Polymerization catalysts for producing polymers with low levels of long chain branching

专利摘要:

公开号:AU2007212128A1
申请号:U2007212128
申请日:2007-02-02
公开日:2007-08-16
发明作者:Michael D Jensen；Joel L. Martin；Max P. Mcdaniel；David C. Rohlfing；Matthew G. Thorn；Qing Yang；Youlu Yu
申请人:Chevron Phillips Chemical Co LLC；Chevron Phillips Chemical Co LP；
IPC主号:C08F10-00

专利说明:
WO 2007/092753 PCT/US2007/061519 1 POLYMERIZATION CATALYSTS FOR PRODUCING POLYMERS WITH LOW LEVELS OF LONG CHAIN BRANCHING TECHNICAL FIELD OF THE INVENTION 5 This invention relates to the field of organometal compositions, olefin polymerization catalyst compositions, methods for the polymerization and copolymerization of olefins using a catalyst composition, and polyolefins. BACKGROUND OF THE TNVENTTON 10 It is known that mono-1-olefins (a-olefins), including ethylene, can be polymerized with catalyst compositions employing titanium, zirconium, vanadium, chromium, or other metals, often combined with a solid oxide and in the presence of cocatalysts. These catalyst compositions can be useful for both homopolymerization of ethylene, as well as copolymerization of ethylene with comonomers such as 15 propylene, 1-butene, 1-hexene, or other higher a-olefins. Therefore, there exists a constant search to develop new olefin polymerization catalysts, catalyst activation processes, and methods of making and using catalysts that will provide enhanced catalytic activities and polymeric materials tailored to specific end uses. Polyethylene (PE) produced by any number of methods generally contains 20 small to moderate amounts of long chain branched molecules. In some instances, long chain branching (LCB) is desired to improve bubble stability during film blowing or to enhance the processibility of resins prepared with metallocene catalysts. However for many uses, the presence of LCB is considered undesirable due to the increased elasticity that it typically imparts to the resins. Therefore the ability to 25 control the LCB level in polyethylene using metallocene-based catalysts is a desirable goal. One example of this need is scen in the use of bridged or ansa-metallocene catalysts, which are desirable catalysts for some purposes, but which may tend to produce polymer with LCB levels that are detrimental to film performance. 30 Therefore, new catalyst compositions and methods that allow better control of LCB levels within a desired specification range is a desirable goal.
WO 2007/092753 PCT/US2007/061519 2 SUMMARY OF THE INVENTION This invention encompasses catalyst compositions, methods for preparing catalyst compositions, methods for polymerizing olefins, and ethylene polymers and copolymers. In the course of examining metallocene-based olefin polymerization 5 catalysts, it was discovered that the long-chain branching (LCB) content of PE resins made with such catalysts was related to, among other things, the type of metallocene catalyst employed, and also related to the particular activator, including the particular solid oxide activator or "activator-support" which can constitute one component of the catalyst composition. 10 In one aspect of the present invention, for example, it was discovered that certain metallocene-based catalyst systems can produce high molecular weight polyethylene with low levels of LCB, even under relatively high temperature conditions. Useful metallocenes in preparing the catalyst compositions of this invention include, but are not limited to, tightly-bridged, ansa-metallocenes that 15 comprise a pendant alkenyl (olefin-containing) group attached to at least one of the cyclopentadienyl-type moieties of the tightly-bridged ligand, and also comprises one or two aryl groups, particularly one or two phcnyl groups, bonded to the bridging atom of the tightly-bridged ligand. Thus, in one aspect, the present invention encompasses a catalyst composition 20 comprising at least one tightly-bridged ansa-metallocene compound containing a pendant olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand; optionally, at least one organoaluminum compound; and at least one activator. In one aspect, the at least one activator can be an activator-support comprising a solid 25 oxide treated with an electron-withdrawing anion; a layered mineral; an ion exchangeable activator-support; an organoaluminoxane compound; an organoboron compound; an organoborate compound; or any combination of any of these activators. In another aspect, this invention comprises the contact product of at least one tightly bridged ansa-metallocene compound containing a pendant olefin-containing moiety 30 attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand; optionally, at least one organoaluminum compound; and at least one activator, as provided herein. In this WO 2007/092753 PCT/US2007/061519 3 aspect, this invention encompasses a composition of matter, a catalyst composition for polymerizing olefins, a method of preparing a catalyst composition, a method of polymerizing olefms, new polymers and copolymers of ethylene, and the like, in each case encompassing at least one tightly-bridged ansa-metallocene compound 5 containing a pendant olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand; optionally, at least one organoaluminum compound; and at least one activator. In another aspect, the at least one activator can be a solid oxide activator-support, that is, can be an activator-support comprising a solid oxide treated 10 with an electron-withdrawing anion. In one aspect, the catalyst composition of this invention can comprise the contact product of: 1) at least one ansa-metallocene; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the 15 formula:
(X)(X
2
)(X
3
)(X
4
)M
1 , wherein
M
1 is titanium, zirconium, or hafnium; (X') and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; 20 one substituent on (X') and (X 2 ) is a bridging group having the formula ER R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X') and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R' and R2 is an aryl group; 25 at least one substituent on (X') or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X3) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 30 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and WO 2007/092753 PCT/US2007/061519 4 any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a 5 phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; b) the at least one organoaluminum compound comprises a compound having the formula: Al(X 5
)(X
6 10 wherein (X 5 ) is a hydrocarbyl having from 1 to 20 carbon atoms; (X 6 ) is an alkoxide or an aryloxide, any of which having from I to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive; and c) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an 15 electron-withdrawing anion, a layered mineral, an ion-exchangeable activator support, or any combination thereof; ii) an organoaluminoxanc compound; iii) an organoboron or an organoborate compound; or iv) any combination thereof. 20 In one aspect of this invention, the at least one organoaluminum compound can be optional when: 1) at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 2) the at least one activator comprises at least one organoaluminoxane compound; or 3) both conditions 1 and 2 exist. Thus, while not intending to be bound by theory, it will be recognized by one of ordinary skill that a 25 metallocene-based composition that exhibits catalytic polymerization activity typically comprises the contact product of: 1) a metallocene component; 2) a component that provides an activatable ligand such as an alkyl or hydride ligand to the metallocene, when the metallocene compound does not already comprise such a ligand; and 3) an activator component. In some instances, one component can function as both the component 30 that provides an activatable ligand and the activator component, for example, an organoaluminoxane. In other cases, these two functions can be provided by two separate components, such as an organoaluminum compound that can provide an activatable alkyl WO 2007/092753 PCT/US2007/061519 5 ligand to the metallocene, and a solid oxide treated with an electron-withdrawing anion that can provide the activator function. Further, in some instances, the metallocene compound can already comprise an activatable ligand such as an alkyl ligand, therefore, a component that provides an activatable ligand is not required, but can be an optional 5 component of the contact product. Therefore, by designating the at least one organoaluminum compound as "optional" in the contact product, it is intended to reflect that the organoaluminum compound can be optional when it is not necessary to impart catalytic activity to the composition comprising the contact product, as understood by one of ordinary skill. 10 In another aspect of the present invention, this invention provides a catalyst composition comprising the contact product of at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-support, wherein: a) the at least one ansa-metallocene comprises a compound having the formula:
R
4 A 9 R 4 B R20, E M . n 15 R 3 A R 3 8 (1), wherein M' is zirconium or hafnium; X is, independently, F, C1, Br, or T; E is C or Si; R1 and R2 are independently an alkyl group or an aryl group, either of 20 which having up to 10 carbon atoms, or hydrogen, wherein at least one of R1 or R 2 is an aryl group;
R
3 A and R 3 B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and 25 R 4 ^ and R4B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; WO 2007/092753 PCT/US2007/061519 6 b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or 5 any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, 10 magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or 15 unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof In still another aspect, the present invention provides a catalyst composition comprising the contact product of: 1) at least one ansa-metallocene; and 2) at least one activator, wherein: 20 a) the at least one ansa-metallocene comprises a compound having the formula:
(X')(X
2
)(X
3
)(X
4 )M', wherein M1 is titanium, zirconium, or hafnium; (X1) and (X 2 ) are independently a substituted cyclopentadienyl, a 25 substituted indenyl, or a substituted fluorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula
ER'R
2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or 30 hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X') or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; WO 2007/092753 PCT/US2007/061519 7
(X
