olefin polymerization process and catalyst composition capable of producing an olefin polymer

专利摘要:
CATALYSTS TO PRODUCE WIDE DISTRIBUTION OF MOLECULAR WEIGHT POLYOLEFINS IN THE ABSENCE OF ADDED HYDROGEN. The present invention provides a polymerization process using a dual metallocene catalyst system for the production of wide or biomodal distribution of molecular weights of polymers, generally in the absence of added hydrogen. Polymers produced from the polymerization process are also provided and these polymers can have an Mn in the range of about 9,000 to about 30,000 g / mol, and a small chain branch content that decreases as the molecular weight increases.
公开号:BR112013000397B1
申请号:R112013000397-9
申请日:2011-07-05
公开日:2020-12-29
发明作者:Qing Yang；Max P. Mcdaniel；Tony Crain；Youlu Yu
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 area of olefins, olefin polymerization catalysis, olefin catalyst compositions, methods for the polymerization and copolymerization of olefins, and polyolefins. More specifically, this invention relates to dual catalyst systems to produce polyolefins of molecular weight with wide or bimodal distribution in the absence of added hydrogen.
Molecular weight polyolefins of wide or bimodal distribution (homopolymers, copolymers, terpolymers, and the like) can be produced using various combinations of catalyst systems and polymerization processes. Such widely distributed or bimodal molecular weight polyolefins can be produced using a dual metallocene catalyst system, but generally requiring the presence of added hydrogen for this purpose. The addition of hydrogen gas to certain polymerization reactor systems, however, can adversely affect operating conditions of the reactor, as well as the resulting properties of the polymer produced, for example, polymer molecular weight or melt index.
It would be beneficial to produce polyolefins of wide or bimodal molecular weight distribution using a metallocene-based double catalyst system that does not require the addition of hydrogen in the polymerization reactor. Accordingly, the present invention is directed to this purpose. SUMMARY OF THE INVENTION
The present invention features polymerization processes using dual catalyst systems for the production of broad and / or bimodal polymers, generally in the absence of added hydrogen.
In accordance with an aspect of the present invention, a catalyst composition is provided, and that catalyst composition comprises catalyst component I, catalyst component II, and an activator. In another aspect, an olefin polymerization process is provided and, in this aspect, the process comprises contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, in which the The catalyst composition comprises the catalyst component I, catalyst component II, and an activator.
In these catalyst compositions and polymerization processes, catalyst component I can comprise: a compound having the formula (A); a compound having formula (B); a binuclear compound formed from an alkenyl-substituted compound having formula (A), formula (B), or a combination thereof; or any combination thereof, where:
formula (A) is M1 is Zr or Hf; X1 and X2 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E1 is C or Si; R1 and R2 are independently H, a hydrocarbon group having up to 18 carbon atoms, or R1 and R2 are connected to form a cyclic or heterocyclic group having up to 18 carbon atoms; and R3 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; and
formula (B) is Meso Isomer. where: M2 is Zr or Hf; X3 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 hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E2 is C or Si; R4 is H or a hydrocarbon group having up to 18 carbon atoms; and R5 is a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.
In these catalyst compositions and polymerization processes, catalyst component II may comprise: a compound having formula (C); a compound having formula (D); a compound having formula (E); a compound having formula (F); a binuclear compound formed from an alkenyl-substituted compound having formula (C), formula (D), formula (E), formula (F), or a combination thereof; or any combination thereof, where:
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 hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E3is a bridge group selected from: a cyclic or heterocyclic bridge group having up to 18 carbon atoms, a bridge group having the formula> E3AR7AR8A, where E3A is C or Si, and R7A and R8As are independently H or a hydrocarbon group having up to 18 carbon atoms, a bridge group having the formula —CR7BR8B — CR7CR8C—, where R7B, R8B, R7C, and R8C are independently H or a hydrocarbon group having up to 10 carbon atoms, or a bridge group having the formula —SiR7DR8D — SiR7ER8E—, where R7D, R8D, R7E, and R8Es are independently H or a hydrocarbon group having up to 10 carbon atoms; R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and R111 is a cinclopentadienyl or indenyl group, any substituent on R111 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms;
formula (D) is 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 hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E4is a bridge group selected from: a cyclic or heterocyclic bridge group having up to 18 carbon atoms, a bridge group having the formula> E4AR12AR13A, where E4A is C or Si, and R12A and R13As are independently H or a hydrocarbon group having up to 18 carbon atoms, a bridge group having the formula —CR12BR13B — CR12CR13C—, where R12B, R13B, R12C, and R13C are independently H or a hydrocarbon group having up to 10 carbon atoms, or a bridge group having the formula —SiR12DR13D — SiR12ER13E—, where R12D, R13D, R12E, and R13Es are independently H or a hydrocarbon group having up to 10 carbon atoms; and R14, R15, R16, and R17 are independently H or a hydrocarbon group having up to 18 carbon atoms;
formula (E) is 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 hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; and
E5is a bridge group selected from: a cyclic or heterocyclic bridge group having up to 18 carbon atoms, a bridge group having the formula> E5AR20AR21A, where E5A is C or Si, and R20A and R21As are independently H or a hydrocarbon group having up to 18 carbon atoms, a bridge group having the formula - (CH2) n—, where n is an integer from 2 to 6, inclusive, or a bridge group having the formula —SiR20BR21B — SiR20CR21C—, where R20B , R21B, R20C, and R21C are independently H or a hydrocarbon group having up to 10 carbon atoms; and
formula (F) is; where: M6 is Zr or Hf; X10 and X11 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; and R112 and R113 are independently a cyclopentadienyl, indenyl or fluorenyl group, any substituent on R112 and R113 is independently H or a hydrocarbon group having up to 18 carbon atoms. Polymers produced from the polymerization of olefins using these catalyst systems, resulting in homopolymers, copolymers, and the like, can be used to produce various articles of manufacture. In some aspects of this invention, an ethylene polymer produced here can be characterized by having the following properties of polymers: wide and / or bimodal molecular weight distribution (MWD); and / or Mn in the range of about 9,000 to about 30,000 g / mol; and / or an Mw / Mn ratio of about 4 to about 20; and / or a small chain branch content that decreases as the molecular weight increases. BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 illustrates the definitions of D90 and D10 on a molecular weight distribution curve.
FIG. 2 shows a representation of the molecular weight distributions of the polymers of Examples 1-4.
FIG. 3 shows a representation of the molecular weight distributions of the polymers of Examples 5-6.
FIG. 4 shows a representation of the molecular weight distributions of the polymers of Examples 7-10.
FIG. 5 shows a representation of the molecular weight distribution and the short chain branching distribution of the polymer of Example 5.
FIG. 6 shows a representation of the molecular weight distribution and the short chain branching distribution of the polymer of Example 6.
FIG. 7 shows a representation of the molecular weight distribution and the short chain branching distribution of the polymer of Example 11.
FIG. 8 shows a representation of the molecular weight distribution and the short chain branching distribution of the polymer of Example 12.
FIG. 9 presents a representation of the molecular weight distributions of the polymers of Examples 13-16. DEFINITIONS
To define more clearly the terms used here, the following definitions are provided. To the extent that any disclaimer or use provided by any document incorporated herein by reference in conflict with the definition or use provided here, the definition or use provided here prevails.
The term "polymer" is used here generically to include olefin homopolymers, copolymers, terpolymers, and the like. 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) shown here. 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 the comonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer would be categorized as 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 (e.g., ethylene) and an olefin comonomer (e.g., 1-hexene) to produce a copolymer.
Hydrogen in this disclosure can refer to either hydrogen (H2) that is used in a polymerization process, or a hydrogen atom (H), which can be present, for example, in a metallocene compound. When used to denote a hydrogen atom, hydrogen will be presented as "H," whereas if the intention is to present 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, aluminoxane compounds, organoboro or organoborate, and ionizing ion compounds, as shown 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 by which the compound can operate. In one aspect of this invention, the term "co-catalyst" is used to distinguish that component of a catalyst composition from metallocene compounds.
The terms “chemically treated solid oxide,” “support activator,” “treated solid oxide compound,” and the like, are used at present to indicate a relatively high porosity inorganic oxide solid, which may exhibit Lewis or Br0nsted acid behavior , and which has been treated with an electron removing component, typically an anion, and which is calcined. The electron removing component is typically an electron removing anion source compound. Thus, the chemically treated solid oxide may comprise the calcined contact product of at least one solid oxide with at least one electron-removing anion source compound. Typically, the chemically treated solid oxide comprises at least one acid solid oxide compound. The terms "support" and "activator-support" are not used to imply that these components are inert, and such components are not to be understood as an inert component of a 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 a binder that can be activated (eg, an alkyl, a hydride) in the metallocene, when the metallocene compound does not comprise such a binder, in 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 ionic compounds, and the like. Aluminoxane, organoboro or organoborate compounds, and ionizing ionic 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 ionic materials are typically referred to as co-catalysts.
The term "boron fluororgan compound" is used at present with its common meaning to refer to neutral compounds of the BY3 form. The term "fluororgan borate compound" also has its common meaning to refer to the monoanionic salts and salts of a boron fluororgan compound of the form [cation] + [BY4] -, where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as "organobromine or organoborate compounds".
The term "metallocene," as used herein, describes a compound comprising at least a q3 to q5-cycloalkadienyl-type moiety, wherein fractions q3 to q5-cycloalkadienyl include cyclopentadienyl binders, indenyl binders, fluorenyl binders, and the like, including partially saturated or substituted derivatives or the like. Possible substitutes in these binders can include H, so this invention comprises partially saturated binders such as tetrahydroindenyl, tetrahydrofluorenyl, octahidrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially saturated substituted indenyl, partially saturated substituted fluorenyl, and the like. In some contexts, metallocene is referred to simply as the "catalyst," and likewise the term "co-catalyst" is used at present to refer to, for example, an organoaluminium compound. Metallocene is also used generically here to encompass binocular metallocene compounds, i.e. compounds comprising two metallocene fractions linked by 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 actual product or composition resulting from the contact or reaction of the initial components of the claimed catalyst composition / mixture / system, the nature of the active catalytic site , or the fate of the co-catalyst, the metallocene compounds, any olefin monomer used to prepare a pre-contacted mixture, or the activator (eg, activator-support), after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture," "catalyst system," and the like, encompass the initial components of the composition, as well as any products may result from contacting these starting components, and this includes both catalyst systems or heterogeneous and homogeneous compositions.
The term "contact product" is used in the present to describe compositions in which components are contacted together in any order, in any way, and for any length of time. For example, components can be contacted by mixing or mixing. In addition, contacting any component may occur in the presence or absence of any other component of the compositions described here. Combining additional materials or components can be done by any suitable method. In addition, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Although "contact product" may include reaction products, it is not necessary for the respective components to react with one another. Similarly, the term "contacting" is used at present to refer to materials that can be mixed, mixed, slurryed, dissolved, reacted, treated, or otherwise contacted in another way.
The term "pre-contacted" mixture is used at present to describe a first mixture of the catalyst components that are contacted for a first period of time before the first mixture is used to form a "post-contacted" or second mixture of the catalyst components that are contacted for 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 organoaluminium compound (or compounds), before that mixture is contacted with a support activator (s ) and optional additional organoaluminium compound. Therefore, pre-contacted describes components that are used to contact each other, but before contacting the components in the second, post-contacted mix. Accordingly, this invention may occasionally distinguish between a component used to prepare the pre-contacted mixture and that component after the mixture has been prepared. For example, according to this description, it is possible for the pre-contacted organoaluminium compound, since it is contacted with the metallocene compound and the olefin monomer, to react to form at least one different chemical compound, formulation, or structure of the distinct organoaluminium compound used to prepare the pre-contacted mixture. In this case, the pre-contacted organoaluminium compound or component is described as comprising an organoaluminium compound that was used to prepare the pre-contacted mixture.
In addition, the pre-contacted mixture can describe a mixture of a metallocene compound (s) and organoaluminium compound (s), before contacting that mixture with an activator-support (s). Such a pre-contacted mixture may also describe a mixture of a metallocene compound (s), olefin monomer (s), and activator-support (s), before this mixture is contacted with an organoaluminum co-catalyst compound or compounds.
Similarly, the term "post-contacted" mixture is used at present to describe the second mixture of catalyst components that are contacted for a second period of time, and a constituent of which is the first "pre-contacted" mixture or catalyst components who were contacted for a first period of time. Typically, the term "post-contacted" mixture is used at present to describe the mixture of metallocene compound (s), olefin monomer (s), organoaluminium compound (s), and activator-support (s) formed from the contacting the pre-contacted mixture of a portion of these components with any additional components added to make up the post-contacted mixture. The support activator generally 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 as or different from the organoaluminium compound used to prepare the pre-contacted mixture, as described here. Accordingly, this invention may also occasionally distinguish between the component used to prepare the post-contacted mixture and that component after the mixture has been prepared.
Although any methods, devices, and materials similar or equivalent to those described here 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 and presenting, for example, the constructions and methodologies that are described in the publications, which can be used in connection with the described invention. The publications described throughout the text are provided only for your previous submission of the filing date of this application. Nothing should be understood as an admission that the inventors are not entitled to anticipate such a divination by virtue of a previous invention.
For any particular compound shown here, any specific or general structure shown also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents, unless stated otherwise.
Similarly, unless stated otherwise, the specific or general structure also encompasses all enantiomers, diateromers, and other optical isomers whether in the enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a person skilled in the art.
Applicants have several types of scope 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 particle sizes, a range of catalytic activities, a range of molecular weights, and others. When applicants present or claim a range of any kind, the applicant's intention is to individually present or claim each possible number that such range could reasonably encompass, including end points of scope as well as any sub-ranges and combinations of sub-ranges encompassed in the gift. For example, when the applicant submits or claims a chemical fraction having a certain number of carbon atoms, the applicant's intention is to individually present or claim each possible number that such scope could encompass, consistent with the present disclosure. For example, the presentation that a fraction is a C1 a C18 hydrocarb group, or in alternative language a hydrocarb group having up to 18 carbon atoms, as used here, refers to a fraction that can be selected independently of a hydrocarb 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 interval between these two numbers (for example example, a C1 a C8 hydrocarb group), and also including any combination of the interval between those two numbers (for example, a C2 a C4 and a C12 to C16 hydrocarb group).
Similarly, another representative example follows the Mn of an ethylene polymer provided in one aspect of this invention. By disclosing that Mn of an ethylene polymer can be in the range of about 9,000 to about 30,000 g / mol, Applicants intend to quote that Mn can be about 9,000, about 10,000, about 11,000, about 12,000 , about 13,000, about 14,000, about 15,000, about 16,000, about 17,000, about 18,000, about 19,000, about 20,000, about 21,000, about 22,000, about 23,000, about 24,000, about of 25,000, about 26,000, about 27,000, about 28,000, about 29,000, or about 30,000 g / mol. In addition, Mn can be within the range of about 9,000 to about 30,000 g / mol (for example, about 10,000 to about 25,000 g / mol), and this also includes any combination of the range between about 9,000 and about 30,000 g / mol (for example, Mn is in the range of about 9,000 to about 15,000 g / mol, or about 18,000 to about 28,000 g / mol). Likewise, all other scope presented here must be interpreted in a similar way to these two examples.
Claimants reserve the right to subject to the condition or to exclude any individual members of any such group, including any sub-ranges or combinations of sub-ranges within the group, which may be claimed under the scope or in any similar manner, if for whatever reason the claimant chooses to claim less than the total disclosure measure, for example, to consider the reference that claimants may not be aware of when filing the application. In addition, Claimants reserve the right to subject or exclude any individual substitutes, analogs, compounds, binders, structures, or groups thereof, or any members of a claimed group, if for any reason the claimant chooses to claim less than that the total measure of disclosure, for example, to consider the reference that applicants may not be aware of when filing the application.
The terms "the", "one", etc., are intended to include plural alternatives, e.g., at least one, unless otherwise specified. For example, the disclosure of "a support activator" or "a metallocene compound" is intended to encompass one, or mixtures or combinations of more than one support activator or 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" the 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) catalyst component I, (ii) catalyst component II, and (iii) an activator.
The following abbreviations are used in this disclosure: Bu - butyl D10 - the molecular weight in which 10% of the polymer by weight has the highest molecular weight. D15 - the molecular weight greater than 15% of the polymer by weight has D85 - the molecular weight greater than 85% of the polymer by weight has D90 - the molecular weight greater than 90% of the polymer by weight has Et - ethyl GPC - gel permeation chromatography HLMI - high charge fusion index M - molecular weight Me - methyl MI - fusion index Mn - average number of molecular weight Mw - average weight of molecular weight MWD - distribution of molecular weight Mz - average-z molecular weight Ph - phenyl Pr - propyl SCB - short chain branches SCBD - short chain branch distribution t-Bu - tert-butyl or t-butyl 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 the catalyst composition, such a catalyst composition comprising catalyst component I, catalyst component II, and an activator.
In another aspect, an olefin polymerization process is provided and, in this aspect, the process comprises contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, in which the The catalyst composition comprises the catalyst component I, catalyst component II, and an activator. In another aspect, the polymerization process can be conducted in the absence of added hydrogen.
Olefin homopolymers, copolymers, terpolymers, and the like, can be produced using the catalyst compositions and methods for olefin polymerization shown here. For example, an ethylene polymer of the present invention can be characterized in that it has a wide and / or bimodal molecular weight distribution (MWD); and / or Mn in the range of about 9,000 to about 30,000 g / mol; and / or an Mw / Mn ratio of about 4 to about 20; and / or a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D90 to the number of SCB per 1000 total carbon atoms of the polymer in D10 in a range from 1.1 to about 20 . CATALYST COMPONENT I
A catalyst composition of the present invention comprises catalyst component I, which can comprise: a compound having formula (A); a compound having formula (B); a binuclear compound formed from an alkenyl-substituted compound having formula (A), formula (B), or a combination thereof; or any combination thereof.
Formula (A) is M1 is Zr or Hf; X1 and X2 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl carbon group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E1 is C or Si; R1 and R2 are independently H, a hydrocarbon group having up to 18 carbon atoms, or R1 and R2 are connected to form a cyclic or heterocyclic group having up to 18 carbon atoms; and R3 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.
Formula (B) is Meso Isomer. where: M2 is Zr or Hf; X3 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 hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E2 is C or Si; R4 is H or a hydrocarbon group having up to 18 carbon atoms; and R5 is a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.
Unless otherwise specified, formulas (A) and (B) above, any other structural formula as shown here, and any metallocene species presented here are not designed to present stereochemistry or isomeric positioning of different fractions (eg, these formulas they are not intended to present cis or trans isomers, or R or S diastereisomers), although such compounds are contemplated and encompassed by these formulas and / or structures. Thus, all compounds within formula (B) are in the meso isomer of such compounds.
Hydrocarbyl is used herein to specify a hydrocarbon radical group that includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkyl, and the like, and includes all derivatives substituted, unsubstituted, linear, and / or branched. 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 hydrocarbiloxide group, therefore, is used generically to include both the alkoxide and aryloxide groups, and these groups can comprise up to about 18 carbon atoms. Illustrative and non-limiting examples of alkoxide and aryloxide groups (i.e., hydrocarbiloxide group) include methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like. The term hydrocarbilamino group is used generically to refer collectively to alkylamino, arylamino, dialkylamino, and diarylamino groups. Unless otherwise specified, the hydrocarbilamino groups of this invention comprise up to about 18 carbon atoms. Hydrocarbylsilyl groups include, but are not limited to, alkylsilyl groups, alkenylsilyl groups, arylsilyl groups, arylalkylsilyl groups, and the like, which have up to about 18 carbon atoms. For example, illustrative hydrocarbylsilyl groups can include trimethylsilyl and phenyloctylsilyl. These hydrocarbiloxide, hydrocarbilamino, and hydrocarbylsilyl groups can have up to 12 carbon atoms; alternatively, up to 10 carbon atoms; or alternatively, up to 8 carbon atoms, in other aspects of the present invention.
Unless otherwise specified, 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 diateromers are included within this definition. As an example, unless otherwise specified, the term propyl is intended to exclude n-propyl and iso-propyl, while the term butyl is intended to exclude n-butyl, iso-butyl, t-butyl, sec-butyl , and others. For example, non-limiting examples of octyl isomers include 2-ethyl hexyl and neooctyl. Suitable examples of alkyl groups that can be used 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 necessity. For example, specific alkenyl group substitutes 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 disclosure, aryl is intended to exclude aryl and arylalkyl groups, and these include, but are not limited to, phenyl, alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl, phenyl-substituted alkyl, naphthyl-substituted alkyl, and the like. Thus, 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 substituted aryl fraction used here is intended to exclude all regioisomers; for example, the term tolyl is intended to exclude any possible substitute position, which is, ortho, meta, or para.
In formula (A), M1 is Zr or Hf and E1 is C or Si.
X1 and X2 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.
X1 and X2 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X1 and X2 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X1 and X2 are independently benzyl, phenyl, or methyl. In yet another aspect, both X1 and X2 can be Cl; alternatively, both X1 and X2 can be benzyl; alternatively, both X1 and X2 can be phenyl; or alternatively, both X1 and X2 can be methyl.
In formula (A), R1 and R2 are independently H; a hydrocarbyl group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms; or R1 and R2 are connected to form a cyclic or heterocyclic group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. Cyclic groups include cycloalkyl and cycloalkenyl fractions and such fractions may include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. For example, bonding atoms E1, R1, and R2 can form a cyclopentyl or cyclohexyl moiety. Groups of cyclic heteroatoms-substituted can be formed with nitrogen, oxygen, or sulfur heteroatoms. While these heterocyclic groups can have up to 12 or 18 carbon atoms, heterocyclic groups can have groups of 3 members, 4 members, 5 members, 6 members, or 7 members in some aspects of this invention.
In one aspect of the present invention, R1 and R2 are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl , phenyl, tolyl, or benzyl. In another aspect, R1 and R2 are the same, and are either methyl, ethyl, propyl, butyl, pentyl, or phenyl. In another aspect, R1 and R2 are independently H or an alkyl or alkenyl terminal group having up to 8 carbon atoms. In yet another aspect, at least one of R1 and R2 is a terminal alkenyl group having up to 8 carbon atoms or, alternatively, up to 6 carbon atoms.
R3 in formula (A) is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms. In one aspect, R3 can be the hydrocarbyl group having up to 12 carbon atoms, while in another aspect, R3 can be a hydrocarbylsilyl group having up to 12 carbon atoms (e.g., R3 can be trimethylsilyl). In another aspect, R3 can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl , or benzyl. In yet another aspect, R3 is an alkyl or alkenyl terminal group having up to 8 carbon atoms, or alternatively, up to 6 carbon atoms. In yet another aspect, R3 is methyl, ethyl, propyl, butyl, pentyl, or hexyl.
It is contemplated in aspects of the invention that X1 and X2 independently can be F, Cl, Br, I, methyl, benzyl, or phenyl in formula (A), while R1 and R2 independently can be H or a hydrocarbon group having up to 12 atoms of carbon, and R3 can be a hydrocarbyl group having up to 12 carbon atoms. In another aspect, R1, R2, and R3 independently can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl , phenyl, tolyl, or benzyl.
Non-limiting examples of loop-metallocene compounds having formula (A) which are suitable for use in catalyst component I include, but are not limited to, the following:



