisobutylaluminium, tri-n-hexylaluminium, tri-n-octylaluminium, diisobutylaluminum hydride, diethylaluminium ethoxide, diethylaluminium chloride or any combination thereof.
[0004]
4. Composition according to claim 1, characterized in that the catalyst composition additionally comprises an aluminoxane compound, an organoboro or organoborate compound, an ionizing ion compound or any combination thereof.
[0005]
5. Composition, according to claim 1, characterized by the fact 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 bridging chain of 2 to 4 silicon atoms, where any substituents on atoms in the bridging chain independently are 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; and q is 2.
[0006]
6. Composition, according to claim 5, characterized by the fact that: M is Zr or Hf; CpA and CpB are independently a cyclopentadienyl or indenyl group; each RA and RB independently is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyla, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl or benzyl; and E is —SiMe2 — SiMe2—.
[0007]
7. Composition according to claim 1, characterized by the fact that the loop-metallocene compound having formula (I) comprises:
[0008]
8. Composition according to claim 1, characterized by the fact that E is a jumper chain having the formula - (SiR11AR11B) v—, where v is an integer from 2 to 8, and R11A and R11B they are independently H or a hydrocarbyl group having up to 18 carbon atoms or up to 12 carbon atoms.
[0009]
9. Composition according to claim 1, characterized by the fact that the electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitan phospho-tungstate or combinations thereof.
[0010]
10. Composition according to claim 1, characterized by the fact that the electron-withdrawing anion is selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate or combinations thereof.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/899,753|US8637616B2|2010-10-07|2010-10-07|Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects|

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US12/899,753|2010-10-07|

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PCT/US2011/055026|WO2012048067A2|2010-10-07|2011-10-06|Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects|BR122019024202-0A| BR122019024202B1|2010-10-07|2011-10-06|olefin polymerization process|