3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 R, wherein RA is an alkyl group or an aryl group, any 5 of which having up to 12 carbon atoms; wherein at least one (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of 10 aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; and b) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an 15 electron-withdrawing anion, a layered mineral, an ion-exchangeable activator support, or any combination thereof; ii) an organoaluminoxanc compound; iii) an organoboron compound or an organoborate compound; or iv) any combination thereof. 20 Yet another aspect of the present invention provides a catalyst composition comprising the contact product of: 1) at least one ansa-metallocene; and 2) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: R4
R
4 B
R,,,,
RE M R2VOE 25 R 3 A R 3 B (IV), wherein
M
1 is zirconium or hafnium; WO 2007/092753 PCT/US2007/061519 8 X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2
CH
2 Ph; or
CH
2 SiMe 2
CH
2 Ph; E is C or Si; 5 R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R' or R2 is an aryl group; R and R 3 B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; 10 n is an integer from 0 to 10, inclusive; and
R
4 A and R 4 " are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; and b) the at least one activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein 15 the solid oxide is silica, alumina, silica-alumina, aluninophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, 20 phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof In a further aspect of this invention, the activator-support can comprise a solid 25 oxide treated with an electron-withdrawing anion, wherein the solid oxide comprises silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof. In this aspect, the electron-withdrawing anion can comprise fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, 30 fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted WO 2007/092753 PCT/US2007/061519 9 or unsubstituted alkylsulfate, and the like, including any combination thereof. In addition, the activator-support can further comprises a metal or metal ion such as zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof. Also in this aspect, the electron-withdrawing anion can be fluoride, chloride, bromide, 5 iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, and the like, including any combination thereof. 10 In yet another aspect of this invention, the activator-support can comprise a layered mineral, an ion-exchangeable activator-support, or any combination thereof. In this aspect, the activator-support can comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non 15 layered aluminosilicate mineral, or any combination thereof. In another aspect, this invention further provides a process for producing a polymerization catalyst composition comprising contacting: at least one ansa metallocene compound; optionally, at least one organoaluminum compound; and at least one activator; to produce the composition, wherein the at least one ansa 20 metallocene, the at least one organoaluminum compound, and the at least one activator are defined herein. In still another aspect, this invention affords a method of polymerizing olefins, comprising contacting ethylene and an optional a-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition is provided as disclosed 25 herein. In yet further aspect, the present invention provides ethylene polymers and copolymers, and articles made therefrom, produced by contacting ethylene and an optional ca-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition is provided as disclosed herein. 30 In one aspect of this invention, the activity of the catalyst compositions of this invention can be enhanced by precontacting some of the polymerization reaction components to form a first mixture, for a first period of time, before this mixture is WO 2007/092753 PCT/US2007/061519 10 then contacted with the remaining polymerization reaction components, forming a second mixture, for a second period of time. For example, the ansa-metallocene compound can be precontacted with some other polymerization reaction components, including, but not limited to, for example, an ot-olefin monomer and an 5 organoaluminum cocatalyst, for some period of time before this mixture is contacted with the remaining polymerization reaction components, including, but not limited to, a solid oxide activator-support. The first mixture is typically termed the "precontacted" mixture and comprises precontacted components, and the second mixture is typically termed the "postcontacted" mixture and comprises postcontacted 10 components. For example, the mixture of at least one metallocene, at least one olefin monomer, and at least one organoaluminum cocatalyst compound, before this mixture is contacted with the activator-support, is one type of "precontacted" mixture. The mixture of metallocene, monomer, organoaluminum cocatalyst, and acidic activator support, formed from contacting the precontacted mixture with the acidic activator 15 support, is thus termed the "postoontacted" mixture. This terminology is used regardless of what type of reaction, if any, occurs between components of the mixtures. For example, according to this description, it is possible for the precontacted organoaluminum compound, once it is admixed with the metallocene or metallocenes and the olefin monomer, to have a different chemical formulation and 20 structure from the distinct organoaluminum compound used to prepare the precontacted mixture. This invention also comprises methods of making catalyst compositions that utilize at least one ansa-metallocene catalyst, optionally at least one organoaluminum compound, and at least one activator. The methods of this invention include 25 precontacting any selected catalyst components, for example, the metallocene catalyst and an organoaluminum cocatalyst with an olefm, typically but not necessarily, a monomer to be polymerized or copolymerized, prior to contacting this precontacted mixture with any remaining catalyst components, in this example, the solid oxide activator-support. 30 In yet another aspect, the present invention further comprises new catalyst compositions, methods for preparing catalyst compositions, and methods for polymerizing olefins that can result in improved productivity. In one aspect, these WO 2007/092753 PCT/US2007/061519 11 methods can be carried out without the need for using large excess concentrations of the expensive organoaluminoxane cocatalyst such as methyl aluminoxane (MAO), or the catalyst composition can be substantially free of aluminoxanes such as MAO. That is, the catalyst compositions of this invention can have polymerization activity in 5 the substantial absence of aluminoxanes. However, this invention also provides a catalyst composition comprising an ansa-metallocene compound and an aluminoxane. Therefore, in this aspect, the catalyst composition is not required to comprise either an acidic activator-support wherein the activator-support comprises a chemically-treated solid oxide, and the catalyst composition is also not required to comprise an 10 organoaluminum compound. Additionally, this invention encompasses a process comprising contacting at least one monomer and the catalyst composition under polymerization conditions to produce the polymer. Thus, this invention comprises methods for polymerizing olefins using the catalyst compositions prepared as described herein. 15 The present invention also encompasses new polyolefins. This invention also comprises an article that comprises the polymer produced with the catalyst composition of this invention. These and other features, aspects, embodiments, and advantages of the present invention will become apparent after a review of the following detailed description of 20 the disclosed features. BRIEF DESCRIPTION OF THE FIGURES FIGURE 1 illustrates the structures of specific metallocenes used in the inventive Examples. 25 FIGURE 2 illustrates the structures of specific metallocenes used in the comparative Examples. FIGURE 3 illustrates data obtained from SEC-MALS analysis of the ethylene homopolymer produced in inventive Examples 1-4 (plot of R. versus M,). FIGURE 4 illustrates data obtained from SEC-MALS analysis of the ethylene 30 homopolymer produced in inventive Examples 5-7 (plot of R, versus M,). FIGURE 5 illustrates data obtained from SEC-MALS analysis of the ethylene homopolymer produced in inventive Examples 10 and 11 (plot of R. versus Mw).
WO 2007/092753 PCT/US2007/061519 12 FIGURE 6 provides a plot of zero shear viscosity versus molecular weight, specifically, log(qo) versus log (Mw) for polymers prepared according to inventive Examples 1-11. FIGURE 7 provides a plot of zero shear viscosity versus molecular weight, 5 specifically, log(io) versus log (Mw) for polymers prepared according to comparative Examples 14-16. FIGURE 8 provides comparison gel permeation chromatograms (GPCs) for ethylene homopolymer of inventive Examples 1-11 (El-Eli) and comparative Examples 14-16 (E14-E16). 10 DETAILED DESCRIPTION OF THE INVENTION The present invention provides new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, olefin polymers and articles prepared therefrom. In one aspect, 15 this invention encompasses a catalyst composition comprising at least one tightly bridged ansa-metallocene compound comprising an olefin-containing moiety pendant to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand, at least one activator, and optionally at least one organoaluminum compound. In another aspect, this invention comprises methods for 20 making the catalyst composition disclosed herein, and in yet a further aspect, this invention comprises methods for polymerizing olefins employing the catalyst composition disclosed herein. As described above, the designation of the at least one organoaluminum compound as an optional component in the contact product, it is intended to reflect that the organoaluminum compound can be optional when it is not 25 necessary to impart catalytic activity to the composition comprising the contact product, as understood by one of ordinary skill. A detailed description of the contact product components follows. Catalyst Composition and Components 30 The Metallocene Compounds In one aspect, the present invention provides a catalyst composition comprising at least one tightly-bridged ansa-metallocene compound comprising an WO 2007/092753 PCT/US2007/061519 13 olefin-containing moiety bonded to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand, at least one activator, and optionally at least one organoaluminum compound as further disclosed herein. As used herein, the term bridged or ansa-metallocene refers simply to a 5 metallocene compound in which the two q 5 -cycloalkadienyl-type ligands in the molecule are linked by a bridging moiety. Useful ansa-metallocenes are typically "tightly-bridged", meaning that the two n 5 -cycloalkadienyl-type ligands are connected by a bridging group wherein the shortest link of the bridging moiety between the l5 cycloalkadienyl-type ligands is a single atom. Thus, the length of the bridge or the 10 chain between the two 5 -cycloalkadienyl-type ligands is one atom, although this bridging atom is substituted. The metallocenes of this invention are therefore bridged bis(q 5 -cycloalkadienyl)-type compounds, wherein the i 5 -cycloalkadienyl portions include substituted cyclopentadienyl ligands, substituted indenyl ligands, substituted fluorcnyl ligands, and the like, wherein one substituent on these cyclopentadienyl 15 type ligands is a bridging group having the formula ER'R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and wherein E is bonded to both cyclopentadienyl-type ligands. In this aspect, R 1 and R 2 can be independently selected from an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group. 