Compounds within formula (B) that are suitable for use in catalyst component I are the meso isomer of the respective compounds. In formula (B), M2 is Zr or Hf and E2 is C or Si.
X3 can be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.
X3 can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X3 is Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X3 is benzyl, phenyl, or methyl. In yet another aspect, X3 can be Cl; alternatively, X3 can be benzyl; alternatively, X3 can be phenyl; or alternatively, X3 may be methyl.
In formula (B), R4 is H or a hydrocarbyl group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. In one aspect of the present invention, R4 is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In another aspect, R4 is methyl, ethyl, propyl, butyl, pentyl, or phenyl. In yet another aspect, R4 is an alkyl group having up to 8 carbon atoms.
R5 in formula (B) is a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms. In one aspect, R5 can be a hydrocarbyl group having up to 12 carbon atoms, while in another aspect, R5 can be a hydrocarbylsilyl group having up to 12 carbon atoms (eg, R5 can be an alkylsilyl, such as trimethylsilyl, or an alkenylsilyl ). In another aspect, R5 can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In yet another aspect, R5 is an alkyl or alkenyl terminal group having up to 8 carbon atoms, or alternatively, up to 6 carbon atoms. In yet another aspect, R5 is methyl, ethyl, propyl, butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, pentenyl, or hexenyl; or alternatively, R5 is propyl, butyl, propenyl, or butenyl.
According to one aspect of this invention, X3 can be F, Cl, Br, I, methyl, benzyl, or phenyl, while R4 can be a hydrocarbyl group having up to 12 carbon atoms, and R5 can be a hydrocarbyl group having up to 12 carbon atoms. According to another aspect, R4 and / or R5 can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl , phenyl, tolyl, or benzyl.
Non-limiting examples of loop-metallocene compounds, in their meso isomer forms, having formula (B) which are suitable for use in catalyst component I include, but are not limited to the following:



and the like, or any combination thereof.
Other representative metallocene compounds that can be used in catalyst component I in some aspects of this invention are disclosed in US Patent No. 7,026,494 and US Patent Publication 2009/0088543, the disclosures of which are incorporated herein by reference in their entirety.
The catalyst component I can also comprise a binuclear compound formed from an alkenyl-substituted compound having formula (A), formula (B), or a combination thereof. For example, a binuclear compound can be formed from an alkenyl-substituted compound having formula (A), an alkenyl-substituted compound having formula (B), two different alkenyl-substituted compounds having formula (A) , an alkenyl-substituted compound having formula (A) and an alkenyl-substituted compound having formula (B), and others. Binuclear metallocenes are described in Patent Application No. US 12 / 489,630 and Patent Publication No. US 2009/0170690, 2009/0170691, and 2009/0171041, the disclosures of which are incorporated herein by reference in their entirety. For example, binocular metallocene compounds can be formed from the following illustrative compounds having formula (A):