20 In this aspect, one substituent on the metallocene's cyclopentadienyl-type ligands can be a bridging group having the formula >CR R2, >SiRR 2 , >GeR R2, or >SnR R2, wherein R' and R 2 can be independently selected from an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group. Examples of bridging ER'R 2 groups include, 25 but are not limited to, >CPh 2 , >SiPh 2 , >GePh 2 , >SnPh 2 , >C(tolyl) 2 , >Si(tolyl) 2 , >Ge(tolyl) 2 , >Sn(tolyl) 2 , >CMePh, >SiMePh, >GeMePh, >SnMePh, >CEtPh, >CPrPh, >CBuPh, >CMe(tolyl), >SiMe(tolyl), >GeMe(tolyl), >SnMe(tolyl), >CHPh, >CH(tolyl), and the like. Further, at least one substituent on at least one of the 11 -cycloalkadienyl-type 30 ligands is a substituted or an unsubstituted olefin-containing hydrocarbyl group, having up to 12 carbon atoms, which is referred to herein as an "alkenyl group," WO 2007/092753 PCT/US2007/061519 14 regardless of the regiochemistry of the alkene functionality. In this aspect, this olefin containing hydrocarbyl group is bonded to one of the 11 5 -cycloalkadienyl-type ligands of the bridging ligand, wherein the olefinic bond is distal from the 15 cycloalkadienyl-type ligand, and therefore can be described as a pendant alkenyl 5 group. Thus, one substituent on a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl of the metallocene comprises an alkenyl group, in which case the ansa-metallocenes can be described as containing a hydrocarbyl chain attached to one of the cyclopentadienyl-type ligands which comprises an olefinic portion. 10 In another aspect, the at least one ansa-metalloceno of this invention comprises a compound having the formula:
(X')(X
2
)(X
3
)(X
4 )M', wherein M1 is titanium, zirconium, or hafnium; (X') and (X 2 ) are independently a substituted cyclopentadienyl, a 15 substituted indenyl, or a substituted fluorenyl; one substituent on (X') and (X 2 ) is a bridging group having the formula
ERR
2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X') and (X 2 ), and wherein R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or 20 hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X') or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;
(X
3 ) and (X 4 ) are independently: 1) F, Cl, Br, or 1; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a 25 hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein R is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is 30 independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a WO 2007/092753 PCT/US2007/061519 15 phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen. In another aspect of the present invention, the olefin-containing hydrocarbyl group is bonded to one of the T 1 5 -cycloalkadienyl-type ligands of the bridging ligand, 5 that is, the alkenyl group, can have up to about 20 carbon atoms. In another aspect, the alkenyl group can have up to about 12 carbon atoms, up to about 8 carbon atoms, or up to about 6 carbon atoms. Examples of alkcnyl groups include, but arc not limited to, butenyl, pentenyl, hexenyl, heptenyl, or octenyl. In another aspect, the alkenyl group is 3-butenyl or 4-pentenyl. Thus, in one aspect, the pendant unsaturated 10 group can contain the carbon-carbon double bond from about 3 to about 7 carbon atoms removed from the cyclopentadienyl-type ligand itself, and in another aspect, from 3 to about 4 carbon atoms removed from the cyclopentadienyl-type ligand itself. In still another aspect, the olefin-containing hydrocarbyl group, that is the alkenyl group, can be substituted or unsubstituted. For example, any substituent on 15 the alkenyl group, when present, can be selected independently from an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a boron group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; a halide; or hydrogen. 20 Hydrogen is listed as a possible substituent on the alkenyl group in the context that hydrogen can add to an unsaturated moiety within the alkenyl group, as long as it does not destroy the alkenyl group. Thus, hydrogen is a possible substituent on any unsaturated moiety within the alkenyl group so long as it does not add across the very olefin moiety necessary for this group to be considered an alkenyl group. Further, this 25 description of other substituents on the alkenyl group atom can include substituted, unsubstituted, branched, linear, or heteroatom-substituted analogs of these moieties. Examples of olefinic hydrocarbyl groups, specifically alkenyl groups, that can be bonded to at least one cyclopentadienyl-type moiety include, but are not limited to, 3-butenyl (CH 2
CH
2
CH=CH
2 ), 4-pentenyl (CH 2
CH
2
CH
2
CH=CH
2 ), 5-hexenyl 30 (CH 2
CH
2
CH
2
CH
2
CH=CH
2 ), 6-heptenyl (CH 2
CH
2
CH
2
CH
2
CH
2
CH=CH
2 ), 7-octenyl
(CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH=CH
2 ), 3-methyl-3-butenyl [CH 2
CH
2
C(CH
3 )=CH2], 4 methyl-3-pentenyl [CH 2
CH
2
CH=C(CH
3 )2, 1,1 -dimethyl-3-butenyl WO 2007/092753 PCT/US2007/061519 16
[C(CH
3
)
2
CH
2
CH=CH
2 ], 1,1 -dimethyl-4-pentenyl [C(CH 3
)
2
CH
2
CH
2
CH=CH
2 ], and the like, or any substituted analog thereof. In one aspect, the unsaturated group bonded to the bridging group can be 3-butenyl (CH 2
CH
2
CH=CH
2 ), 4-pentenyl
(CH
2
CH
2
CH
2
CH=CH
2 ), or a substituted analog thereof. 5 In addition to containing a bridging group having the formula ER'R 2 and at least one an alkenyl group as disclosed herein, the cyclopentadienyl-type ligands can also have other substituents. For example, these substituents can be selected from the same chemical groups or moieties that can serve as the (X 3 ) and (X 4 ) ligands of the ansa-metallocenes. Thus, any additional substituent on the cyclopentadienyl-type 10 ligands; and any substituent on the substituted alkenyl group; and (X 3 ) and (X 4 ) can be independently selected from an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a boron group, or a substituted analog thereof, any of which having from 1 to about 20 15 carbon atoms; a halide; or hydrogen; as long as these groups do not terminate the activity of the catalyst composition. Further, this list includes substituents that can be characterized in more than one of those categories such as bcnzyl. This list also includes hydrogen, therefore the notion of a substituted indenyl and substituted fluorenyl includes partially saturated indenyls and fluorenyls including, but not 20 limited to, tetrahydroindenyl groups, tetrahydrofluorenyl groups, and octahydrofluorenyl groups. Examples of each of these substituent groups include, but are not limited to, the following groups. In each example presented below, unless otherwise specified, R is independently selected from: an aliphatic group; an aromatic group; a cyclic group; 25 any combination thereof; any substituted derivative thereof, including but not limited to, a halide-, an alkoxide-, or an amide-substituted analog or derivative thereof; any of which has from 1 to about 20 carbon atoms; or hydrogen. Also included in these groups are any unsubstituted, branched, or linear analogs thereof. Examples of aliphatic groups, in each occurrence, include, but are not limited 30 to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each WO 2007/092753 PCT/US2007/061519 17 occurrence having from one to about 20 carbon atoms. Thus, aliphatic groups include, but are not limited to, hydrocarbyls such as paraffins and alkenyls. For example, aliphatic groups as used herein include methyl, ethyl, propyl, n-butyl, tert butyl, sec-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, 5 decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, and the like. Examples of aromatic groups, in each occurrence, include, but are not limited to, phenyl, naphthyl, anthracenyl, and the like, including substituted derivatives thereof, in each occurrence having from 6 to about 25 carbons. Substituted derivatives of aromatic compounds include, but are not limited to, tolyl, xylyl, 10 mesityl, and the like, including any heteroatom substituted derivative thereof. Examples of cyclic groups, in each occurrence, include, but are not limited to, cycloparaffins, cycloolefins, cycloacetylenes, arenes such as phenyl, bicyclic groups and the like, including substituted derivatives thereof, in each occurrence having from about 3 to about 20 carbon atoms. Thus heteroatom-substituted cyclic groups such as 15 furanyl are included herein. In each occurrence, aliphatic and cyclic groups are groups comprising an aliphatic portion and a cyclic portion, examples of which include, but arc not limited to, groups such as: -(CH2)mC6HqRs-q wherein m is an integer from 1 to about 10, and q is an integer from 1 to 5, inclusive; -(CH2)mC6HqRu1 wherein m is an integer from 20 1 to about 10, and q is an integer from 1 to 11, inclusive; or -(CH2)mC5HqR9gq wherein m is an integer from 1 to about 10, and q is an integer from 1 to 9, inclusive. In each occurrence and as defined above, R is independently selected from: an aliphatic group; an aromatic group; a cyclic group; any combination thereof; any substituted derivative thereof, including but not limited to, a halide-, an alkoxide-, or an amide 25 substituted derivative or analog thereof; any of which has from 1 to about 20 carbon atoms; or hydrogen. In one aspect, aliphatic and cyclic groups include, but are not limited to: -CH 2
C
6
H
5 ; -CH 2
C
6
H
4 F; -CH 2
C
6
H
4 Cl; -CH 2
C
6
H
4 Br; -CH 2
C
6
H
4 1; CH 2
C
6
H
4 OMe; -CH 2
C
6
H
4 OEt; -CH 2
C
6
H
4
NH
2 ; -CH 2
C
6
H
4 NMe 2 ; -CH 2
C
6
H
4 NEt 2 ; CH 2
CH
2
C
6
H
5 ; -CH 2
CH
2
C
6
H
4 F; -CH 2
CH
2
C
6
H
4 Cl; -CH 2
CH
2
C
6
H
4 Br; -CH 2
CH
2
C
6
H
4 I; 30 -CH 2
CH
2
C
6
H
4 OMe; -CH 2
CH
2
C
6
H
4 OEt; -CH 2
CH
2
C
6
H
4
NH
2 ; -CH 2
CH
2
C
6
H
4 NMe 2 ; CH 2
CH
2
C
6
H
4 NEt 2 ; any regioisomer thereof, and any substituted derivative thereof.
WO 2007/092753 PCT/US2007/061519 18 Examples of halides, in each occurrence, include fluoride, chloride, bromide, and iodide. In each occurrence, oxygen groups are oxygen-containing groups, examples of which include, but are not limited to, alkoxy or aryloxy groups (-OR) and the like, 5 including substituted derivatives thereof, wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms. Examples of alkoxy or aryloxy groups (-OR) groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like. 10 In each occurrence, sulfur groups are sulfur-containing groups, examples of which include, but are not limited to, -SR and the like, including substituted derivatives thereof, wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms. 15 In each occurrence, nitrogen groups are nitrogen-containing groups, which include, but are not limited to, -NR 2 or pyridyl groups, and the like, including substituted derivatives thereof, whcrcin R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms. 20 In each occurrence, phosphorus groups are phosphorus-containing groups, which include, but are not limited to, -PR 2 , and the like, including substituted derivatives thereof, wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms. 25 In each occurrence, arsenic groups are arsenic-containing groups, which include, but are not limited to, -AsR 2 , and the like, including substituted derivatives thereof, wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms. In each occurrence, carbon groups are carbon-containing groups, which 30 include, but are not limited to, alkyl halide groups that comprise halide-substituted alkyl groups with I to about 20 carbon atoms, alkenyl or alkenyl halide groups with 1 WO 2007/092753 PCT/US2007/061519 19 to about 20 carbon atoms, aralkyl or aralkyl halide groups with I to about 20 carbon atoms, and the like, including substituted derivatives thereof. In each occurrence, silicon groups are silicon-containing groups, which include, but are not limited to, silyl groups such alkylsilyl groups, arylsilyl groups, 5 arylalkylsilyl groups, siloxy groups, and the like, which in each occurrence have from 1 to about 20 carbon atoms. For example, silicon groups include trimethylsilyl and phenyloctylsilyl groups. In each occurrence, boron groups are boron-containing groups, which include, but are not limited to, -BR 2 , -BX 2 , -BRX, wherein X is a monoanionic group such as 10 halide, hydride, alkoxide, alkyl thiolate, and the like, and wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms. In another aspect of this invention, (X 3 ) and (X 4 ) are independently selected from an aliphatic group, a cyclic group, a combination of an aliphatic group and a 15 cyclic group, an amido group, a phosphido group, an alkyloxide group, an aryloxide group, an alkanesulfonate, an arenesulfonate, or a trialkylsilyl, or a substituted derivative thereof, any of which having from 1 to about 20 carbon atoms; or a halide. In yet another aspect, (X 3 ) and (X4) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide 20 group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms. In still another aspect, (X3) and (X4) are independently selected from a hydrocarbyl having from 1 to about 10 carbon atoms, or a halide. In another aspect, (X 3 ) and (X 4 ) are independently selected from 25 fluoride, chloride, bromide, or iodide. In yet another aspect, (X 3 ) and (X 4 ) are chloride. In still another aspect, (X 3 ) and (X4) are independently a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 . A further aspect of the invention provides that the at least one ansa metallocene of this invention comprises a compound having the formula: WO 2007/092753 PCT/US2007/061519 20 R4A / R 4 B R20 M
R
3 A 3B (1), wherein: M1 is zirconium or hafnium; X is, independently, F, Cl, Br, or I; E is C or Si; 5 R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R' or Rz is an aryl group;
R
3 A and R 3 B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; 10 n is an integer from 0 to 10, inclusive; and
R
4 A and R 4 B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; In yet another aspect, the at least one ansa-metallocene of this invention comprises a compound having the formula: R4A R 4 B R2,E M A -n 15 R 3 A 3 B (11), wherein M1 is zirconium or hafnium; X is F, Cl, Br, or I; E is C or Si;
R
1 and R 2 are independently an alkyl group or an aryl group, either of 20 which having up to 10 carbon atoms, or hydrogen, wherein at least one of R1 or R 2 is an aryl group; WO 2007/092753 PCT/US2007/061519 21 RA and R 3 are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl; n is an integer from 1 to 6, inclusive; and R and R 4 B are independently a hydrocarbyl group having up to 6 5 carbon atoms, or hydrogen. In still another aspect, the at least one ansa-metallocene of this invention comprises a compound having the formula: R4A 9 / R 4 B R2E Ml-aX R2V X
R
3 3 B (111), wherein M1 is zirconium or hafnium; 10 X is Cl, Br, or I; E is C or Si;
R
1 and R2 arc independently methyl or phenyl, wherein at least one of R1 or R 2 is phenyl;
R
3 A and R 3 B are independently H or methyl; 15 n is 1 or 2; and R and R 4 B are independently H or t-butyl. In yet another aspect, the at least one ansa-metallocene of this invention can comprise a compound having the formula: R4A / R 4 B R201E ,3 n
R
3 A 3 B (IV), wherein 20 M 1 is zirconium or hafnium; WO 2007/092753 PCT/US2007/061519 22 X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2
CH
2 Ph; or
CH
2 SiMe 2
CH
2 Ph; E is C or Si; 5 R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R1 or R 2 is an aryl group; RA and R are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; 10 n is an integer from 0 to 10, inclusive; and R4 and R 4 B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen. In a further aspect, the at least one ansa-metallocene of this invention comprises a compound having the formula: t-Bu t-Bu tBu tBu t-B t-Bu Ph/,, CI Ph.C Ph Ph Zr-Cl 15 t-Bu t-Bu t-Bu t-Bu t-BU t-Bu Ph, - ,.C Ph&,,,. zr"""' 0 Ph, Ch"I1P Ph" C t-Bu t-Bu t-Bu t-Bu C MCIPh C H ..... M-CI C Ph-C' Ph Cl or any combination thereof.
WO 2007/092753 PCT/US2007/061519 23 In still another aspect, the at least one ansa-metallocene of this invention can t-Bu t-Bu Ph- Z r C comprise, or can be selected from, t-Bu t-Bu t-Bu - t-BU t-Bu t-Bu Ph, .. Z nC 1 Ph -,,,,,. . Ph ,... H CII'll, Ph Z C Ph, PhM Ph Zr Ch- -IPh" -C t-Bu t-Bu Phi ' M-CI Ph Cl ,or any combination thereof. Yet another aspect of the 5 present invention provides a metalloceno compound having the formula t-BU ' t-BU Ph p' wherein M 2 is Zr or Hf. Numerous processes to prepare metallocene compounds that can be employed in this invention have been reported. For example, U.S. Patent Nos. 4,939,217, 5,191,132, 5,210,352, 5,347,026, 5,399,636, 5,401,817, 5,420,320, 5,436,305, 10 5,451,649, 5,496,781, 5,498,581, 5,541,272, 5,554,795, 5,563,284, 5,565,592, 5,571,880, 5,594,078, 5,631,203, 5,631,335, 5,654,454, 5,668,230, 5,705,578, 5,705,579, 6,187,880, and 6,509,427 describe such methods. Other processes to prepare metallocene compounds that can be employed in this invention have been reported in references such as: K6ppl, A. Alt, H. G. J. Mol. Catal A. 2001, 165, 23; WO 2007/092753 PCT/US2007/061519 24 Kajigaeshi, S.; Kadowaki, T.; Nishida, A.; Fujisaki, S. The Chemical Society of Japan, 1986, 59, 97; Alt, H. G.; Jung, M.; Kehr, G. J. Organomet. Chem. 1998, 562, 153-181; Alt, H. G.; Jung, M. J. Organomet. Chem. 1998, 568, 87-112; Jung, M., Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1997; Piefer, B., 5 Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1995; and Zenk, R., Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1994. The following treatises also describe such methods: Wailes, P. C.; Coutts, R. S. P.; Weigold, H. in Organometallic Chemistry of Titanium, Zironium, and Hafnium, Academic; New York, 1974. ; Cardin, D. J.; Lappert, M. F.; and Raston, C. L.; 10 Chemistry of Organo-Zirconium and -Hafnium Compounds; Halstead Press; New York, 1986. The Organoaluminum Compound In one aspect, the present invention provides a catalyst composition 15 comprising at least one tightly-bridged ansa-metallocene compound comprising an olefin-containing moiety bonded to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand, at least one solid oxide activator-support, and optionally at least one organoaluminum compound. Thus, the designation of the at least one organoaluminum compound as optional is intended to 20 reflect that the organoaluminum compound can be optional when it is not necessary to impart catalytic activity to the composition comprising the contact product, as understood by one of ordinary skill, as disclosed herein. Organoaluminum compounds that can be used in this invention include, but are not limited to, compounds with the formula: 25 Al(X 5
)(
6
)
3 -m, wherein (X 5 ) is a hydrocarbyl having from I to about 20 carbon atoms; (X 6 ) is alkoxide or aryloxide, any of which having from I to about 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive. In one aspect, (X 5 ) is an alkyl having from 1 to about 10 carbon atoms. Examples of (X 5 ) moieties include, but are 30 not limited to, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, and the like. In another aspect, examples of (X 5 ) moieties include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, 1-hexyl, 2-hexyl, 3-hexyl, WO 2007/092753 PCT/US2007/061519 25 isohexyl, heptyl, octyl, and the like. In another aspect, (X 6 ) can be independently selected from fluoride, chloride, bromide, methoxide, ethoxide, or hydride. In yet another aspect, (X 6 ) can be chloride. In the formula A1(X).(X 6
)
3 -, n is a number from 1 to 3 inclusive, and 5 typically, n is 3. The value of n is not restricted to be an integer, therefore this formula includes sesquihalide compounds, other organoaluminum cluster compounds, and the like. Generally, examples of organoaluminum compounds that can be used in this invention include, but are not limited to, trialkylaluminum compounds, 10 dialkylaluminium halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. Examples of organoaluminum compounds that are useful in this invention include, but are not limited to trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), 15 trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof. If the particular alkyl isomer is not specified, the compound is intended to encompasses all isomers that can arise from a particular specified alkyl group. Thus, in another aspect, examples of organoaluminum compounds that can be used in this 20 invention include, but are not limited to, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof. In one aspect, the present invention comprises precontacting the ansa 25 metallocene with at least one organoaluminum compound and an olefin monomer to form a precontacted mixture, prior to contact this precontacted mixture with the solid oxide activator-support to form the active catalyst. When the catalyst composition is prepared in this manner, typically, though not necessarily, a portion of the organoaluminum compound is added to the precontacted mixture and another portion 30 of the organoaluminum compound is added to the postcontacted mixture prepared when the precontacted mixture is contacted with the solid oxide activator. However, all of the organoaluminum compound can be used to prepare the catalyst in either the WO 2007/092753 PCT/US2007/061519 26 precontacting or postcontacting step. Alternatively, all the catalyst components can be contacted in a single step. Further, more than one organoaluminum compounds can be used, in either the precontacting or the postcontacting step, or in any procedure in which the catalyst 5 components are contacted. When an organoaluminum compound is added in multiple steps, the amounts of organoaluminum compound disclosed herein include the total amount of organoaluminum compound used in both the precontacted and postcontacted mixtures, and any additional organoaluminum compound added to the polymerization reactor. Therefore, total amounts of organoaluminum compounds are 10 disclosed, regardless of whether a single organoaluminum compound is used, or more than one organoaluminum compound. In another aspect, typical organoaluminum compounds used in this invention include, but are not limited to, triethylaluminum (TEA), tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 15 The Activator In one aspect, the present invention encompasses a catalyst composition comprising at least onc tightly-bridged ansa-metallocene compound as disclosed herein; optionally, at least one organoaluminum compound; and at least one activator. In another aspect, the at least one activator can be an activator-support comprising a 20 solid oxide treated with an electron-withdrawing anion; a layered mineral; an ion exchangeable activator-support; an organoaluminoxane compound; an organoboron compound; an organoborate compound; or any combination of any of these activators, each of which is provided herein. 25 Chemically-Treated Solid Oxide Activator-Supports In one aspect, the present invention encompasses catalyst compositions comprising an acidic activator-support, which can comprise a chemically-treated solid oxide, and which is typically used in combination with an organoaluminum compound. In another aspect, the activator-support comprises at least one solid oxide 30 treated with at least one electron-withdrawing anion; wherein the solid oxide can be silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed WO 2007/092753 PCT/US2007/061519 27 oxides thereof, and. the like, or any mixture or combination thereof; and wherein the electron-withdrawing anion can be fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, 5 substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof. The activator-support includes the contact product of at least one solid oxide compound and at least one electron-withdrawing anion source. In one aspect, the solid oxide compound comprises an inorganic oxide. The solid oxide can be 10 optionally calcined prior to contacting the electron-withdrawing anion source. The contact product can also be calcined either during or after the solid oxide compound is contacted with the electron-withdrawing anion source. In this aspect, the solid oxide compound can be calcined or uncalcined. In another aspect, the activator-support can comprise the contact product of at least one calcined solid oxide compound and at 15 least one electron-withdrawing anion source. The activator-support exhibits enhanced activity as compared to the corresponding untreated solid oxide compound. The activator-support also functions as a catalyst activator as compared to the corresponding untreated solid oxide. While not intending to be bound by theory, it is believed that the activator-support can 20 function as solid oxide supporting compound with an additional ionizing, polarizing, or bond weakening function, collectively termed an "activating" function, by weakening the metal-ligand bond between an anionic ligand and the metal in the metallocene. Thus, the activator-support is considered to exhibit an "activating" function, regardless of whether it is ionizes the metallocene, abstracts an anionic 25 ligand to form an ion pair, weakens the metal-ligand bond in the metallocene, simply coordinates to an anionic ligand when it contacts the activator-support, or any other mechanisms by which ionizing, polarizing, or bond weakening might occur. In preparing the metallocene-based catalyst composition of this invention, the activator support is typically used along with a component that provides an activatable ligand 30 such as an alkyl or hydride ligand to the metallocene, including but not limited to at least one organoaluminum compound, when the metallocene compound does not already comprise such a ligand.