The first compound has an alkenyl substituent on the indenyl group and can be used to form a binuclear compound as described in Patent Publication No. US 2009/0170691. The second compound has an alkenyl substituent on the carbon-binding atom and can be used to form a binuclear compound as described in Patent Publication No. US 2009/0170690. The first compound and the second compound can be used together to form a heterodinuclear compound as described in patent application No. US 12 / 489,630. CATALYST COMPONENT II
A catalyst composition of the present invention comprises catalyst component II, which may comprise: a compound having formula (C); a compound having formula (D); a compound having formula (E); a compound having formula (F); a binuclear compound formed from an alkenyl-substituted compound having formula (C), formula (D), formula (E), formula (F), or a combination thereof; or any combination thereof.
Formula (C) is; where: M3 is Zr or Hf; X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E3is a bridge group selected from: a cyclic or heterocyclic bridge group having up to 18 carbon atoms, a bridge group having the formula> E3AR7AR8A, where E3A is C or Si, and R7A and R8As are independently H or a hydrocarbon group having up to 18 carbon atoms, a bridge group having the formula —CR7BR8B — CR7CR8C—, where R7B, R8B, R7C, and R8C are independently H or a hydrocarbon group having up to 10 carbon atoms, or a bridge group having the formula —SiR7DR8D — SiR7ER8E—, where R7D, R8D, R7E, and R8Es are independently H or a hydrocarbon group having up to 10 carbon atoms; R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and R111 is a cinclopentadienyl or indenyl group, any substituent on R111 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.
Formula (D) is 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 hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E4is a bridge group selected from: a cyclic or heterocyclic bridge group having up to 18 carbon atoms, a bridge group having the formula> E4AR12AR13A, where E4A is C or Si, and R12A and R13As are independently H or a hydrocarbon group having up to 18 carbon atoms, a bridge group having the formula —CR12BR13B — CR12CR13C—, where R12B, R13B, R12C, and R13C are independently H or a hydrocarbon group having up to 10 carbon atoms, or a bridge group having the formula —SiR12DR13D — SiR12ER13E—, where R12D, R13D, R12E, and R13Es are independently H or a hydrocarbon group having up to 10 carbon atoms; and R14, R15, R16, and R17 are independently H or a hydrocarbon group having up to 18 carbon atoms.
Formula (E) is M5 is Zr or Hf; X8 and X9 are independently F; Cl; Br; OBR2 or SO3R, where R is an alkyl or carbon group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; and E5 is a bridge group selected from: a cyclic or heterocyclic bridge group having up to 18 carbon atoms, a bridge group having the formula> E5AR20AR21A, where E5A is C or Si, and R20A and R21As are independently H or a hydrocarbyl group having up to 18 carbon atoms, a bridge group having the formula - (CH2) n—, where n is an integer from 2 to 6, inclusive, or a bridge group having the formula —SiR20BR21B — SiR20CR21C—, where R20B, R21B, R20C, and R21C are independently H or a hydrocarbon group having up to 10 carbon atoms.
Formula (F) is; where: M6 is Zr, or Hf; X10 and X11 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; and R112 and R113 are independently a cyclopentadienyl, indenyl or fluorenyl group, any substituent on R112 and R113 is independently H or a hydrocarbon group having up to 18 carbon atoms.
As noted above, unless otherwise specified, formulas (C), (D), (E), and (F), or any other structural formula as shown here, and any metallocene species presented here are not designed to present stereochemistry or isomeric positioning of different fractions (eg, these formulas are not intended to present cis or trans isomers, or R or S diastereisomers), although such compounds are contemplated and encompassed by these formulas and / or structures.
In formula (C), M3 is Zr or Hf. X4 and X5 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.
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, both X4 and X5 can be methyl.
In formula (C), E3 is a bonding group. According to one aspect of this invention, E3 can be a cyclic or heterocyclic bridge group having up to 18 carbon atoms, or alternatively, up to 12 carbon atoms. Cyclic groups include cycloalkyl and cycloalkenyl fractions and such fractions may include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. For example, E3 can be a cyclopentyl or cyclohexyl fraction. Groups of cyclic heteroatoms-substituted can be formed with nitrogen, oxygen, or sulfur heteroatoms. While these heterocyclic groups can have up to 12 or 18 carbon atoms, heterocyclic groups can be groups of 3 members, 4 members, 5 members, 6 members, or 7 members in some aspects of this invention.
According to another aspect of this invention, E3 is a bridge group having the formula> E3AR7AR8A, where E3A is C or Si, and R7A and R8As are independently H or a hydrocarbon group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. carbon. For example, R7A and R8A independently can be H or an alkyl, alkenyl (e.g., a terminal alkenyl), or aryl group having up to 12 carbon atoms. Illustrative non-limiting examples of suitable "aryl" fractions for R7A and / or R8A include phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like. In one aspect, R7A and R8As are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In another aspect, R7A and R8As are the same, and are methyl, ethyl, propyl, butyl, pentyl, or phenyl. In yet another aspect, at least one of R7A and R8A is phenyl. In yet another aspect, at least one of R7A and R8A is a terminal alkenyl group having up to 6 carbon atoms.
According to another aspect of this invention, E3 is a bridge group having the formula —CR7BR8B — CR7CR8C—, in which R7B, R8B, R7C, and R8C are independently H or a hydrocarbon group having up to 10 carbon atoms or, alternatively, up to 6 carbon atoms. For example, R7B, R8B, R7C, and R8C independently can be H or an alkyl or an alkenyl group having up to 6 carbon atoms; alternatively, R7B, R8B, R7C, and R8C independently can be H, methyl, ethyl, propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R7B, R8B, R7C, and R8C independently can be H, methyl, or ethyl; alternatively, R7B, R8B, R7C, and R8C can be H; or alternatively, R7B, R8B, R7C, and R8C can be methyl.
According to another aspect of this invention, E3 is a bridge group having the formula —SiR7DR8D — SiR7ER8E—, in which R7D, R8D, R7E, and R8Es are independently H or a hydrocarbon group having up to 10 carbon atoms or, alternatively, up to 6 carbon atoms. Accordingly, in aspects of this invention, R7D, R8D, R7E, and R8E independently can be H or an alkyl or an alkenyl group having up to 6 carbon atoms; alternatively, R7D, R8D, R7E, and R8E independently can be H, methyl, ethyl, propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R7D, R8D, R7E, and R8E independently can be H, methyl, or ethyl; alternatively, R7D, R8D, R7E, and R8E can be H; or alternatively, R7D, R8D, R7E, and R8E can be methyl.
R9 and R10 in the fluorenyl group in formula (C) are independently H or a hydrocarbon group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Accordingly, R9 and R10 independently may be H or a hydrocarbon group having up to 8 carbon atoms, such as, for example, alkyl groups: methyl, ethyl, propyl, butyl, pentyl, or hexyl, and the like. In some aspects, R9 and R10 are independently methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl, while in other aspects, R9 and R10 are independently H or t-butyl. For example, both R9 and R10 can be H or, alternatively, both R9 and R10 can be t-butyl.
In formula (C), R111 is cyclopentadienyl or indenyl. Generally, R111 is the cyclopentadienyl group. Any substituent on R111 can be H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; or alternatively, any substituent can be H or a hydrocarbyl or hydrocarbylsilyl group having up to 12 carbon atoms. Possible substitutes in R111 can include H, so this invention comprises partially saturated binders such as tetrahydroindenyl, partially saturated indenyl, and the like.
In one aspect, R111 has no additional substitutions in addition to those shown in formula (C), e.g., no substituents other than the linking group E3. In another aspect, R111 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, R111 group may have a single H, methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, or substituted 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 R111 both have no additional substituents or group R111 can have a single one selected from H or an alkyl, alkenyl, alkylsilyl, or alkenylsilyl group having up to 8 carbon atoms. In these and other aspects, E3 can be cyclopentyl or cyclohexyl; alternatively, E3 can be a bridge group having the formula> E3AR7AR8A, where E3A is C or Si, and R7A and R8As are independently 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, E3 can be a bridge group having the formula —CR7BR8B — CR7CR8C—, where R7B, R8B, R7C, and R8C are independently H or methyl; or alternatively, E3 can be a bridge group having the formula —SiR7DR8D — SiR7ER8E—, where R7D, R8D, R7E, and R8Es are independently H or methyl.
Non-limiting examples of loop-metallocene compounds having formula (C) that are suitable for use in catalyst component II include, but are not limited to, the following:









and the like, or any combination thereof.
In formula (D), M4 is Zr or Hf. X6 and X7 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.
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 is a bonding group. According to one aspect of this invention, E4 can be a cyclic or heterocyclic bridging group having up to 18 carbon atoms, or alternatively, up to 12 carbon atoms. Cyclic groups include cycloalkyl and cycloalkenyl fractions and such fractions may include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. For example, E4 can be a cyclopentyl or cyclohexyl fraction. Groups of cyclic heteroatoms-substituted can be formed with nitrogen, oxygen, or sulfur heteroatoms. While these heterocyclic groups can have up to 12 or 18 carbon atoms, heterocyclic groups can be 3 members, 4 members, 5 members, 6 members, or 7 members groups in some aspects of this invention.
According to another aspect of this invention, E4 is a bridge group having the formula> E4AR12AR13A, where E4A is C or Si, and R12A and R13As are independently H or a hydrocarbon group having up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. carbon. For example, R12A and R13A independently can be H or an alkyl, alkenyl (e.g., a terminal alkenyl), or aryl group having up to 12 carbon atoms. Illustrative non-limiting examples of suitable "aryl" fractions for R12A and / or R13A include phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like. In one aspect, R12A and R13A independently can be an alkyl, a terminal alkenyl, or aryl group having up to 10 carbon atoms. In another aspect, R12A and R13As are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In yet another aspect, R12A and R13As are the same, and are methyl, ethyl, propyl, butyl, pentyl, or phenyl. In yet another aspect, at least one of R12A and R13A is phenyl and / or at least one of R12A and R13A is an alkenyl group terminal having up to 8 carbon atoms.
According to another aspect of this invention, E4 is a bridge group having the formula —CR12BR13B — CR12CR13C—, in which R12B, R13B, R12C, and R13C are independently H or a hydrocarbyl group having up to 10 carbon atoms or, alternatively, up to 6 carbon atoms. For example, R12B, R13B, R12C, and R13C independently can be H or an alkyl or an alkenyl group having up to 6 carbon atoms; alternatively, R12B, R13B, R12C, and R13C independently can be H, methyl, ethyl, propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R12B, R13B, R12C, and R13C independently can be H, methyl, ethyl, propyl, or butyl; alternatively, R12B, R13B, R12C, and R13C independently can be H, methyl, or ethyl; alternatively, R12B, R13B, R12C, and R13C can be H; or alternatively, R12B, R13B, R12C, and R13C can be methyl.
According to another aspect of this invention, E4 is a bridge group having the formula —SiR12DR13D — SiR12ER13E—, in which R12D, R13D, R12E, and R13Es are independently H or a hydrocarbon group having up to 10 carbon atoms or, alternatively, up to 6 carbon atoms. Accordingly, in aspects of this invention, R12D, R13D, R12E, and R13E independently can be H or an alkyl or an alkenyl group having up to 6 carbon atoms; alternatively, R12D, R13D, R12E, and R13E independently can be H, methyl, ethyl, propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R12D, R13D, R12E, and R13E independently can be H, methyl, ethyl, propyl, or butyl; alternatively, R12D, R13D, R12E, and 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 on the fluorenyl groups in formula (D) are independently H or a hydrocarbon group having up to 18 carbon atoms or, alternatively, having up to 12 carbon atoms. Accordingly, R14, R15, R16, and R17 independently may be H or a hydrocarbon 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 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 aspects, E4 can be cyclopentyl or cyclohexyl; alternatively, E4 can be a bridge group having the formula> E4AR12AR13A, where E4A is C or Si, and R12A and R13As are independently 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, E4 can be a bridge group having the formula —CR12BR13B— CR12CR13C—, where R12B, R13B, R12C, and R13C are independently H or methyl; or alternatively, E4 can be a bridge group having the formula - SiR12DR13D — SiR12ER13E—, where R12D, R13D, R12E, and R13Es are independently H or methyl.
Non-limiting examples of loop-metallocene compounds having formula (D) that are suitable for use in catalyst component II include, but are not limited to, the following:



In formula (E), M5 is Zr or Hf. X8 and X9 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms. 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 linking group. According to one aspect of this invention, E5 can be a cyclic or heterocyclic bridging group having up to 18 carbon atoms, or alternatively, up to 12 carbon atoms. Cyclic groups include cycloalkyl and cycloalkenyl fractions and such fractions may include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. For example, E5 can be a cyclopentyl or cyclohexyl fraction. Groups of cyclic heteroatoms-substituted can be formed with nitrogen, oxygen, or sulfur heteroatoms. While these heterocyclic groups can have up to 12 or 18 carbon atoms, heterocyclic groups can be groups of 3 members, 4 members, 5 members, 6 members, or 7 members in some aspects of this invention.
According to another aspect of this invention, E5 is a bridge group having the formula> E5AR20AR21A, in which E5A is C or Si, and R20A and R21As are independently H or a hydrocarbon group having up to 18 carbon atoms or, alternatively, up to 12 atoms of carbon. For example, R20A and R21A independently can be H or an alkyl, alkenyl (e.g., a terminal alkenyl), or aryl group having up to 12 carbon atoms. Illustrative non-limiting examples of suitable "aryl" fractions for R20A and / or R21A include phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like. In one aspect, R20A and R21A independently can be an alkyl, a terminal alkenyl, or an aryl group having up to 10 carbon atoms. In another aspect, R20A and R21As are independently H, methyl. ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In yet another aspect, R20A and R21As are the same, and are methyl, ethyl, propyl, butyl, pentyl, or phenyl. In yet another aspect, at least one of R20A and R21A is phenyl and / or at least one of R20A and R21A is an alkenyl group terminal having up to 8 carbon atoms.
According to another aspect of this invention, E5 is a bridge group having the formula - (CH2) n—, where n is an integer from 2 to 6, inclusive. The integer n can be 2, 3, or 4 in some aspects of this invention.
According to another aspect of this invention, E5 is a bridge group having the formula —SiR20BR21B — SiR20CR21C—, in which R20B, R21B, R20C, and R21C are independently H or a hydrocarbon group having up to 10 carbon atoms or, alternatively, up to 6 carbon atoms. Accordingly, in aspects of this invention, R20B, R21B, R20C, and R21C independently can be H or an alkyl or an alkenyl group having up to 6 carbon atoms; alternatively, R20B, R21B, R20C, and R21C independently can be H, methyl, ethyl, propyl, butyl, allyl, 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 aspects, E5 can be cyclopentyl or cyclohexyl; alternatively, E5 can be a bridge group having the formula> E5AR20AR21A, where E5A is C or Si, and R20A and R21As are independently 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, E5 can be a bridge group having the formula - (CH2) n—, where n is equal to 2, 3, or 4; or alternatively, E5 can be a bridge 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 in catalyst component II include, but are not limited to, the following:


In formula (F), M6 is Zr or Hf. X10 and X11 can independently be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group. The hydrocarbiloxide group, the hydrocarbilamino group, the hydrocarbylsilyl group and R can have up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.
X10 and X11 independently can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X10 and X11 independently are Cl, benzyl, phenyl, or methyl in one aspect of this invention. In another aspect, X10 and X11 are independently benzyl, phenyl, or methyl. In yet another aspect, both X10 and X11 can be Cl; alternatively, both X10 and X11 can be benzyl; alternatively, both X10 and X11 can be phenyl; or alternatively, both X10 and X11 can be methyl.
In formula (F), R112 and R113 are independently a cyclopentadienyl, indenyl or fluorenyl group. Generally, R112 and R113 are independently a cinclopentadienyl or indenyl group. Any substituent on R112 and R113 independently can be H or a hydrocarbyl group having up to 18 carbon atoms, or alternatively, any substituent can be H or a hydrocarbyl group having up to 12 carbon atoms. Possible substitutes at R112 and R113 can include H, so this invention comprises partially saturated binders such as tetrahydroindenyl, tetrahydrofluorenyl, octahidrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, and the like.
In one aspect, R112 and R113 have no substitutions other than those shown in formula (F), e.g., R112 and R113 independently can be an unsubstituted cyclopentadienyl or unsubstituted indenyl. In another aspect, R112 and / or R113 can have one or two substituents, and each substituent independently can be H or a hydrocarbon group having up to 10 carbon atoms, such as, for example, an alkyl, alkenyl, or aryl group. In yet another aspect, R112 and / or R113 can have one or two substituents, and each substitute independently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl , heptenyl, octenyl, phenyl, tolyl, or benzyl, while in other respects, each substituent independently can be methyl, ethyl, propyl, butyl, ethylenyl, propenyl, butenyl, or pentenyl.
In some aspects of this invention, X10 and X11 can independently be F, Cl, Br, I, benzyl, phenyl, or methyl, while R112 and R113 are independently an unsubstituted or unsubstituted cyclopentadienyl group. Alternatively, R112 and R113 can independently be substituted with one or two substituents, and those substituents can independently be H or a hydrocarbon group having up to 10 carbon atoms, such as, for example, methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, tolyl, or benzyl.
Non-limiting examples of unbound metallocene compounds having formula (F) that are suitable for use in catalyst component II include, but are not limited to, the following:
and the like, or any combination thereof.
Other representative metallocene compounds that can be used in the catalyst component II in some aspects of this invention are set out in U.S. Patent Nos. 7,199,073, 7,312,283, 7,456,243, and 7,521,572, the disclosures of which are incorporated herein by reference in their entirety.
Catalyst component II can also comprise a binuclear compound formed from an alkenyl-substituted compound having formula (C), formula (D), formula (E), formula (F), or a combination thereof.
For example, a binuclear compound can be formed from an alkenyl-substituted compound having formula (C), an alkenyl-substituted compound having formula (D), two different alkenyl-substituted compounds having formula (E) , an alkenyl-substituted compound having the formula (C) and an alkenyl-substituted compound having the formula (E), and others. Binuclear metallocenes are described in Patent Application No. US 12 / 489,630 and Patent Publication No. US 2009/0170690, 2009/0170691, and 2009/0171041, the disclosures of which are incorporated herein by reference in their entirety.
For example, binocular metallocene compounds can be formed from the following illustrative metallocene compounds having formula (C), formula (D), formula (E), and formula (F), respectively:

The metallocene compound having the formula (C) has an alkenyl substitute in the cyclopentadienyl group and can be used to form a binuclear compound as described in US Patent Publication No. 2009/0170691. The metallocene compounds having formula (D) and formula (E) have an alkenyl substitute on the silicon binding atom and can be used to form a binuclear compound as described in US Patent Publication No. 2009/0170690. The unbound metallocene compound having the formula (F) has an alkenyl substitute in the indenyl group and can be used to form a binuclear compound as described in Patent Publication No. US 2009/0171041. In addition, any of the two of these metallocene compounds with alkenyl substituents having formula (C), formula (D), formula (E), or formula (F) can be used together to form a heterodinuclear compound as described in Patent Application US No. 12 / 489,630. SUPPORT ACTIVATOR
The present invention encompasses several catalyst compositions containing an activator, which can be an activator-support. In one aspect, the support activator comprises a chemically treated solid oxide. Alternatively, the support activator may comprise a clay mineral, pillar clay, an exfoliated clay, an exfoliated jelly clay in another oxide matrix, a layered silicate material, a layered silicate material, an aluminosilicate mineral layered, an aluminosilicate mineral in layerless, or any combination thereof.
Generally, chemically treated solid oxides have improved acidity compared to the untreated solid oxide compound. The chemically treated solid oxide also functions as an activating catalyst compared to the 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 in the enhanced activity of the catalyst composition as a whole, compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that chemically treated solid oxide can function as an activator, even in the absence of an organoaluminium compound, aluminoxane compounds, organoboro or organoborate, ionizing ionic compounds, and the like.
The chemically treated solid oxide may comprise a solid oxide treated with an electron-removing anion. Although it is not intended to be limited by the following statement, it is believed that treatment of the solid oxide with an electron removing component increases or improves the acidity of the oxide. Therefore, the activator-support either has Lewis or Br0nsted acidity that is typically greater than the Lewis or Br0nsted acidity strength of untreated solid oxide, or the activator-support has a greater number of acid sites than solid oxide. untreated, or both. One method for quantifying the acidity of treated solid oxide and untreated solid oxide materials is by comparing the polymerization activities of treated and untreated oxides under acid catalyzed reactions.
Chemically treated solid oxides of this invention are generally formed from an inorganic solid oxide which exhibits Lewis acidic or Br0nsted acid behavior and has a relatively high porosity. The solid oxide is chemically treated with an electron removing component, typically an electron removing 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. Yet in 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 an inorganic solid oxide comprising oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of periodic table, or comprising oxygen and one or more elements selected from the lanthanide or 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, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3 , MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including mixed oxides thereof, and combinations thereof. For example, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination of these. themselves.
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 of single or multiple chemical phases with more than one metal combined with oxygen to form the solid oxide compound. Examples of mixed oxides that can be used in the support activator of the present invention include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay materials, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide of this invention also encompasses oxide materials such as silica-coated alumina, as described in Patent Publication No. US 2010-0076167, the disclosure of which is incorporated herein by reference in its entirety.
The electron remover component used to treat the solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide being treated (compared to the solid oxide that is not treated with at least one electron removing anion). According to one aspect of the present invention, the electron-removing component is an electron-removing 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 an electron-removing anion include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorsulfate, fluorborate, phosphate, fluorophosphate, trifluoracetate, triflate, fluorzirconate, fluortitanate, phosphor tungstate, and the like, and the like mixtures and combinations thereof. In addition, other ionic and non-ionic compounds that serve as sources for these electron-removing anions can also be employed in the present invention. It is contemplated that the electron-removing anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and the like, or any combination thereof, in some aspects of this invention. In other respects, the electron-removing anion may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorsulfate, fluorborate, phosphate, fluorophosphate, trifluoracetate, triflate, fluorzirconate, fluortitanate, and the like, or any combination thereof.
Therefore, for example, the support activator (eg, 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, silica-alumina fluoride, silica chloride -alumina, silica-alumina brominated, silica-alumina sulphate, silica-zirconia fluoride, silica-zirconia chloride, silica-zirconia bromine, silica-zirconia sulphate, silica-titania fluoridate, silica-coated fluoridated alumina, silica-coated alumina, sulphate-coated alumina phosphated silica-coated alumina, and the like, or combinations thereof. In some respects, the support activator comprises fluoridated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, it comprises fluoride silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, comprises fluoridated silica-zirconia; alternatively, it comprises silica-zirconia chloride; or alternatively, it comprises silica-coated fluorinated alumina.
When the electron-removing component comprises an electron-removing anion salt, the counterion or cation of that salt can be selected from any that allows the salt to reverse or decompose back to acid during calcination. Factors that indicate the suitability of the particular salt to serve as a source for the electron-removing anion include, but are not limited to, the solubility of the salt in the desired solvent, absence of adverse cation reactivity, ion matching effects between the cation and anion, hygroscopic properties acquired in the salt by the cation, and the like, and thermal stability of the anion. Examples of suitable cations in the electron-removing anion salt include, but are not limited to, ammonia, trialkyl ammonia, tetraalkyl ammonia, tetraalkyl phosphonium, H +, [H (OEt2) 2] +, and the like.
In addition, combinations of one or more different electron-removing anions are used to adjust the specific acidity of the support activator to the desired level. Combinations of electron removing 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 to employ one or two sources of electron-removing anion compounds in two or more separate contact steps.
Therefore, an example of such a process by which a chemically treated solid oxide is prepared is as follows: a selected solid oxide, or combination of solid oxides, is contacted with a first electron-removing anion source compound to form a first mixture; this first mixture is calcined and then contacted with a second electron-removing anion source compound to form a second mixture; the second mixture is then calcined to form a treated oxide solid. In such a process, the first and second compound electron-removing anion source can be either the same or different compounds.
According to another aspect of the present invention, the chemically treated solid oxide comprises a solid material inorganic oxide, a mixed material oxide, or a combination of inorganic oxide materials, which is chemically treated with an electron removing component, and optionally treated with an source of metal, 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, zinc-impregnated alumina chloride, titanium-impregnated alumina fluoride, zinc-impregnated alumina fluoride, zinc-impregnated silica-alumina chloride, silica fluoride -zinc-impregnated alumina, sulfated zinc-impregnated alumina, chlorinated zinc aluminate, fluorinated zinc aluminate, sulfated zinc aluminate, silica-coated alumina treated with hexafluortitanic acid, silica-coated alumina treated with zinc and then fluoridated, 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, may include, but is not limited to, gel transformation, gel co-transformation, impregnation of one compound into another, and the like . If desired, the metal-containing compound is added to or impregnated with the solid oxide in the form of a solution, and subsequently converted to metal supported by calcination. Accordingly, the solid inorganic oxide can further comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals. For example, zinc is generally used to impregnate solid oxide and can provide enhanced catalyst activity at a lower 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-removing anion. Following any contact method, the contacted mixture of solid compound, electron removing anion, and the metal ion is typically calcined. Alternatively, a solid oxide material, an electron-removing 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-removing anion sources. It is not necessary for the solid oxide to be calcined before contacting the electron-removing anion source. The contact product is typically calcined either before or after the solid oxide is contacted with the electron-removing anion source. The solid oxide can be calcined or non-calcined. Various processes for preparing solid oxide activator-supports that can be used in this invention have been reported. For example, such methods are described in US Patent No. 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, 6,632, 6,6, 6,6, 6,6, 6,6 Disclosures are hereby incorporated by reference in their entirety.
In accordance with an aspect of the present invention, the solid oxide material is chemically treated by contacting it with an electron removing component, typically an electron removing anion source. In addition, the solid oxide material is optionally chemically treated with a metal ion, and then calcined to form a solid oxide containing metal or impregnated with chemically treated metal. According to another aspect of the present invention, the solid oxide material and electron-removing anion source are contacted and calcined simultaneously. The method by which the oxide is contacted with the electron removing component, typically a salt or acid from an electron removing anion, may include, but is not limited to, gel transformation, gel co-transformation, impregnation of an compound in another, and the like. Therefore, following any contact method, the contacted mixture of solid oxide, electron-removing anion, and optional metal ion, is calcined. Activator-support solid oxide (ie, chemically treated solid oxide) Therefore it can be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with an electron-removing anion source compound (or compounds) to form a first mixture; and 2) calcining the first mixture to form the solid activator-support oxide. According to another aspect of the present invention, activator-support solid oxide (chemically treated solid oxide) is produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with the first electron-removing anion source compound for form a first mixture; 2) calcining the first mixture to produce a first calcined mixture; 3) contacting the first calcined mixture with a second electron-removing anion source compound to form a second mixture; and 4) calcining the second mixture to form the solid activator-support oxide.
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-removing anion source compound, where the solid oxide compound is calcined before, during or after contacting the source electron-removing anion, and where there is a substantial absence of aluminoxane compounds, organoboro or organoborate, and ionizing ionic compounds.
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 hours . 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. Calcination can be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Therefore, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350 ° C to about 550 ° C. Any suitable ambient atmosphere can be used during calcination. Generally, calcination is conducted in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.
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 the solid oxide chemically treated as a solid particle. For example, solid oxide material can be treated with a sulfate source (called a "sulfating agent"), a chloride ion source (called a "chlorination agent"), a fluoride ion source (called a “Fluorination agent”), or a combination thereof, and calcined to provide the solid activating oxide. Useful acid-support activators include, but are not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, silica-alumina chloride, silica-alumina chloride, silica-alumina fluoride, silica-alumina sulfate, silica-zirconia bromine, chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluoridated silica-titania, alumina treated with hexafluortitanic acid, silica-coated alumina treated with hexafluortitanic acid, silica-alumina treated with hexafluorhydrofluoric acid , fluoride boria-alumina, silica treated with tetrafluorboric acid, alumina treated with tetrafluorboric acid, alumina treated with hexafluorfosforic acid, pillar clay, such as 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 solid fluoride oxide in the form of a solid particle. The fluoride solid oxide can be formed by contacting a solid oxide with a fluorination agent. The fluoride ion can be added to the oxide by forming a slurry of the oxide in a suitable solvent such as alcohol or water including, but not limited to, one or three carbon alcohols because of its volatility and low surface tension. Examples of suitable fluorination agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluorborate (NH4BF4), ammonium silicofluoride (hexafluorsilicate) ((NH ) 2SiF6), ammonia hexafluorphosphate (NH4PF6), hexafluortitanic acid (H2TiF6), ammonia hexafluortitanic acid ((NH4) 2TiF6), hexafluorzironic acid (H2ZrF6), AlF3, NH4AlF4, combinations of the same, and the same. Triflic acid and ammonia triflate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as the fluorination agent, due to its ease of use and availability.
If desired, the solid oxide is treated with a fluorination agent during the calcination step. Any fluorination agent capable of intensively contacting the solid oxide during the calcination step can be used. For example, in addition to the fluorination agents previously described, volatile organic fluorination agents can be used. Examples of volatile organic fluorination agents useful in this aspect of the invention include, but are not limited to, freons, perfluorhexane, perfluorbenzene, fluoromethane, trifluorethanol, and the like, and combinations thereof. The calcination temperature should generally be high enough to decompose the compound and release fluoride. Hydrogen gas fluoride (HF) or fluorine (F2) can also be used with solid oxide if fluoridated while calcining. Silicon tetrafluoride (SiF4) and compounds containing tetrafluorborate (BF4-) can also be used. A convenient method of contacting the solid oxide with the fluorination agent is to vaporize a fluorination 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 solid particle. The solid oxide chloride is formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide to form a slurry of the oxide in a suitable solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a chloride source and intensively contacting the oxide during the calcination step can be used, such as SiCl4, SiMe2Cl2, TiCl4, BCl3, 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 can also be used with solid oxide during calcination. A convenient method of contacting the oxide with the chlorinating agent is to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.
The amount of fluoride or chloride ion present before calcination the solid oxide is generally about 1 to about 50% by weight, where the percentage weight 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 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, the halide oxide can be dried by any suitable method including, but not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible to start the 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, silica-alumina compounds with a high alumina content can be used, in which the alumina content of these silica-alumina compounds typically range from about 60% to about 90%, or from about 65% to about 80%, alumina by weight. According to yet another aspect of this invention, the solid oxide component comprises alumina without silica, and 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 solid particle.
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 by a process in which the alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt such as ammonium sulfate. This process is usually carried out 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, one or three carbon alcohols because of their volatility and low surface tension.
According to one aspect of this invention, the amount of sulfate ion present before calcination is from 0.5 to about 100 parts by weight of sulfate ion to about 100 parts by weight of oxide solid. 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 oxide solid, and further according to another aspect of this invention, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of oxide solid. 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 calcination immediately.
According to another aspect of the present invention, the activator-support used in the preparation of the catalyst compositions of this invention comprises an activator-support ion exchanger, including but not limited to silicate and aluminosilicate compounds or minerals, with or without layered structures. layers, and combinations thereof. In another aspect of this invention, ion-exchanged layered aluminosilicates such as pillar clays are used as support activators. When the acid support activator comprises an ion exchanger support activator, it can optionally be treated with at least one electron removing anion such as those shown here, although typically the ion exchanger support activator is not treated with an anion electron remover.
According to another aspect of the present invention, the support activator of this invention comprises clay minerals having interchangeable cations and layers capable of expanding. Typical clay mineral activator-supports include, but are not limited to, aluminosilicate in ion exchange layers such as pillar clays. Although the term "support" is used, it should not be interpreted as an inert component of a catalyst composition, instead it should be interpreted as an active part of the catalyst composition, because of its close association with the metallocene component.
In accordance with another aspect of the present invention, the clay materials of this invention encompass materials either in their natural state or which has been treated with various ions by wetting, ion exchange, or pillars. Typically, the activator-support clay material of this invention comprises clays that have been subjected to ion exchange with large cations, including cations from highly charged polynuclear metal complexes. However, the activator-support clay material of this invention also engages clays that have undergone ion exchange with simple salts, including, but not limited to, Al (III), Fe (II), Fe (III) salts, and Zn (II) with binders such as halide, acetate, sulfate, nitrate, or nitrite.
According to another aspect of the present invention, the support activator comprises a pillar clay. The term “pillar clay” is used to refer to clay materials that have been subjected to ion exchange with typically large cations of highly charged polynuclear metal complexes. Examples of such ions include, but are not limited to, Keggin ions which have charges such as 7+, various polyoxometallates, other large ions. Therefore, the term pillars refers to the simple exchange reaction that the interchangeable cations of a clay material are replaced with 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 in column-like structures. Therefore, once the clay is dried and calcined to produce the supporting pillars between layers of clay, the expanded lattice structure is maintained and the porosity is improved. The resulting pores may vary in shape and size as a function of the pillar material and the main clay material used. Examples of pillars and pillar clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); US Patent No. 4,452,910; US Patent No. 5,376,611; and US Patent No. 4,060,480; whose disclosures are hereby incorporated by reference in their entirety.
The pillar formation process uses clay minerals having interchangeable cations and layers capable of expanding. Any pillar clay that can enhance the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, suitable clay minerals for pillar formation include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; haloisites; vermiculites; micas; fluorine; 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 clay in an activator-support pillar comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
Pillar clay can be pretreated if desired. For example, a pillar bentonite is pretreated by drying at about 300 ° C under an inert atmosphere, typically anhydrous nitrogen, for about 3 hours, before adding it to the polymerization reactor. Although an exemplary 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, zeolites, inorganic oxides, phosphate inorganic oxides, and the like. In one aspect, typical support materials that are used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boron, torus, aluminophosphate, aluminum phosphate, silica-titania, silica / titania coprecipitate, 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 support activator. Once the pre-contacted mixture of metallocene compound (s), olefin monomer, and organoaluminium compound is contacted with the activator-support, the composition still comprising the activator-support is called a “post-contacted” mixture. The post-contacted mixture can be left in contact for a second period of time before being loaded into the reactor where the polymerization process will be 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 still comprising the organoaluminium is called a “post-contacted” mixture. The post-contacted mixture can be left in contact for a further period of time before being introduced into the polymerization reactor. ORGANOALUMINUM COMPOUNDS
In some respects, catalyst compositions of the present invention may comprise one or more organoaluminium compounds. Such compounds can include, but are not limited to, compounds having the formula: (RC) 3Al; where RC is an aliphatic group having 1 to 10 carbon atoms. For example, RC can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.
Other organoaluminium compounds that can be used in the catalyst composition as shown here can include, but are not limited to, compounds having the formula: Al (XA) m (XB) 3-m, where XA is the hydrocarbyl; XB is an alkoxide or an aryloxide, a halide, or a hydride; and m is 1 to 3, inclusive. Hydrocarbyl is used herein to specify a hydrocarbon radical group and includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkyl, and the like, and includes all substituted , unsubstituted, branched, linear, and / or substituted heteroatoms derived therefrom.
In one aspect, XA is the hydrocarbon 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 one having from 1 to 18 carbon atoms, a halide, or a hydride. In another aspect of the present invention, XB is selected independently from fluorine and chlorine. In yet another aspect, XB is chlorine.
In the formula, Al (XA) m (XB) 3-m, m is a number from 1 to 3 inclusive, and typically, m is 3. The value of m is not restricted to being an integer; therefore, this formula includes sesquihalide compounds or other compounds from organoalumin clusters.
Examples of organoaluminium compounds suitable for use in accordance with the present invention include, but are not limited to, trialkylaluminium compounds, dialkylaluminium halide compounds, dialkylaluminium alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. Specific non-limiting examples of suitable organoaluminium compounds include trimethylaluminium (TMA), triethylaluminium (TEA), tri-n-propylalumin (TNPA), tri-n-butylalumin (TNBA), triisobutylalumin (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 the pre-contacted mixture, before contacting that pre-contacted mixture with an activator-support to form the catalyst composition. When the catalyst composition is prepared in this manner, typically, but not necessarily, a portion of the organo-aluminum compound is added to the pre-contacted mixture and another portion of the organo-aluminum compound is added to the post-contacted mixture prepared when the pre-contacted mixture is contacted with the solid activator-support oxide. However, the entire organoaluminium compound can be used to prepare the catalyst composition either 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 either in the pre-contact or post-contact stage. When an organoaluminium compound is added in multiple steps, the amounts of the organoaluminium compound shown here include the total amount of the organoaluminium compound used in both pre-contacted and post-contacted mixtures, and any additional organoaluminium compound added in the polymerization reactor. Therefore, total amounts of organoaluminium compounds are presented 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 aluminoxane compounds, compositions, mixtures, or discrete 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 aluminoxane is provided as the poly (hydrocarbyl aluminum oxide), or in which aluminoxane is provided as a combination of an aluminum alkyl compound and a source of active protons such as water . Aluminoxanes are also referred to as poly (hydrocarbyl aluminum oxides) or organoaluminoxanes.
The other catalyst components are typically 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 the three. Cyclic aluminoxane compounds having the formula:
wherein R in that formula is a linear or branched alkyl having 1 to 10 carbon atoms, and p is an integer from 3 to 20, are encompassed by this invention. The AlRO fraction shown here also constitutes the repeat unit in a linear aluminoxane. Therefore, linear aluminoxanes having the formula:
wherein R in this formula is a linear or branched alkyl having 1 to 10 carbon atoms, and q is an integer from 1 to 50, are also encompassed by this invention.
In addition, aluminoxanes may have cage structures of the formula Rt5r + αRbr-αAl4rO3r, where Rt is a linear or branched terminal group having from 1 to 10 carbon atoms; Rb is a straight or branched alkyl bonding group having 1 to 10 carbon atoms; aft 3 or 4; and α is equal to nAl (3) - nO (2) + nO (4), where nAl (3) is the number of aluminum atoms of three coordinates, nO (2) is the number of oxygen atoms of two coordinates, and nO (4) is the number of oxygen atoms of four coordinates.
Therefore, aluminoxanes that can be used in the catalyst compositions of the present invention are generally represented by formulas such as (R-Al-O) p, R (R-Al-O) qAlR2, and the like. In these formulas, the group R is typically a straight or branched C1-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxane compounds that can be used 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 (isobutyl aluminum oxide), respectively. Also included in the scope of the invention is the use of an aluminoxane in combination with a trialkylaluminium, such as that disclosed in US Patent No. 4,794,096, incorporated herein by reference in its entirety.
The present invention contemplates many values of p and q in the formulas of aluminoxane (R-Al-O) p and R (R-Al-O) qAlR2, respectively. In some respects, p and q are at least 3. However, depending on how organoaluminoxane is prepared, stored and used, the value of p and q can vary within a single sample of aluminoxane, and such combinations of organoaluminoxanes are contemplated in this document.
In preparing a catalyst composition containing an aluminoxane, the molar ratio of total moles of aluminum to aluminoxane (or aluminoxanes) to the total moles of the 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 at intervals from about 0.01 mg / L to about 1000 mg / L, from about 0.1 mg / L to about 100 mg / L, or from about 1 mg / L L at about 50 mg / L.
Organoaluminoxanes can be prepared in several ways. Examples of organoaluminoxane preparations are shown in US Patent Nos. 3,242,099 and 4,808,561, the disclosures of which are incorporated herein by reference in their entirety. For example, water in an inert organic solvent can be reacted with an aluminum alkyl cup, such as (RC) 3Al, to form the desired organoaluminoxane compound. Although it is not intended to be limiting by any statement, it is believed that this synthetic method can yield a mixture of both linear and cyclic R-Al-O aluminoxane species, where both are encompassed by this invention. Alternatively, organoaluminoxanes are prepared by reacting an aluminum alkyl compound, such as (RC) 3Al, 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, boron fluorane compounds and borate fluorane compounds are contemplated.
Any boron fluororgane or fluororgane borate compound can be used with the present invention. Examples of fluororgan borate compounds that can be used in the present invention include, but are not limited to, fluorinated aryl borates such as N, N-dimethylaniline tetrakis (pentafluorfenyl) - borate, triphenylcarbene tetrakis (pentafluorfenyl) borate, lithium tetrakis- ( pentafluorfenil) borate, N, N-dimethylanilino tetrakis [3,5-bis (trifluormethyl) phenyl] borate, triphenylcarbene tetrakis [3,5-bis (trifluormethyl) phenyl] borate, and the like, or mixtures thereof. Examples of boron fluororgane compounds that can be used as co-catalysts in the present invention include, but are not limited to, tris (pentafluorfenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and the like, or mixtures of the same. Although not limited by the following theory, these examples of fluororgan borate and boron fluororgan compounds, and related compounds, are considered to form “poor coordination” anions when combined with organometallic or metallocene compounds, as presented in US Patent 5,919,983, whose disclosure 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 organobromic compound can be used. According to one aspect of this invention, the molar ratio of the total moles of organoboro compound or organoborate (or compounds) to the total moles of metallocene compounds in the catalyst composition is in the range of about 0.1: 1 to about 15 :1. Typically, the amount of boron fluororgane or fluororgane borate compound used is about 0.5 mol to about 10 mol of boron / borate compound per mol of metallocene compounds (catalyst component I, catalyst component II, and any other metallocene compound (s)). According to another aspect of this invention, the amount of boron fluororgan or fluororgan borate is from about 0.8 moles to about 5 moles of boron / borate compound per mole of metallocene compounds. IONIZING IONIC COMPOUNDS
The present invention further provides a catalyst composition that can comprise an ionic ionic compound. An ionic compound is an ionic compound that can function as a co-catalyst to enhance the activity of the catalyst composition. Although it is not intended to be bound by any theory, it is believed that the ionic ionic 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, although it is not intended to be bound by any theory, it is believed that the ionic ionic 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 ionic ionic compound is an independent activator or co-catalyst whether it ionizes the metallocene, abstracts a ligand so as to form an ion pair, weakens the metal-ligand bond in the metallocene, simply coordinates in a ligand, or activates the metallocene by another mechanism.
In addition, it is not necessary for the ionic ion compound to activate the metallocene compound (s) only. The activation function of the ionic ionic compound may be evident in the enhanced activity of the catalyst composition as a whole, compared to a catalyst composition that does not contain an ionic ionic compound.
Examples of ionizing ionic compounds include, but are not limited to the following compounds: tri (n-butyl) ammonia tetrakis (p-tolyl) borate, tri (n-butyl) ammonia tetrakis (m-tolyl) borate, tri (n-butyl) ) tetrakis ammonia (2,4-dimethylphenyl) borate, tri (n-butyl) ammonia tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonia tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tri (n-butyl) ammonia tetrakis (pentafluorfenyl) borate, N, N-dimethylanilino tetrakis (p-tolyl) borate, N, N-dimethylanilino tetrakis (m-tolyl) borate, N, N-dimethylaniline tetrakis (2,4- dimethylphenyl) borate, N, N-dimethylanilino tetrakis (3,5-dimethylphenyl) borate, N, N-dimethylanilino tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylaniline tetrakis (pentafluorfenyl) borate , triphenylcarbene tetrakis (p-tolyl) borate, triphenylcarbene tetrakis (m-tolyl) borate, triphenylcarbene tetrakis (2,4-dimethylphenyl) borate, triphenylcarbene tetrakis (3,5-dimethylphenyl) borate, triphenylcarbonate trifluormethyl) phenyl] borate, triphenylcarbene tetrakis (p entafluorfenil) borate, tropilium tetrakis (p-tolyl) borate, tropilium tetrakis (m-tolyl) borate, tropilium tetrakis (2,4-dimethylphenyl) borate, tropilium tetrakis (3,5-dimethylphenyl) borate, tropilium tetrakis [3,5 -bis (trifluormethyl) phenyl] borate, tropilium tetrakis (pentafluorfenyl) borate, lithium tetrakis (pentafluorfenil) borate, lithium tetrafenylborate, lithium tetrakis (p-tolyl) borate, lithium tetrakis (m-tolyl) 2,4-lithium -dimethylphenyl) borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluorborate, sodium tetrakis (pentafluorfenyl) borate, sodium tetrafenylborate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, sodium 2,4-dimethylphenyl) borate, sodium tetrakis (3,5-dimethylphenyl) borate, sodium tetrafluorborate, potassium tetrakis (pentafluorfenyl) borate, potassium tetrafenylborate, potassium tetrakis (p-tolyl) borate, potassium tetrakis (m-tolyl), borate potassium tetrakis (2,4-dimethylphenyl) borate, potassium tetrakis (3,5-dimethylphenyl) borate, potassium tetrafluorborate, lithium tetrakis (pentafluorfenil) aluminate, lithium tetrafenylaluminate, lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate, lithium tetrakis (2,4-dimethylphenyl) aluminate, lithium tetrakis (3,5-dimethylphenyl) aluminate, lithium , sodium tetrakis (pentafluorfenil) aluminate, sodium tetrafenylaluminate, sodium tetrakis (p-tolyl) aluminate, sodium tetrakis (m-tolyl) aluminate, sodium tetrakis (2,4-dimethylphenyl) aluminate, sodium tetrakis (3,5-dimethylphenyl) aluminate , sodium tetrafluoraluminate, potassium tetrakis (pentafluorfenyl) aluminate, potassium tetrafenylaluminate, potassium tetrakis (p-tolyl) aluminate, potassium tetrakis (m-tolyl) - aluminate, potassium tetrakis (2,4-dimethylphenyl) - dimethylphenyl) aluminate, potassium tetrafluoraluminate, and the like, or combinations thereof. Ionizing ion compounds useful in this invention are not limited to these; other examples of ionizing ionic compounds are presented in US Patent Nos. 5,576,259 and 5,807,938, the disclosures of which are incorporated herein by reference in their entirety. OLEFINE MONOMERS
Unsaturated reagents that can be used 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 polymerization homoprocesses 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 greater amount of ethylene (> 50 mol percentage) and a lower amount of comonomer (<50 mol percentage), although this is not a requirement. Comonomers that can be copolymerized with ethylene generally have 3 to 20 carbon atoms in their molecular chain.
Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins can be used 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 (eg, 1-octene), the four normal nonenes, the five normal decenes, and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins including, but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above. Styrene can also be 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 this regard, Examples of suitable olefin comonomers include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-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 similar, 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 the reactor zone to produce the copolymer is about 0.01 to about 50% by weight 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 the reactor zone is from about 0.01 to about 40 percent weight of comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into the reactor zone is about 0.1 to about 35 percent weight of comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into the reactor zone is about 0.5 to about 20 percent weight of comonomer based on the total weight of the monomer and comonomer.
Although it is not intended to limit by any theory, where branched, substituted, or functionalized olefins are used as reagents, it is believed that a steric impediment can prevent and / or delay the polymerization process. Therefore, branched and / or cyclic portions of the olefins removed in some way from the carbon-carbon double bond would not be expected to prevent the reaction so that the same olefin substitutes located closer to the carbon-carbon double bond can. According to one aspect of the present invention, at least one monomer / reagent is ethylene, so the polymerizations are either a homopolymerization involving only ethylene, or copolymerizations with different acyclic, cyclic, terminal, internal, linear, branched, substituted or not -replaced. 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
The present invention employs catalyst compositions containing catalyst component I, catalyst component II, and at least one activator. Catalyst compositions can be used to produce polyolefins - homopolymers, copolymers, and the like - for a variety of purposes and applications. Catalyst components I and II have been discussed above. In aspects of the present invention, it is contemplated that catalyst component I may contain more than one metallocene compound and / or catalyst component II may contain more than one metallocene compound. In addition, additional metallocene compounds - in addition to those specified in catalyst component I or catalyst component II - can be used in the catalyst composition and / or the polymerization process, as long as the additional metallocene compound (s) does not deviate from the advantages here presented. In addition, more than one activator can also be used.
Generally, catalyst compositions of the present invention comprise catalyst component I, catalyst component II, and at least one activator. In aspects of the invention, at least one activator can comprise at least one activator-support. Support activators useful in the present invention have been presented above. Such catalyst compositions may further comprise one or more of an organoaluminium compound or compounds (suitable organoaluminium compounds have also been discussed above). Therefore, a catalyst composition of this invention may comprise catalyst component I, catalyst component II, at least one activator-support, and at least one organoaluminium compound. For example, at least one activator-support can comprise fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, silica-alumina fluoridated, silica-alumina chlorinated, silica-alumina brominated, silica-alumina sulfated, silica-zirconia fluorinated, silica-chlorinated -zirconia, brominated silica-zirconia, sulphate silica-zirconia, fluoride silica-titania, fluoride silica-coated, alumina sulfate silica-coated, phosphate silica-coated alumina, and the like, or combinations thereof. Additionally, at least one organoaluminium compound may comprise trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride , and the like, or combinations thereof.