WO 2007/092753 PCT/US2007/061519 28 In still another aspect, the activator-support of this invention comprises a solid inorganic oxide material, a mixed oxide material, or a combination of inorganic oxide materials, that is chemically-treated with an electron-withdrawing component, and optionally treated with at least one other metal ion. Thus, the solid oxide of this 5 invention encompasses oxide materials such as alumina, "mixed oxide" compounds such as silica-alumina or silica-zirconia or silica-titania, and combinations and mixtures thereof. The mixed metal oxide compounds such as silica-alumina, with more than one metal combined with oxygen to form a solid oxide compound, can be made by co-gellation, impregnation or chemical deposition, and are encompassed by 10 this invention. In yet another aspect of this invention, the activator-support further comprises a metal or metal ion such as zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof. Examples of activator-supports that further comprise a metal or metal ion include, but are not limited to, zinc 15 impregnated chlorided alumina, zinc-impregnated fluorided alumina, zinc impregnated chlorided silica-alumina, zinc-impregnated fluorided silica-alumina, zinc-impregnated sulfated alumina, or any combination thereof. In another aspect, the activator-support of this invention comprises a solid oxide of relatively high porosity, which exhibits Lewis acidic or Bronsted acidic 20 behavior. The solid oxide is chemically-treated with an electron-withdrawing component, typically an electron-withdrawing anion, to form a activator-support. While not intending to be bound by the following statement, it is believed that treatment of the inorganic oxide with an electron-withdrawing component augments or enhances the acidity of the oxide. Thus, the activator-support exhibits Lewis or 25 Bronsted acidity which is typically greater than the Lewis or Bronsted acidity of the untreated solid oxide. One method to quantify the acidity of the chemically-treated and untreated solid oxide materials is by comparing the polymerization activities of the treated and untreated oxides under acid catalyzed reactions. In one aspect, the chemically-treated solid oxide comprises a solid inorganic 30 oxide comprising oxygen and at least one element selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or comprising oxygen and at least one element selected from the lanthanide or actinide elements. (See: Hawley's WO 2007/092753 PCT/US2007/061519 29 Condensed Chemical Dictionary, 11 Ed., John Wiley & Sons; 1995; Cotton, F.A.; Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced Inorganic Chemistry, 6 Ed., Wiley-Interscience, 1999.) Usually, the inorganic oxide comprises oxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, 5 Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn or Zr. Suitable examples of solid oxide materials or compounds that can be used in the chemically-treated solid oxide of the present invention include, but are not limited to, A1 2 0 3 , B 2 0 3 , BeO, Bi 2
O
3 , CdO, CoO 4 , Cr 2
O
3 , CuO, Fe 2
O
3 , Ga 2
O
3 , La 2
O
3 , Mn 2
O
3 , MoO 3 , NiO, P 2 0 5 , Sb 2 0 5 , SiO 2 , Sn0 2 , SrO, ThO 2 , TiO 2 , V 2 0 5 , W0 3 , Y 2 0 3 , ZnO, 10 ZrO 2 , and the like, including mixed oxides thereof, and combinations thereof. Examples of mixed oxides that can be used in the activator-support of the present invention include, but are not limited to, mixed oxides of any combination of Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, P, Sb, Si, Sn, Sr, Th, Ti, V, W, Y, Zn, Zr, and the like. Examples of mixed oxides that can be used in the activator 15 support of the present invention also include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, many clay minerals, pillared clays, alumina titania, alumina-zirconia, aluminophosphate, and the like. In a further aspect of this invention, the solid oxide material is chemically treated by contacting it with at least one electron-withdrawing component, typically 20 an electron-withdrawing anion source. Further, the solid oxide material is optionally chemically-treated with at least one other metal ion, that can be the same as or different from any metal element that constitutes the solid oxide material, then calcining to form a metal-containing or metal-impregnated chemically-treated solid oxide. Alternatively, a solid oxide material and an electron-withdrawing anion source 25 are contacted and calcined simultaneously. The method by which the oxide is contacted with an electron-withdrawing component, typically a salt or an acid of an electron-withdrawing anion, includes, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like. Typically, following any contacting method, the contacted mixture of oxide compound, electron-withdrawing 30 anion, and optionally the metal ion is calcined. The electron-withdrawing component used to treat the oxide can be any component that increases the Lewis or Bronsted acidity of the solid oxide upon WO 2007/092753 PCT/US2007/061519 30 treatment. In one aspect, the electron-withdrawing component is typically an electron-withdrawing anion derived from a salt, an acid, or other compound such as a volatile organic compound that can serve as a source or precursor for that anion. Examples of electron-withdrawing anions include, but are not limited to, fluoride, 5 chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, and the like, including any mixtures and combinations 10 thereof. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions can also be employed in the present invention. In one aspect, the chemically-treated solid oxide comprises a sulfated solid oxide, and in another aspect, the chemically-treated oxide comprises sulfated alumina. The terms alkanesulfonate and alkyl sulfate refer to anions having the general 15 formula [RBSO 2 O] and [(RBO)SO 2 O]~, respectively, wherein RB is a linear or branched alkyl group having up to 20 carbon atoms, that is optionally substituted with at least one group selected independently from F, Cl, Br, I, OH, OMc, OEt, OCF 3 , Ph, xylyl, mesityl, or OPh. Thus, the alkanesulfonate and alkyl sulfate may be referred. to as being either substituted or unsubstituted. In one aspect, the alkyl group of the 20 alkanesulfonate or alkyl sulfate can have up to 12 carbon atoms. In another aspect, the alkyl group of the alkanesulfonate or alkyl sulfate can have up to 8 carbon atoms, or up to 6 carbon atoms. In yet another aspect, examples of alkanesulfonates include, but are not limited to, methanesulfonate, ethanesulfonate, 1-propanesulfonate, 2 propanesulfonate, 3-methylbutanesulfonate, trifluoromethanesulfonate, trichloro 25 methanesulfonate, chloromethanesulfonate, 1-hydroxyethanesulfonate, 2-hydroxy-2 propanesulfonate, 1 -methoxy-2-propanesulfonate, and the like. In still another aspect, examples of alkyl sulfates include, but are not limited to, methylsulfate, ethylsulfate, 1-propylsulfate, 2-propylsulfate, 3-methylbutylsulfate, trifluoromethanesulfate, trichloromethylsulfate, chloromethylsulfate, 1-hydroxyethylsulfate, 2-hydroxy-2 30 propylsulfate, 1-methoxy-2-propylsulfate, and the like. The term arenesulfonate refers to anions having the general formula [Ar S0 2 0]-, wherein Ar^ is an aryl group having up to 14 carbon atoms, that is WO 2007/092753 PCT/US2007/061519 31 optionally substituted with at least one group selected independently from F, Cl, Br, I, Me, Et, Pr, Bu, OH, OMe, OEt, OPr, OBu, OCF 3 , Ph, OPh, or RC, wherein Rc is a linear or branched alkyl group having up to 20 carbon atoms. Thus, the arenesulfonate may be referred to as a substituted or an unsubstituted arenesulfonate. 5 Because the aryl group ArA can be substituted with an alkyl side chain, Rc, which includes a long alkyl side chain, the term arenesulfonate is intended to include the detergents. In one aspect, the aryl group of the arenesulfonate can have up to 10 carbon atoms. In another aspect, the aryl group of the arenesulfonate can have 6 carbon atoms. In yet another aspect, examples of arenesulfonates include, but are not 10 limited to, benzenesulfonate, naphthalenesulfonate, p-toluenesulfonate, n toluenesulfonate, 3,5-xylenesulfonate, trifluoromethoxybenzenesulfonate, trichloro methoxybenzenesulfonate, trifluoromethylbenzenesulfonate, trichloromethylbenzene sulfonate, fluorobenzenesulfonate, chlorobenzenesulfonate, 1 -hydroxyethane benzenesulfonate, 3-fluoro-4-methoxybenzenesulfonate, and the like. 15 When the electron-withdrawing component comprises a salt of an electron withdrawing anion, the counterion or cation of that salt can be any cation that allows the salt to rcvcrt or decompose back to the acid during calcining. Factors that dictate the suitability of the particular salt to serve as a source for the electron-withdrawing anion include, but are not limited to, the solubility of the salt in the desired solvent, 20 the lack of adverse reactivity of the cation, ion-pairing effects between the cation and anion, hygroscopic properties imparted to the salt by the cation, and the like, and thermal stability of the anion. Examples of suitable cations in the salt of the electron withdrawing anion include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H*, [H(OEt 2
)
2 ]*, and the like. 25 Further, combinations of one or more different electron withdrawing anions, in varying proportions, can be used to tailor the specific acidity of the activator-support to the desired level. Combinations of electron withdrawing components can be contacted with the oxide material simultaneously or individually, and any order that affords the desired activator-support acidity. For example, one aspect of this 30 invention is employing two or more electron-withdrawing anion source compounds in two or more separate contacting steps. Thus, one example of such a process by which an activator-support is prepared is as follows. A selected solid oxide compound, or WO 2007/092753 PCT/US2007/061519 32 combination of oxide compounds, is contacted with a first electron-withdrawing anion source compound to form a first mixture, this first mixture is then calcined, the calcined first mixture is then contacted with a second electron-withdrawing anion source compound to form a second mixture, followed by calcining said second 5 mixture to form a treated solid oxide compound. In such a process, the first and second electron-withdrawing anion source compounds are typically different compounds, although they can be the same compound. In one aspect of the invention, the solid oxide activator-support is produced by a process comprising: 10 1) contacting a solid oxide compound with at least one electron-withdrawing anion source compound to form a first mixture; and 2) calcining the first mixture to form the solid oxide activator-support. In another aspect of this invention, the solid oxide activator-support is produced by a process comprising: 15 1) contacting at least one solid oxide compound with a first electron withdrawing anion source compound to form a first mixture; and 2) calcining the first mixture to produce a calcined first mixture; 3) contacting the calcined first mixture with a second electron-withdrawing anion source compound to form a second mixture; and 20 4) calcining the second mixture to form the solid oxide activator-support. Thus, the solid oxide activator-support is sometimes referred to simply as a treated solid oxide compound. Another aspect of this invention producing or forming the solid oxide activator-support by contacting at least one solid oxide with at least one electron 25 withdrawing anion source compound, wherein the at least one solid oxide compound is calcined before, during or after contacting the electron-withdrawing anion source, and wherein there is a substantial absence of aluminoxanes and organoborates. In one aspect of this invention, once the solid oxide has been treated and dried, can be subsequently calcined. Calcining of the treated solid oxide is generally 30 conducted in an ambient or inert atmosphere, typically in a dry ambient atmosphere, at a temperature from about 200'C to about 900'C, and for a time of about 1 minute to about 100 hours. In another aspect, calcining is conducted at a temperature from WO 2007/092753 PCT/US2007/061519 33 about 300'C to about 800'C and