In another aspect of the present invention, a catalyst composition is provided that comprises catalyst component I, catalyst component II, at least one activator-support, and at least one organoaluminium compound, wherein that catalyst composition is substantially free of aluminoxane, organobromine compounds. or organoborate, ionizing ionic 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 ionic compounds. In these respects, the catalyst composition has a catalyst activity, to be discussed below, in the absence of these additional materials. For example, a catalyst composition of the present invention may consist essentially of catalyst component I, catalyst component II, a support activator, and an organoaluminium compound, in which no other material is present in the catalyst composition that would increase / decrease the activity of the catalyst composition for more than about 10% of the catalyst activity of the catalyst composition in the absence of such materials.
However, in other aspects of this invention, these activators / co-catalysts can be used. For example, a catalyst composition comprising catalyst component I, catalyst component II, and an activator-support, can further comprise an optional co-catalyst. Suitable co-catalysts in this regard include, but are not limited to, aluminoxane compounds, organobromine or organoborate compounds, ionizing ionic compounds, and the like, or any combination thereof. More than one co-catalyst can be present in the catalyst composition.
In a different aspect, a catalyst composition is provided that does not require an activator-support. Such a catalyst composition may comprise catalyst component I, catalyst component II, and at least one activator, wherein at least one activator comprises at least one aluminoxane compound, at least one organobromine or organoborate compound, at least one ionizing compound, or combinations of the ionic compounds. themselves.
In a particular aspect contemplated here, the catalyst composition is a double catalyst composition comprising an activator (one or more than one), only a catalyst I composed of metallocene, and only a catalyst II composed of metallocene. In these and other respects, the catalyst composition can comprise at least one activator; only a compound having formula (A), formula (B), or a binuclear compound formed from an alkenyl-substituted compound having formula (A), formula (B), or a combination thereof; and only a compound having formula (C), formula (D), formula (E), formula (F), or a binuclear compound formed from an alkenyl-substituted compound having formula (C), formula (D) , formula (E), formula (F), or a combination thereof. In some respects, the catalyst composition may comprise at least one activator, only a metallocene compound having formula (A) or formula (B), and only a metallocene compound having formula (C), formula (D), formula (E), or formula (F). For example, the catalyst composition can comprise at least one activator, only one metallocene compound having formula (A), and only one metallocene compound having formula (C); alternatively, the catalyst composition may comprise at least one activator, only a metallocene compound having formula (A), and only a metallocene compound having formula (D); alternatively, the catalyst composition can comprise at least one activator, only a metallocene compound having formula (A), and only a metallocene compound having formula (E); alternatively, the catalyst composition can comprise at least one activator, only a metallocene compound having formula (A), and only a metallocene compound having formula (F); alternatively, the catalyst composition can comprise at least one activator, only a metallocene compound having formula (B), and only a metallocene compound having formula (C); alternatively, the catalyst composition can comprise at least one activator, only a metallocene compound having formula (B), and only a metallocene compound having formula (D); alternatively, the catalyst composition can comprise at least one activator, only a metallocene compound having formula (B), and only a metallocene compound having formula (E); or alternatively, the catalyst composition can comprise at least one activator, only a metallocene compound having formula (B), and only a metallocene compound having formula (F). In these aspects, only two metallocene compounds are present in the catalyst composition, i.e., one catalyst component I composed of loop-metallocene and one catalyst component II composed of metallocene. It is also contemplated that the double metallocene catalyst composition may contain lesser amounts of an added metallocene compound (s), but this is not a necessity, and generally the double catalyst composition may consist essentially of the two aforementioned metallocene compounds, and in absence of any additional metallocene compounds, wherein any additional metallocene compounds would not increase / decrease the activity of the catalyst composition by more than about 10% of the catalyst activity of the catalyst composition in the absence of additional metallocene compounds.
This invention further encompasses methods of producing such catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
The metallocene compound of the catalyst component I, the metallocene compound of the catalyst component II, or both, may be pre-contacted with an olefinic monomer if desired, not necessarily the olefin monomer will be polymerized, and an organoaluminium compound for a first period before contacting this pre-contacted mixture with an activator-support. The first contact time period, the pre-contact time, between the metallocene compound, the olefinic monomer, and the organoaluminium compound typically range from a time period of about 1 minute to about 24 hours, for example, from about 0.05 hours to about 1 hour. Pre-contact times of about 10 minutes to about 30 minutes are also used. Alternatively, the pre-contact process is carried out in multiple stages, instead of a last stage, in which multiple mixtures are prepared, each comprising a different set of catalyst components. For example, at least two catalyst components are contacted forming a first mixture, then contacting the first mixture with at least one other catalyst component forming a second mixture, and others.
Multiple pre-contact steps can be performed in a single container or multiple containers. In addition, multiple pre-contact steps can be performed in series (sequentially), in parallel, or a combination of them. For example, a first mixture of two catalyst components can be formed in a first container, the second mixture comprising the first mixture plus an additional catalyst component can be formed in the first container or the second container, which is typically placed below the first container.
In another aspect, one or more of the catalyst components can be divided and used in different pre-contact treatments. For example, part of a catalyst component is loaded into a first pre-contact container to pre-contact with at least one other catalyst component, while the rest of the same catalyst component is loaded into a second pre-contact container to pre-contact with at least one other catalyst component, or is directly supplied to the reactor, or a combination thereof. Pre-contact can be carried out on any suitable equipment, such as tanks, agitated 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, catalyst component I, catalyst component II, activator-support, organo-aluminum co-catalyst, and optionally an unsaturated hydrocarbon) are contacted in the polymerization reactor simultaneously while the polymerization reaction is carried out. fulfilled. 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 continuously fed into the reactor, or it can be a step-by-step process, or batch in batch in which a batch of pre-contacted product is added to produce the catalyst composition. This pre-contact step can be performed for a period that can vary from a few seconds to several days or more. , or longer. In this regard, the continuous pre-contact stage 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 a catalyst component I composed of metallocene and / or metallocene catalyst component II, olefin monomer, and co-catalyst organoaluminium is contacted with the support activator, this composition (with the addition of the activator- support) is called a “post-contacted mix.” 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 support activator generally vary from about 1 minute to about 24 hours. In another aspect, the post-contact time is in the range of about 0.05 hours to about 1 hour. The pre-contact step, the post-contact step, or both can increase the productivity of the polymer compared to the same catalyst composition that is prepared without pre-contacting or post-contacting. However, neither the pre-contact step nor the post-contact step is necessary.
The post-contacted mixture can be heated to a temperature and for a period of time sufficient to allow adsorption, impregnation, or interaction of the pre-contacted mixture and the activator-support, so that the portion of the components of the pre-contacted mixture is immobilized, adsorbed, or deposited. Where heating is used, the post-contacted mixture is usually heated to a temperature of between about 0 ° F to about 150 ° F, or about 40 ° F to about 95 ° F.
According to one aspect of this invention, the weight ratio of catalyst component I to catalyst component II in the catalyst composition is generally in the range of about 100: 1 to about 1: 100. In another aspect, the weight ratio is in the range of about 75: 1 to about 1:75, about 50: 1 to about 1:50, or about 30: 1 to about 1: 30. In yet another aspect, the weight ratio of catalyst component I to catalyst component II in the catalyst composition is in the range of about 25: 1 to about 1:25. For example, the weight ratio can be in the range of about 20: 1 to about 1:20, from about 15: 1 to about 1:15, from about 10: 1 to about 1:10 from about 5: 1 to about 1: 5; from about 4: 1 to about 1: 4, or from about 3: 1 to about 1: 3.
When the pre-contact step is used, the molar ratio of the total mole of olefin monomer to the total mole of metallocene (s) in the pre-contacted mixture is typically in the range of about 1:10 to about 100,000: 1. The total moles of each component are used for this reason to consider aspects of this invention where more than one olefin monomer and / or more than one metallocene is used in the pre-contact step. In addition, this molar ratio can be in the range of about 10: 1 to about 1,000: 1 in another aspect of the invention.
Generally, the weight ratio of the organoaluminium compound to the activator-support 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 activator-support is in the range of about 3: 1 to about 1: 100, or about 1: 1 to about 1:50.
In some aspects of this invention, the weight ratio of metallocene compounds (total catalyst component I and catalyst component II) to the support activator is in the range of about 1: 1 to about 1: 1,000,000. If more than one support activator is used, this ratio is based on the total weight of the support activator. In another aspect, this weight ratio is in 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 metallocene compounds to the activator-support 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 activator-support per hour (abbreviated gP / (gAS-hr)) . In another aspect, the catalyst activity is greater than about 150, greater than about 250, or greater than about 500 gP / (gAS-hr). In yet another aspect, catalyst compositions of this invention are characterized by having the catalyst activity greater than about 1000, greater than about 1500, or greater than about 2000 gP / (gAS-hr). In yet another aspect, the catalyst activity is greater than about 2500 gP / (gAS-hr). This activity is measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90 ° C and a reactor pressure of about 450 psig (3103 kPa).
As discussed above, any combination of the metallocene compound of the catalyst component I and / or the catalyst component II, the support activator, the organoaluminium compound, and the olefin monomer, can be pre-contacted in some 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 the pre-contact step between any combination of these catalyst components is used for a first period of time, that pre-contacted mixture can be used in a subsequent post-contact step between any other combination of the catalyst components for a second time period. For example, one or more metallocene compounds, the organoaluminium compound, and 1-hexene can be used in the pre-contact step for a first period of time, and this pre-contacted mixture can then be contacted with the activator-support for form the post-contacted mixture that is contacted for a second period of time before starting the polymerization reaction. For example, the first contact time, the pre-contact time, between any combination of the metallocene compound (s), the olefinic monomer, the activator-support, and the organoaluminium compound can be about 1 minute at about 24 hours, about 3 minutes to about 1 hour, or about 10 minutes to about 30 minutes. The post-contacted mixture is optionally left in contact for a second period of time, the post-contact time, before starting the polymerization process. According to one aspect of this invention, the post-contact times between the pre-contacted mixture and any remaining catalyst components are about 1 minute to about 24 hours, or about 0.1 hour 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. One such process for polymerizing olefins in the presence of a catalyst composition of the present invention comprises contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises the catalyst component I, catalyst component II, and at least one activator. Catalyst component I can comprise a compound having formula (A); a compound having formula (B); a binuclear compound formed from an alkenyl-substituted compound having formula (A), formula (B), or a combination thereof; or any combination thereof. Catalyst component II can comprise a compound having formula (C); a compound having formula (D); a compound having formula (E); a compound having formula (F); a binuclear compound formed from an alkenyl-substituted compound having formula (C), formula (D), formula (E), formula (F), or a combination thereof; or any combination thereof
According to one aspect of the invention, the polymerization process employs a catalyst composition comprising the catalyst component I, catalyst component II, and at least one activator, wherein at least one activator comprises at least one activator-support. Such a catalyst composition may further comprise at least one organoaluminium compound. Suitable organoaluminium compounds may include, but are not limited to, trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide , diethyl aluminum chloride, and the like, or any combination thereof.
According to another aspect of the invention, the polymerization process employs a catalyst composition comprising only a catalyst I composed of metallocene (e.g., a metallocene compound having formula (A) or formula (B)); only a metallocene compound II catalyst (e.g., a metallocene compound having formula (C) or formula (D) or formula (E) or formula (F)); at least one support activator; and at least one organoaluminium compound.
According to yet another aspect of the invention, the polymerization process employs a catalyst composition comprising the catalyst component I, catalyst component II, and at least one activator, wherein at least one activator comprises at least one aluminum compound, at least one compound organoboro or organoborate, at least one ionic ionic compound, or combinations thereof.
The catalyst compositions of the present invention are intended for any method of polymerizing olefin 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 batch reactor, slurry reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations thereof. The polymerization conditions for the various types of reactor are well known to those skilled in the art. Gas phase reactors may comprise fluidized bed reactors or horizontal staged reactors. Slurry reactors can comprise vertical or horizontal circuits. High pressure reactors can comprise autoclave reactors or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes can use intermittent or continuous product discharge. Processes may also include direct partial or complete recylation of unreacted monomer, unreacted comonomer, and / or diluent.
Polymerization reactor systems of the present invention can 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 by a transfer device making it possible to transfer the polymers resulting from the first polymerization reactor in the second reactor. The desired polymerization conditions in one of the reactors may differ from the operational conditions of other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continuous polymerization. Multiple reactor systems can include any combination including, but not limited to, multiple circuit reactors, multiple gas phase reactors, a combination of gas phase circuits and reactors, multiple high pressure reactors, or a combination of high pressure reactors with gas phase circuit and / or reactors. 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 slurry circuit reactor comprising vertical or horizontal circuits. Monomer, diluent, catalyst, and comonomer can be continuously supplied to the circuit reactor where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of that reactor from the suspension comprising polymer particles and the diluent. The effluent from the reactor can be dried instantly to remove the solid polymer from the liquids comprising the diluent, monomer and / or comonomer. Various technologies can be used for this separation step including, but not limited to, instant drying which can include any combination of heat addition and pressure reduction; separation by means of cyclone action in either cyclone or hydrocyclone; or separation by centrifugation.
A typical slurry polymerization process (also known as the particle formation process) is disclosed, 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 the slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under the 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 bulk conditions where no diluents are used. An example is the polymerization of the propylene monomer as disclosed in US Patent No. 5,455,314, which is incorporated by reference here 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 flow of recycling containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product can be removed from the reactor and a new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for polymerizing gas phase olefins in multiple stages, in which olefins are polymerized in gas phase in at least two independent gas phase polymerization zones while supplying a polymer containing catalyst formed in a first zone polymerization process for a second polymerization zone. A type of gas phase reactor is disclosed in U.S. Patent Nos. 5,352,749, 4,588,790, and 5,436,304, each of which is incorporated herein by reference in its entirety.
According to yet another aspect of the invention, the 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. Monomer can be trapped in an inert gas stream and introduced into a reactor zone. Primers, catalysts, and / or catalyst components can be trapped in a gas 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 ideal polymerization reaction conditions.
According to yet another aspect of the invention, the polymerization reactor can comprise a polymerization solution reactor in which the monomer / comonomer is contacted with the catalyst composition by suitable stirring means. A carrier comprising an inert organic diluent or excess monomer can be used. If desired, the monomer / comonomer can have its vapor phase placed 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 the polymer solution in a reaction medium. Stirring can be used to obtain better 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 may further comprise any combination of at least one raw material supply system, at least one supply system for catalyst or catalyst components, and / or at least one polymer recovery system. Suitable reactor systems for the present invention can further comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis, 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. Polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. An appropriate polymerization temperature can be any temperature below the depolymerization temperature according to the Gibbs free energy equation. Typically, this includes about 60 ° C to about 280 ° C, for example, or about 60 ° C to about 110 ° C, depending on the type of polymerization reactor. In some reactor systems, the polymerization temperature is generally in the range of about 70 ° C to about 90 ° C, or from about 75 ° C to about 85 ° C.
Adequate 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 (6895 kPa). Pressure for gas phase polymerization is normally about 200 to 500 psig (1379 to 3447 kPa). High pressure polymerization in a tubular reactor or autoclave reactor is generally performed at about 20,000 to 75,000 psig (137895 to 517107 kPa). Polymerization reactors can also be operated in a supercritical region occurring at generally high temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
Aspects of this invention are directed to olefin polymerization processes comprising contacting a catalyst composition with an olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce an olefin polymer. The olefin polymer produced by the process can have an Mn in the range of about 9,000 to about 30,000 g / mol. In addition, or alternatively, the olefin polymer may have an Mw / Mn ratio of about 4 to about 20. In addition, or alternatively, the olefin polymer may have a wide and / or bimodal molecular weight distribution. In addition, or alternatively, the olefin polymer may have a small chain branch content that decreases as the molecular weight increases.
Aspects of this invention are also directed to olefin polymerization processes conducted in the absence of added hydrogen. Accordingly, an olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises the catalyst component I, catalyst component II, and at least one activator, and in which the polymerization process is conducted in the absence of added hydrogen. As shown above, catalyst component I can comprise a compound having formula (A); a compound having formula (B); a binuclear compound formed from an alkenyl-substituted compound having formula (A), formula (B), or a combination thereof; or any combination thereof. In addition, catalyst component II can comprise a compound having formula (C); a compound having formula (D); a compound having formula (E); a compound having formula (F); a binuclear compound formed from an alkenyl-substituted compound having formula (C), formula (D), formula (E), formula (F), or a combination thereof; or any combination thereof.
As would be recognized by a person skilled in the art, hydrogen can be generated in-situ by olefin catalyst compositions in various olefin polymerization processes, and the amount generated can vary depending on the specific catalyst composition and metallocene compound (s) used, the type of polymerization process used, the polymerization reaction codes used, and others. Therefore, although hydrogen may not be added to the polymerization reactor, it is contemplated that polymerization processes according to this invention can be carried out in the presence of about 1 to about 1000 ppm hydrogen or, more typically, in the presence of about 5 ppm at about 750 ppm, or in the presence of about 10 ppm at about 500 ppm hydrogen. Thus, hydrogen contents in the polymerization reactor can be in a range of about 12 ppm to about 475 ppm, from about 15 ppm to about 450 ppm, from about 20 ppm to about 425 ppm, or about from 25 ppm to about 400 ppm.
While in many aspects of this invention, hydrogen is not added during the polymerization process, applicants contemplate that the beneficial properties of the polymer resulting from the use of presented dual catalyst compositions (ie, catalyst component I and catalyst component II) are not limited to only circumstances where hydrogen is not added to the polymerization reactor. For example, Applicants contemplate that low levels of added hydrogen can be used, and the amount of hydrogen added may depend on the desired polymer molecular weight and / or polymer melt index, among other considerations.
According to one aspect of this invention, the ratio of hydrogen to the olefin monomer in the polymerization process can be controlled. This weight ratio can generally range from about 1 ppm to about 1000 ppm of hydrogen, based on the weight of the olefin monomer. For example, the reagent or hydrogen supply ratio for the olefin monomer can be controlled in a weight ratio that falls within a range of about 5 ppm to about 900 ppm, from about 7 ppm to about 750 ppm, or from about 10 ppm to about 500 ppm. In addition, the reagent or hydrogen supply ratio for the olefin monomer can be controlled in a weight ratio over a range of about 15 ppm to about 475 ppm, from about 20 ppm to about 450 ppm, or from about 25 ppm to about 400 ppm, in some aspects of that invention.
In polymerizations of ethylene, the ratio of hydrogen supply to ethylene monomer, irrespective of the comonomer (s) used, can be controlled in a weight ratio within a range of about 1 ppm to about 1000 ppm; alternatively, from about 5 ppm to about 900 ppm; alternatively, from about 7 ppm to about 750 ppm; alternatively, from about 10 ppm to about 500 ppm; alternatively, from about 15 ppm to about 475 ppm; alternatively, from about 20 ppm to about 450 ppm; or alternatively, from about 25 ppm to about 400 ppm.
In another aspect, the ratio of reagent or hydrogen supply to olefin monomer is kept substantially constant during the course of the polymerization for a particular polymer classification. That is, the hydrogen: olefin ratio is selected at a particular ratio within the range of about 1 ppm to about 1000 ppm, and maintained at a ratio within about +/- 25% during the occurrence of the polymerization. For example, if the desired ratio is 100 ppm, then keeping the hydrogen: olefin ratio substantially constant would maintain the supply 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 course of the polymerization operation for a particular polymer classification.
However, in another aspect, it is contemplated that monomer, comonomer (or comonomers), and / or hydrogen can be periodically pulsed to the reactor, for example, in a manner similar to that used in US Patent No. 5,739,220 and Patent Publication No. US 2004/0059070, the disclosures 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 product for final use that will be formed by the polymer resin and the method of formation of that final product can determine the properties and attributes of the desired polymer. Mechanical properties include stress, bending, impact, creep, stress and hardness testing. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization temperature, density, stereoregularity, crack growth, long chain branching, and rheological measurements.
This invention is also directed to, and encompasses the polymers produced by any of the polymerization processes presented here. Manufacturing articles can be formed of, and / or can comprise the polymers produced in accordance with this 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 various 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 about 0.001 to about 100 g / 10 min. melting indices in the range of about 0.001 to about 75 g / 10 min, about 0.01 to about 50 g / 10 min, or about 0.05 to about 30 g / 10 min, are contemplated in some aspects of that invention. For example, a polymer of the present invention can have a melt index (MI) in the range of about 0.05 to about 25, or about 0.1 to about 10 g / 10 min.
Ethylene polymers produced according to this invention can have an HLMI / MI ratio in the range of about 5 to about 150, such as, for example, from about 10 to about 125, from about 10 to about from 100, from about 15 to about 90, from about 15 to about 80, from about 20 to about 70, or from about 25 to about 65.
The density of ethylene-based polymers produced using the catalyst systems and processes presented here typically fall within the range of about 0.88 to about 0.97 g / cm3. In one aspect of this invention, the density of an ethylene polymer is in the range of about 0.90 to about 0.95 g / cm3. In yet another aspect, the density is in the range of about 0.91 to about 0.945 g / cm3, such as, for example, from about 0.92 to about 0.945 g / cm3.
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 weight (Mw) to the average molecular weight number (Mn) - in a range of about 4 to about 20. In some aspects presented here, the Mw / Mn ratio is in the range of about 4 to about 18, about 4 to about 16, about 4.2 to about 16 , or from about 4.2 to about 15. For example, the Mw / Mn of the polymer can be within a range of about 4.2 to about 12, about 4.2 to about 10, about 4.3 to about from 8, or from about 4.3 to about 7.5.
The Mz / Mw ratio for the polymers of this invention is generally in the range of about 2.2 to about 10. Mz is the z-average of molecular weight, and Mw is the average weight of molecular weight. According to one aspect, the Mz / Mw of the ethylene polymers of this invention is in the range of about 2.2 to about 8, about 2.2 to about 7, about 2.3 to about 7, about 2.4 to about 6, or about 2.5 to about 5.
Ethylene polymers may have, in some aspects of this invention, an Mn within a range of about 7,000 to about 40,000 g / mol, such as, for example, about 8,000 to about 35,000, or about 9,000 at about 30,000 g / mol. Accordingly, the Mn of the ethylene polymer can be within a range of about 9,000 to about 28,000 g / mol in aspects of this invention; alternatively, from about 9,500 to about 26,000 g / mol; alternatively, from about 9,500 to about 25,000 g / mol; alternatively, from about 10,000 to about 25,000 g / mol; alternatively, from about 10,500 to about 24,000 g / mol; or alternatively, from about 11,000 to about 23,000 g / mol.
Ethylene polymers (eg, copolymers) produced using the polymerization processes and catalyst systems described above may have a small chain branch content that decreases as the molecular weight increases, ie, higher molecular weight components of the polymer generally have lesser comonomer incorporation incorporation than the lower molecular weight components, or decreasing incorporation of comonomer with decreasing molecular weight. Generally, the amount of comonomer incorporation at higher molecular weights can be about 20% less, or about 30% less, or about 50% less, or about 70% less, or about 90% less, than lower molecular weights. For example, the number of short chain branches (SCB) per 1000 total carbon atoms may be higher in Mn than in Mw. Ethylene polymers of this invention may have SCBD (short chain branch distribution) which is similar to SCBD found in ethylene polymers produced using traditional Ziegler-Natta catalyst systems.
In addition, SCBD (short chain branch distribution) of polymers of the present invention can be characterized by the ratio of the number of SCB per 1000 total carbon atoms of the polymer in D90 to the number of SCB per 1000 total carbon atoms of the polymer in D10, ie, (SCB in D90) / (SCB in D10). D90 is the molecular weight in which 90% of the polymer by weight has the highest molecular weight, and D10 is the molecular weight in which 10% of the polymer by weight has the highest molecular weight. D90 and D10 are shown graphically in FIG. 1 for a molecular weight distribution curve as a function of increasing a logarithm of molecular weight. According to one aspect of the present invention, a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D90 to the number of SCB per 1000 total carbon atoms of the polymer in D10 is in a range from about 1.1 to about 20. For example, the ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D90 to the number of SCB per 1000 total carbon atoms of the polymer in D10 can be in the range of about 1.1 to about 10, or about 1.2 to about 6, or from about 1.2 to about 3. Generally, polymers shown here have about 1 to about 20 chain branches short (SCB) per 1000 total carbon atoms at D90, and this typically varies with the density of the polymer.
Likewise, the polymer SCBD of the present invention can be characterized by the ratio of the number of SCB per 1000 total carbon atoms of the polymer in D85 to the number of SCB per 1000 total carbon atoms of the polymer in D15, ie, (SCB in D85) / (SCB in D15). D85 is the molecular weight in which 85% of the polymer by weight has the highest molecular weight, and D15 is the molecular weight in which 15% of the polymer by weight has the highest molecular weight. According to one aspect of the present invention, a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D85 to the number of SCB per 1000 total carbon atoms of the polymer in D15 is at a range from about 1.1 to about 18. For example, the ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D85 to the number of SCB per 1000 total carbon atoms of the polymer in D15 it can be in the range of about 1.1 to about 10, or about 1.2 to about 6, or about 1.2 to about 4, or from about 1.2 to about 2.5.
An illustrative and non-limiting example of an ethylene polymer of the present invention can be characterized by a wide and / or bimodal molecular weight distribution; and / or an Mn in the range of about 9,000 to about 30,000 g / mol; and / or an Mw / Mn ratio of about 4 to about 20; and / or a ratio of the number of SCBs per 1000 total carbon atoms of the polymer in D90 to the number of SCBs per 1000 total carbon atoms of the polymer in D10 in a range from 1.1 to about 10; and / or a ratio of the number of SCBs per 1000 total carbon atoms of the polymer in D85 to the number of SCBs per 1000 total carbon atoms of the polymer in D15 in a range of 1.1 to about 8. Such illustrative polymers can also still be characterized by an MI in a range of about 0.01 to about 50 g / 10 min, and / or an HLMI / MI ratio in a range of about 20 to about 80, and / or a density in a range from about 0.91 to about 0.945 g / cm3.
Ethylene polymers, or homopolymers, copolymers, terpolymers, and the like, can be formed into various articles of manufacture. Items that may comprise polymers of this invention include, but are not limited to, an agricultural film, an auto part, a bottle, a drum, a fiber or fabric, a food packaging film or container, a food service item, a bowl of food, a geomembrane, a household container, a liner, a molded product, a medical device or material, a pipe, a tape or daughter, a toy and the like. Various processes can be used to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming and the like. In addition, additives and modifiers are actually added to these polymers in order to provide processing benefits for the polymer or attributes for the end use product. EXAMPLES
The invention is further illustrated by the following examples, which should not be interpreted in any way to impose limitations on the scope of this invention. Various other aspects, modalities, modifications, and equivalents thereof, which, after reading the following description, can be suggested to a person skilled in the art without departing from the principles of the present invention or the scope of the appended claims.
Melting index (MI, g / 10 min) was determined according to ASTM D1238 at 190 ° C with a weight of 2,160 grams.
High charge melt index (HLMI, g / 10 min) was determined according to ASTM D1238 at 190 ° C with a weight of 21,600 grams.
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 TCB. An injection volume of 200 μL was used with the nominal polymer concentration of 1.5 mg / mL. Dissolution of the sample in stabilized TCB was performed by heating at 150 ° C for 5 hours with occasional, slight agitation. The columns used were three PLgel Mixed A LS columns (7.8x300mm) and were calibrated with a wide standard linear polyethylene (Phillips Marlex® BHB 5003) by which the molecular weight was determined.
Short chain branch distribution (SCBD) data were obtained using a SEC-FTIR high temperature heated flow cell (Polimer Laboratories) as described by PJ DesLauriers, DC Rohlfing, and ET Hsieh, Polimer, 43, 159 (2002) .
The sulfated alumina support activator (abbreviated SA) used in Examples 1-6 and 11-16 was prepared according to the following procedure. Boemite was obtained from W.R. Grace Company under the name “Alumina A” and tandium has a surface area of about 300 m2 / g and a pore volume of about 1.3 ml / g. This matter was obtained as a powder having an average particle size of about 100 microns. This material was impregnated for insipient wetting 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 the powder mixture was placed in a 1.75-inch quartz tube equipped with a sintered quartz disc at the bottom. While the powder was supported on the disc, air (nitrogen can be replaced) dried by passing through a 13X molecular sieve column, was blown upward through the disc at a linear rate of about 1.6 to 1.8 standard cubic feet per hour. 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 600 ° C. At this temperature, the powder was allowed to fluidize for about three hours in dry air. After that, the sulfated alumina (SA) support activator was collected and stored under anhydrous nitrogen, and was used without exposure to the atmosphere.
The silica-alumina activator-support fluoride (abbreviated FSA) used in Examples 7-10 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 ammonia 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 was placed in a tube that was 1.75-inch quartz equipped with a sintered quartz disk at the bottom. While the powder was supported by the disc, air (nitrogen can be replaced) dried by passing through a 13X molecular sieve column, was blown upward through the disc at a linear rate of about 1.6 to 1.8 cubic feet per hour. An electric oven around the quartz tube was then left 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 this temperature, the powder was allowed to fluidize for about three hours in dry air. After that, the silica-alumina activator-support fluoride (FSA) was collected and stored under anhydrous nitrogen, and was used without exposure to the atmosphere.
The polymerization achievements were conducted in a one-gallon (3.8-liter) stainless steel reactor as follows. First the reactor was purged with nitrogen and then with isobutane steam. Approximately 0.3-1.0 mmol of either triisobutylaluminum (TIBA) or triethylaluminium (TEA), 100-200 mg of activator-support SA or FSA, and the desired amount of catalyst component I and / or catalyst component II (see below for structures of these components ) were added in that order through a loading port while venting isobutane vapor. The loading door was closed and about 2 L of isobutane was added. The reactor contents were stirred and heated to 85-90 oC. Then, 8-25 grams of 1-hexene were added to the reactor (no 1-hexene added for examples 13-16), followed by the introduction of ethylene. Hydrogen was used in Examples 14-16, with the hydrogen added in a fixed mass ratio with respect to the ethylene flow. Hydrogen was stored in a 340-mL pressure vessel and added with ethylene via an automated supply system, while the total reactor pressure was maintained at the desired pressure in the range of 390-550 psig (2689-3792 kPa) by the combined addition ethylene / hydrogen (if used) / isobutane. The reactor was maintained and controlled at either 85 ° C or 90 ° C through an operating time of 30 minutes of polymerization. Upon completion, the isobutane and ethylene were vented from the reactor, the reactor was opened and the polymer product was collected and dried. EXAMPLES 1-10 Polymers produced using a double catalyst system
Metallocene compounds of catalyst component I used in these examples have the following structures:

Catalyst component II metallocene compounds used in these examples have the following structures:


These metallocene compounds can be prepared according to any suitable method. Technical representatives are described in US Patent Nos. 7,026,494, 7,199,073, 7,312,283, 7,456,243, and 7,521,572, and US Patent Publication 2009/0088543, the disclosures of which are incorporated herein by reference in their entirety.
The polymerization conditions by examples 1-10 are summarized in Table I, while the resulting polymer properties by examples 1-10 are summarized in Table II. The weight ratio of catalyst components I: II in Examples 1-10 was within a range of about 4: 1 to about 1: 2. The Mn of the polymers of Examples 1-10 was within a range of about 11,000 to about 25,000 g / mol. FIG. 2 illustrates the molecular weight distribution of the polymers of Examples 1-4, FIG. 3 illustrates the molecular weight distribution of the polymers of Examples 5-6, and FIG. 4 illustrates the molecular weight distribution of the polymers of Examples 7-10. FIGS. 2-4 demonstrates that the polymers of Examples 1-10 have a wide and / or bimodal MWD. FIGS. 5-8 illustrates the MWD and SCBD of the polymers of Examples 5, 6, 11, and 12, respectively. These polymers have a bimodal MWD and, in addition, the SCB content decreases as the molecular weight increases. Table I. Polymerization conditions for examples 1-10.

Table II. Polymer Properties of Examples 1-10.
EXAMPLES 13-16 Polymers produced using a catalyst system contain a single metallocene catalyst component I The metallocene composite catalyst component used in these examples had the following structure:

The polymerization conditions for examples 13-16 are summarized in Table III, while the resulting polymer properties for examples 13-16 are summarized in Table IV. FIG. 9 illustrates the molecular weight distribution of the polymers of Examples 13-16. As shown in Tables III-IV and FIG. 9, unexpectedly, the molecular weight distributions of the polymers of Examples 13-16 were not greatly affected by the amount of hydrogen added to the reactor. Table III. Polymerization conditions by example 13-16.

Table IV. Properties of the Polymers of Examples 13-16.

权利要求:
Claims (14)
[0001]
1. Olefin polymerization process, characterized by the fact that it comprises: contacting a catalyst composition with an olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises the catalyst component I, catalyst component II, and at least one activator, in which: the olefin polymer has Mn within a range ranging from 7000 to 40,000 g / mol, catalyst component I comprises: a compound having the formula (A ); on what:
[0002]
2. Process according to claim 1, characterized by the fact that at least one activator comprises at least one activator-support comprising a solid oxide treated with an electron-removing anion, in which: the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; and the electron-removing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorsulfate, fluorborate, phosphate, fluorophosphate, trifluoracetate, triflate, fluorzirconate, fluortitanate, phospho-tungstate, or any combination thereof.
[0003]
3. Process according to claim 1, characterized by the fact that the catalyst composition still comprises at least one organoaluminium compound having the formula: Al (XA) m (XB) 3-m, where: XA is the hydrocarbyl; XB is an alkoxide or an aryloxide, halide, or a hydride; and m is 1 to 3, inclusive.
[0004]
4. Process according to claim 3, characterized by the fact that: at least one organoaluminium compound comprises 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, or any combination thereof; and at least one activator comprises at least one activator-support, and at least one activator-support comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, silica-alumina fluoridated, silica-alumina chlorinated, silica-alumina brominated, sulphate silica-alumina, fluoride silica-zirconia, chloride silica-zirconia, brominated silica-zirconia, sulphate silica-zirconia, fluoride silica-titania, fluoride silica-coated, silica-coated sulfate alumina, phosphate-alumina or any silica-coated alumina or any silica-coated alumina combination thereof.
[0005]
5. Process according to claim 1, characterized in that the at least one activator comprises at least one aluminoxane compound, at least one organobromine or organoborate compound, at least one ionizing ionic compound, or any combination thereof.
[0006]
6. Process according to claim 1, characterized in that the catalyst component I comprises a compound having the formula (A), and in which: X1 and X2 are independently F, Cl, Br, I, methyl, benzyl, or phenyl; and R1, R2, and R3 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl.
[0007]
Process according to claim 1, characterized by the fact that catalyst component II comprises a compound having the formula (C), and in which: X4 and X5 are independently F, Cl, Br, I, benzyl, phenyl, or methyl; E3is a bridge group selected from: a cyclopentyl or cyclohexyl group, a bridge group having the formula> E3AR7AR8A, where E3A is C or Si, and R7A and R8As are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl, a bridge group having the formula —CR7BR8B — CR7CR8C—, where R7B, R8B, R7C, and R8C are independently H or methyl, or a bridge group having the formula —SiR7DR8D — SiR7ER8E—, where R7D, R8D, R7E, and R8Es are independently H or methyl; and R9 and R10 are independently H or t-butyl.
[0008]
8. Process according to claim 1, characterized in that a weight ratio of the catalyst component I to the catalyst component II in the catalyst composition is in the range of 100: 1 to 1: 100.
[0009]
9. Process according to claim 1, characterized by the fact that the process is conducted in a batch reactor, slurry reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, or a combination of them.
[0010]
Process according to claim 1, characterized in that the olefin monomer is ethylene, and at least one olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1- pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3- heptene, 1-octene, 1-decene, styrene, or a mixture thereof.
[0011]
11. Process according to claim 1, characterized by the fact that the process is conducted in the absence of added hydrogen.
[0012]
12. Process according to claim 1, characterized by the fact that the process is conducted in the presence of 10 ppm to 500 ppm hydrogen.
[0013]
13. Process according to claim 1, characterized by the fact that: the polymer has an Mn in a range of 9,000 to 30,000 g / mol; or the polymer has a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the polymer in D90 to the number of SCB per 1000 total carbon atoms of the polymer in D10 in a range of 1.1 to 20; or both.
[0014]
14. Catalyst composition capable of producing an olefin polymer with more short chain branches in Mn than Mw, the catalyst composition comprising catalyst component I, catalyst component II, and at least one activator, characterized by the fact that: catalyst component I comprises : a compound having formula (A); on what: formula (A) is M1 is Zr or Hf; X1 and X2 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E1 is C or Si; R1 and R2 are independently H, a hydrocarbon group having up to 18 carbon atoms, or R1 and R2 are connected to form a cyclic or heterocyclic group having up to 18 carbon atoms; and R3 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; and catalyst component II comprises: a compound having formula (C); on what: formula (C) is; where: M3 is Zr or Hf; X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, where R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbiloxide group, a hydrocarbilamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E3is a bridge group selected from: a cyclic or heterocyclic bridge group having up to 18 carbon atoms, a bridge group having the formula> E3AR7AR8A, where E3A is C or Si, and R7A and R8As are independently H or a hydrocarbon group having up to 18 carbon atoms, a bridge group having the formula —CR7BR8B — CR7CR8C—, where R7B, R8B, R7C, and R8C are independently H or a hydrocarbon group having up to 10 carbon atoms, or a bridge group having the formula —SiR7DR8D — SiR7ER8E—, where R7D, R8D, R7E, and R8Es are independently H or a hydrocarbon group having up to 10 carbon atoms; R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and R11 is a cinclopentadienyl or indenyl group, any substituent on R11 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms.

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

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-07-28| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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

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2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/07/2011, 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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US12/830,571|US8288487B2|2010-07-06|2010-07-06|Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen|

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US12/830,571|2010-07-06|

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PCT/US2011/042935|WO2012006272A2|2010-07-06|2011-07-05|Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen|

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