in another aspect, calcining is conducted at a temperature from about 400 0 C to about 700 0 C. In yet another aspect, calcining is conducted from about 1 hour to about 50 hours, and in another aspect calcining is conducted, from about 3 hours to about 20 hours. In still another aspect, calcining can 5 be carried out from about 1 to about 10 hours at a temperature from about 350'C to about 550'C. Further, any type of suitable ambient can be used during calcining. Generally, calcining 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 10 carbon monoxide, can be used. In another aspect of the invention, the solid oxide component used to prepare the chemically-treated solid oxide has a pore volume greater than about 0.1 cc/g. In another aspect, the solid oxide component has a pore volume greater than about 0.5 cc/g, and in yet another aspect, greater than about 1.0 cc/g. In still another aspect, the 15 solid oxide component has a surface area from about 100 to about 1000 m 2/g. In another aspect, solid oxide component has a surface area from about 200 to about 800 2 2 m /g, and in still another aspect, from about 250 to about 600 m /g. The solid oxide material can be treated with a source of halide ion or sulfate ion, or a combination of anions, and optionally treated with at least one metal ion, 20 then calcined to provide the activator-support in the form of a particulate solid. In one aspect, the solid oxide material is treated with a source of sulfate, termed a sulfating agent, a source of chloride ion, termed a chloriding agent, a source of fluoride ion, termed a fluoriding agent, or a combination thereof, and calcined to provide the solid oxide activator. In another aspect, useful acidic activator-supports include, but are not 25 limited to: bromided alumina; chlorided alumina; fluorided alumina; sulfated alumina; bromided silica-alumina, chlorided silica-alumina; fluorided silica-alumina; sulfated silica-alumina; bromided silica-zirconia, chlorided silica-zirconia; fluorided silica-zirconia; sulfated silica-zirconia; chlorided zinc-alumina, triflate treated silica alumina, a pillared clay such as a pillared montmorillonite, optionally treated with 30 fluoride, chloride, or sulfate; phosphated alumina, or other aluminophosphates, optionally treated with sulfate, fluoride, or chloride; or any combination thereof.
WO 2007/092753 PCT/US2007/061519 34 Further, any of the activator-supports can optionally be treated with at least one other metal ion, typically from a metal salt or compound, wherein the metal ion can be the same as or different from any metal that makes up the solid oxide material. In one aspect of this invention, the treated oxide activator-support comprises a 5 fluorided solid oxide in the form of a particulate solid, thus a source of fluoride ion is added to the oxide by treatment with a fluoriding agent. In still another aspect, 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 are not limited to, the one to three carbon alcohols because of their volatility and low surface tension. Examples of 10 fluoriding agents that can be used in this invention include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride
(NH
4
HF
2 ), anmonium tetrafluoroborate (NH 4
BF
4 ), ammonium silicofluoride (hexafluorosilicate) ((NH4) 2 SiF 6 ), ammonium hexafluorophosphate (NH 4
PF
6 ), tetrafluoroboric acid (HBF 4 ), ammonium hexafluorotitanate (NH 4
)
2 TiF 6 , ammonium 15 hexafluorozirconate (NH 4
)
2 ZrF 6 , analogs thereof, and combinations thereof. For example, ammonium bifluoride NH 4
HF
2 can be used as the fluoriding agent, due to its case of use and ready availability. In another aspect of the present invention, the solid oxide can be treated with a fluoriding agent during the calcining step. Any fluoriding agent capable of 20 thoroughly contacting the solid oxide during the calcining step can be used. For example, in addition to those fluoriding agents described previously, volatile organic fluoriding agents can be used. Examples of volatile organic fluoriding agents useful in this aspect of the invention include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and combinations thereof. 25 Gaseous hydrogen fluoride or fluorine itself can also be used with the solid oxide is fluorided during calcining. One convenient method of contacting the solid oxide with the fluoriding agent is to vaporize a fluoriding agent into a gas stream used to fluidize the solid oxide during calcination. Similarly, in another aspect of this invention, the chemically-treated solid 30 oxide comprises a chlorided solid oxide in the form of a particulate solid, thus a source of chloride ion is added to the oxide by treatment with a chloriding agent. The chloride ion can be added to the oxide by forming a slurry of the oxide in a suitable WO 2007/092753 PCT/US2007/061519 35 solvent. In another aspect of the present invention, the solid oxide can be treated with a chloriding agent during the calcining step. Any chloriding agent capable of serving as a source of chloride and thoroughly contacting the oxide during the calcining step can be used. For example, volatile organic chloriding agents can be used. Examples o 5 of volatile organic chloriding agents useful in this aspect of the invention include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, or any combination thereof. Gaseous hydrogen chloride or chlorine itself can also be used with the solid oxide during calcining. One convenient method of contacting the oxide with the chloriding 10 agent is to vaporize a chloriding agent into a gas stream used to fluidize the solid oxide during calcination. When the activator-support comprises a chemically-treated solid oxide comprising a solid oxide treated with an electron-withdrawing anion, the electron withdrawing anion can be typically added to the solid oxide in an amount greater than 15 about 1% by weight of the solid oxide. In another aspect the electron withdrawing anion can be added to the solid oxide in an amount greater than about 2% by weight of the solid oxide, greater than about 3% by weight of the solid oxide, greater than about 5% by weight of the solid oxide, or greater than about 7% by weight of the solid oxide. 20 In one aspect, the amount of electron-withdrawing ion, for example fluoride or chloride ion, present before calcining the solid oxide is generally from about 2 to about 50% by weight, where the weight percents are based on the weight of the solid oxide, for example silica-alumina, before calcining. In another aspect, the amount of electron-withdrawing ion, for example fluoride or chloride ion, present before 25 calcining the solid oxide is from about 3 to about 25% by weight, and in another aspect, from about 4 to about 20% by weight. When halide ion is used as the electron-withdrawing anion, it is used in an amount sufficient to deposit, after calcining, from about 0.1% to about 50% by weight halide ion relative to the weight of the solid oxide. In another aspect, halide is used in an amount sufficient to deposit, 30 after calcining, from about 0.5% to about 40% by weight halide ion relative to the weight of the solid oxide, or from about 1% to about 30% by weight halide ion relative to the weight of the solid oxide. If the fluoride or chloride ion is added during WO 2007/092753 PCT/US2007/061519 36 calcining, such as when calcined in the presence of CCl 4 , there is typically no, or only trace levels, of fluoride or chloride ion in the solid oxide before calcining. Once impregnated with halide, the halided oxide can be dried by any method known in the art including, but not limited to, suction filtration followed by evaporation, drying 5 under vacuum, spray drying, and the like, although it is also possible to initiate the calcining step immediately without drying the impregnated solid oxide. The silica-alumina used to prepare the treated silica-alumina can have a pore volume greater than about 0.5 cc/g. In one aspect, the pore volume can be greater than about 0.8 cc/g, and in another aspect, the pore volume can be greater than about 10 1.0 cc/g. Further, the silica-alumina can have a surface area greater than about 100 m 2 /g. In one aspect, the surface area is greater than about 250 m 2 /g, and in another aspect, the surface area can be greater than about 350 m 2 /g. Generally, the silica alumina of this invention has an alumina content from about 5 to about 95%. In one aspect, the alumina content of the silica-alumina can be from about 5 to about 50%, 15 and in another aspect, the alumina content of the silica-alumina can be from about 8% to about 30% alumina by weight. The sulfated solid oxide comprises sulfate and a solid oxide component such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide is further treated with a metal ion such that the calcined sulfated oxide 20 comprises a metal. In one aspect, the sulfated solid oxide comprises sulfate and alumina. In one aspect of this invention, the sulfated alumina is formed by a process wherein the alumina is treated with a sulfate source, including for example, but not limited to, sulfuric acid or a sulfate salt such as ammonium sulfate, zinc sulfate, aluminum sulfate, nickel sulfate or copper sulfate. In one aspect, this process can be 25 performed by forming a slurry of the alumina in a suitable solvent such as alcohol or water, in which the desired concentration of the sulfating agent has been added. Suitable organic solvents include, but are not limited to, the one to three carbon alcohols because of their volatility and low surface tension. In this aspect, the amount of sulfate ion present before calcining is generally 30 from about 1% to about 50% by weight, from about 2% to about 30 % by weight, of from about 5% to about 25% by weight, where the weight percents are based on the weight of the solid oxide before calcining. Once impregnated with sulfate, the WO 2007/092753 PCT/US2007/061519 37 sulfated oxide can be dried by any method known in the art including, but not limited to, suction filtration followed by evaporation, drying under vacuum, spray drying, and the like, although it is also possible to initiate the calcining step immediately. In addition to being treated with an electron-withdrawing component such as 5 halide or sulfate ion, the solid inorganic oxide of this invention can optionally be treated with a metal source, including metal salts or metal-containing compounds. In one aspect of the invention, these compounds can be added to or impregnated onto the solid oxide in solution form, and subsequently converted into the supported metal upon calcining. Accordingly, the solid inorganic oxide can further comprise a metal 10 selected from zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or a combination thereof. For example, zinc can be used to impregnate the solid oxide because it provides good catalyst activity and low cost. The solid oxide can be treated with metal salts or metal-containing compounds before, after, or at the same time that the solid oxide is treated with the electron-withdrawing anion. 15 Further, 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 salt or metal-containing compound, includes, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like. Following any contacting method, the contacted mixture of oxide compound, electron-withdrawing anion, and 20 the metal ion is typically calcined. Alternatively, a solid oxide material, an electron withdrawing anion source, and the metal salt or metal-containing compound are contacted and calcined simultaneously. In another aspect, the ansa-metallocene compound can be contacted with an olefin monomer and an organoaluminum cocatalyst for a first period of time prior to 25 contacting this mixture with the acidic activator-support. Once the precontacted mixture of metallocene, monomer, and component that provides an activatable ligand to the metallocene, including but not limited to an organoaluminum cocatalyst, is contacted with the acidic activator-support, the composition further comprising the acidic activator-support is termed the "postoontacted" mixture. The postcontacted mixture 30 can be allowed to remain in further contact for a second period of time prior to being charged into the reactor in which the polymerization process will be carried out.
WO 2007/092753 PCT/US2007/061519 38 Various processes to prepare solid oxide activator-supports that can be employed in this invention have been reported. For example, U.S. Patent Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,391,816, 6,395,666, 6,524,987, and 6,548,441, describe such methods, each of 5 which is incorporated by reference herein, in its entirety. Ion-Exchangeable Activator-Supports and Layered Mineral Activator-Supports In one aspect of this invention, the activator-support used in preparing the catalyst compositions of this invention can comprise an ion-exchangeable activator 10 support, including but not limited to silicate and aluminosilicate compounds or minerals, either with layered or non-layered structures, and any combination thereof. In another aspect of this invention, ion-exchangeable, layered aluminosilicates such as pillared clays can be used as activator-supports. When the acidic activator-support comprises an ion-exchangeable activator-support, it can optionally be treated with at 15 least one electron-withdrawing anion such as those disclosed herein, though typically the ion-exchangeable activator-support is not treated with an electron-withdrawing anion. In one aspect, the activator-support of this invention can comprise clay minerals having exchangeable cations and layers capable of expanding. Typical clay 20 mineral activator-supports include, but are not limited to, ion-exchangeable, layered aluminosilicates such as pillared clays. Although the term "support" is used, it is not meant to be construed as an inert component of the catalyst composition, but rather is to be considered an active part of the catalyst composition, because of its intimate association with the ansa-metallocene and the component that provides an activatable 25 ligand to the metallocene, such as an organoaluminum. While not intending to be bound by theory, it is believed that the ion exchangeable activator-support serves as an insoluble reactant that reacts with the ansa-metallocene and organoaluminum components to form a catalyst composition used to produce polymer. In one aspect, the clay materials of this invention encompass materials either 30 in their natural state or that have been treated with various ions by wetting, ion exchange, or pillaring. Typically, the clay material activator-support of this invention comprises clays that have been ion exchanged with large cations, including WO 2007/092753 PCT/US2007/061519 39 polynuclear, highly charged metal complex cations. However, the clay material activator-supports of this invention also encompass clays that have been ion exchanged with simple salts, including, but not limited to, salts of Al(III), Fe(II), Fe(III) and Zn(II) with ligands such as halide, acetate, sulfate, nitrate, or nitrite. 5 In one aspect, the clay activator-support of this invention comprises pillared clays. The term pillared clays is used to refer to clay materials that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometallates, and other large ions. Thus, the term 10 pillaring refers to a simple exchange reaction in which the exchangeable cations of a clay material are replaced with large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the interlayers of the clay and when calcined are converted to metal oxide "pillars," effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce 15 the supporting pillars between clay layers, the expanded lattice structure is maintained and the porosity is enhanced. The resulting pores can vary in shape and size as a function of the pillaring material and the parent clay material used. Examples of pillaring and pillared clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) 20 Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent No. 4,060,480; each of which is incorporated herein in its entirety. The pillaring process utilizes clay minerals having exchangeable cations and layers capable of expanding. Any pillared clay that can enhance the polymerization 25 of olefins in the catalyst composition of the present invention can be used. Therefore, suitable clay minerals for pillaring include, but are not limited to: allophanes; smectites, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layer clays; the fiberous clays 30 including but not limited to sepiolites, attapulgites, and palygorskites; a serpentine clay; illite; laponite; saponite; or any combination thereof. In one aspect, the pillared WO 2007/092753 PCT/US2007/061519 40 clay activator-support comprises bentonite or montmorillonite, noting that the principal component of bentonite is montmorillonite. The pillared clay can be pretreated in the present invention. For example, in one embodiment, a pillared bentonite was pretreated by drying at about 300'C under 5 an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor. This example of a pretreament is not limiting, because prehcating steps such as this many be carried out at many othcr temperatures and times, including a combination of temperature and time steps, all of which are encompassed by this invention. 10 The ion-exchangeable activator-supports such as pillared clays used to prepare the catalyst compositions of this invention can be combined with other inorganic support materials, including, but are not limited to, zeolites, inorganic oxides, phosphated inorganic oxides, and the like. In one aspect, typical support materials that can be used in this regard include, but are not limited to, silica, silica-alumina, 15 alumina, titania, zirconia, magnesia, boria, fluorided alumina, silated alumina, thoria, aluminophosphate, aluminum phosphate, zinc aluminate, phosphated silica, phosphated alumina, silica-titania, coprecipitated silica/titania, fluorided/silated alumina, and any combination or mixture thereof. The amount of ansa-metallocene compound in relation to the ion-exchangable 20 activator-support used to prepare the catalyst composition of this invention is typically from about 0.1 wt% to about 15 wt% ansa-metallocene complex, based on the weight of the activator-support component (not based on the final metallocene clay mixture). It was also found that from about 1 wt% to about 10 wt% ansa mctalloccne works well to afford a catalyst that operates at desired activities. 25 The mixture of ansa-metallocene and clay activator-support can be contacted and mixed for any length of time to allow thorough contact between the ansa metallocene and activator-support. Sufficient deposition of the metallocene component on the clay can be achieved without heating a mixture of clay and metallocene complex. For example, the ansa-metallocene compound and the clay 30 material are simply mixed from about room temperature to about 200'F in order to achieve the deposition of the ansa-metallocene on the clay activator-support. In another aspect, the ansa-metallocene compound and. the clay material are mixed from WO 2007/092753 PCT/US2007/061519 41 about 100'F to about 180OF in order to achieve the deposition of the ansa-metallocene on the clay activator-support. In another aspect, the present invention encompasses catalyst compositions comprising an acidic activator-support, which can comprise a layered mineral. The 5 term "layered mineral" is used herein to describe materials such as clay minerals, pillared clays, ion-exchanged clays, exfoliated clays, exfoliated clays gelled into another oxide matrix, layered minerals mixed or diluted with other materials, and the like, or any combination thereof. When the acidic activator-support comprises a layered mineral, it can optionally be treated with at least one electron-withdrawing 10 anion such as those disclosed herein, though typically the layered mineral is not treated with an electron-withdrawing anion. For example, at least one clay mineral can be used as the activator-support. Clay minerals generally include the large group of finely-crystalline, sheet-like layered minerals that are found in nature in fine-grained sediments, sedimentary 15 rocks, and the like, and which constitute a class of hydrous silicate and aluminosilicate minerals with sheet-like structures and very high surface areas. This term is also used to describe hydrous magnesium silicates with a phyllosilicate structure. Examples of clay minerals that can be used in this invention include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and tri-octahedral 20 (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layer clays; the fiberous clays including but not limited to sepiolites, attapulgites, and palygorskites; a serpentine clay; illite; laponite; saponite; or any combination thereof. Many common clay minerals belong to the kaolinito, 25 montmorillonite, or illite groups of clays. Pillared clays can also be used as the activator-support of this invention, as disclosed herein. Pillared clays comprise clay minerals, typically of the of the smectite group and other phylosilicates in addition to sepiolites and palygorskites, that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations. 30 In one aspect of this invention, when layered minerals are used as activator supports or metallocene activators, the layered minerals are typically calcined prior to their use as activators. Typical calcination temperatures can range from about 100'C WO 2007/092753 PCT/US2007/061519 42 to about 700*C, from about 150'C to about 500*C, or from about 200'C to about 400 0 C. Non-Limiting Examples of the Catayst Composition 5 Examples of the catalyst composition of this invention include, but are not limited to the following. In one aspect or non-limiting example, the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-support, wherein: 10 a) the at least one ansa-metallocene comprises a compound having the formula: 4A
R
4 B R2,E M
R
3 A R 3 B (1), wherein M' is zirconium or hafnium; X is, independently, F, Cl, Br, or I; 15 E is C or Si; R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R' or R2 is an aryl group;
R
3 A and R3B are independently a hydrocarbyl group or a 20 trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10; and
R
4 A and R 4 B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen b) the at least one organoaluminum compound comprises 25 trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, WO 2007/092753 PCT/US2007/061519 43 diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein 5 the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, 10 phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof. Also in this aspect, the at least one ansa-metallocene can also comprise, or can 15 be selected from, a compound having the formula: R4A : R 4 B RLt,,, ya R2IE M
R
3 A R 3 B (11), wherein
M
1 is zirconium or hafnium; X is F, Cl, Br, or I; E is C or Si; 20 R 1 and R2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
R
3 A and R 3 3 are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl; 25 n is an integer from 1 to 6, inclusive; and
R
4 A and R 4 B are independently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen.
WO 2007/092753 PCT/US2007/061519 44 Also in this aspect, the at least one ansa-metallocene can also comprise, or can be selected from, a compound having the formula: R4A- / R 4 B R2., M< n
R
3 A R 3 B (111), wherein
M
1 is zirconium or hafnium; 5 X is Cl, Br, or I; E is C or Si; R' and R 2 are independently methyl or phenyl, wherein at least one of
R
1 or R 2 is phenyl;
R
3 A and R 3 B are independently H or methyl; 10 n is 1 or 2; and
R
4 A and R 4 B are independently H or t-butyl. Also in this aspect, the at least one ansa-metalloccnc can also comprise, or can t-Bu t-Bu t-Bu t-Bu PhilPh be selected from, t-Bu / t-Bu t-Bu t-Bu tBu t-Bu Ph,~ h P~~ Zr2 WO 2007/092753 PCT/US2007/061519 45 t-Bu t-Bu t-Bu t-Bu t-Bu t-Bu Phh/,,,,,,,.""f'.P....,"C' P hi ,c 4,,"', Ph Zr' Ph C Ph CI or any combination thereof. In another aspect or non-limiting example, the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one 5 ansa-metallocene, at least one organoaluminum compound, and at least one activator support, wherein: a) the at least one ansa-metallocene comprises t-Bu t-Bu t-Bu t-Bu t-Bu t-Bu Ph C Ph ~ Zr l CI MCI,,, t-Bu,, t-B00C Ph / t-Bu t-Bu Ph- d'%%C PhC -- %c I Ph"C ZrC t-Bu / t-Bu t-Bu t-Bu Ph/. .,C Ph ,/ CP ,, Ph Ph' C 10 ,or any combination thereof; b) the at least one organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; and c) the at least one activator-support comprises a sulfated solid oxide.
WO 2007/092753 PCT/US2007/061519 46 In still another aspect or non-limiting example, the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator support, wherein: 5 a) the at least one ansa-metallocene comprises t-Bu t-Bu t-Bu t-Bu t-B t-Bu Phi-,, ,,,ffCI Phi I .. MCI f0"-. 11ACI Ph Z C Ph- Ph" t-Bu t-Bu t-Bu t-Bu Ph,,,, Ph-' Hf"'W"C Ph-wO "*C or any combination thereof; b) the at least one organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination 10 thereof; and c) the at least one activator-support comprises sulfated alumina. In still another aspect or non-limiting example, the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one precontacted ansa-metallocene, at least one precontacted organoaluminum compound, 15 at least one precontacted olefin, and at least one postcontacted activator-support, wherein each of the ansa-metallocene, the organoaluminum compound, the olefin, and the activator-support are as disclosed herein. A further aspect of this invention provides for a catalyst composition comprising the contact product of at least one tightly-bridged ansa-metallocene 20 compound containing a pendant olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand, and at least one reagent that can function to convert the metallocene into an active catalyst that is different from the combination of the solid WO 2007/092753 PCT/US2007/061519 47 oxide activator-support and. organoaluminum compound. disclosed herein. Thus, in one aspect, the active catalyst composition can be formed typically upon activating the metallocene, which can include converting the metallocene compound to its cationic form, and by providing it with a hydrocarbyl ligand either before, after, or 5 during its conversion to a cation that can initiate olefin polymerization. The at least one reagent that can convert the metallocene into an active catalyst typically includes a component that provides an activatable ligand such as an alkyl to the metallocene, when the metallocene compound does not already comprise such a ligand, and an activator component, as provided herein. In some instances, both functions can be achieved with 10 one component, for example, an organoaluminoxane. In other instances, these two functions can be provided by two separate components, such as an organoaluminum compound that can provide an activatable alkyl ligand to the metallocene, and another component that can provide the activator function. In one aspect, for example, the activator and alkylation agent for the ansa 15 metallocene compound can be at least one organoaluminoxane, such as methylaluminoxane or isobutylaluminoxane. In another aspect, for example, the activator can be a Lewis acidic organoboron compound capable of abstracting an anionic ligand from the metallocene, such as tris(pentafluorophenyl)boron or triphenylcarbenium tetrakis(pentafluorophenyl)borate, that is used typically in 20 combination with an alkylating agent such as an organoaluminum compound. In still another aspect, a diallylated tightly-bridged ansa-metallocene compound as disclosed herein can be reacted with a Bronsted. acidic borate activator such as tri(n butyl)ammonium tetrakis(p-tolyl)borate or N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate to remove one alkyl ligand to form an alkylated 25 metallocene cation. Yet another aspect provides for a dialkylated tightly-bridged ansa-metallocene compound that can be reacted with a Lewis acidic borate activator such as triphenylcarbenium tetrakis(pentafluorophenyl)borate to remove one alkyl ligand to form an alkylated metallocene cation. Thus, while not intending to be bound by theory, it is believed that the active catalyst comprises an alkylated metallocene 30 cation, and any number of reaction steps can be used to generate such a catalyst. Yet a further aspect of this invention provides for a catalyst composition comprising the contact product of at least one tightly-bridged ansa-metallocene WO 2007/092753 PCT/US2007/061519 48 comprising at least one hydrocarbyl ligand that can initiate olefin polymerization and at least one solid oxide activator-support, without the need for an organoaluminum compound to form the contact product. In this aspect, the ansa-metallocene compound comprises a pendant olefin-containing moiety attached to at least one of 5 the cyclopentadienyl-type ligands, one or two aryl groups bonded to the bridging atom of the bridging ligand, and at least one hydrocarbyl ligand that can initiate olefin polymerization. An organoaluminum compound would not be required to alkylate this type of "pre-alkylated" ansa-metallocene because it already comprises a hydrocarbyl ligand that can initiate olefin polymerization. 10 Organoaluminoxane Activators In one aspect, the present invention provides a catalyst composition comprising, or a catalyst composition comprising the contact product of, at least one ansa-metallocene; optionally, at least one organoaluminum compound; and at least 15 one activator, wherein the activator can be selected independently from: i) an activator-support comprising a solid oxide treated with an clcctron-withdrawing anion, a layered mineral, an ion-exchangeablc activator support, or any combination thereof, ii) at least one organoaluminoxane compound; 20 iii) at least one organoboron or organoborate compound; or iv) any combination thereof. In another aspect, the present invention provides a catalyst composition comprising the contact product of at least one ansa-metallocene; at least one organoaluminum compound; at least one activator-support comprising a solid oxide 25 treated with an electron-withdrawing anion; and optionally, an aluminoxane cocatalyst. In still another aspect, the present invention provides a catalyst composition comprising an ansa-metallocene compound containing a pendant unsaturated moiety, an aluminoxane cocatalyst, an optional activator-support, and an optional organoaluminum compound. However, in one aspect, the catalyst 30 composition of this invention is substantially free of aluminoxanes, and in another aspect, the catalyst composition of this invention have polymerization activity in the substantial absence of aluminoxanes.
WO 2007/092753 PCT/US2007/061519 49 In another aspect, the present invention provides a catalyst composition comprising at least one ansa-metallocene compound and an aluminoxane. In this aspect, the catalyst composition is not required to comprise either an acidic activator support wherein the activator-support comprises a chemically-treated solid oxide, and 5 the catalyst composition is also not required to comprise an organoaluminum compound. Thus, any ansa-metallocene compounds disclosed herein can be combined with any of the aluminoxanes (poly(hydrocarbyl aluminum oxides)) disclosed herein, or any combination of aluminoxanes disclosed herein, to form a catalyst composition of this invention. Further, any ansa-metallocene compounds 10 disclosed herein can be combined with any aluminoxane or combination of aluminoxanes, and optionally an activator-support; optionally, a layered mineral; optionally, an ion-exchangeable activator-support; optionally, at least one organoboron compound; and optionally, at least one organoborate compound, to form a catalyst composition of this invention. 15 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, though any solvent which is substantially inert to the reactants, intermediates, and products of the activation step can be used. The catalyst composition formed in this manner can be collected by 20 methods known to those of skill in the art, including but not limited to filtration, or the catalyst composition can be introduced into the polymerization reactor without being isolated. In one aspect, the aluminoxane compound of this invention is an oligomeric aluminum compound, wherein the aluminoxane compound can comprise linear 25 structures, cyclic, or cage structures, or typically mixtures of all three. Cyclic aluminoxane compounds having the formula: R ; wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 3 to about 10 are encompassed by this invention. The (AlRO), moiety shown WO 2007/092753 PCT/US2007/061519 50 here also constitutes the repeating unit in a linear aluninoxane. Thus, linear aluminoxanes having the formula: R R l-O Al R ; wherein R is a linear or branched alkyl having from I to 10 carbon atoms, and n is an integer 5 from 1 to about 50, are also encompassed by this invention. Further, aluminoxanes can also have cage structures of the formula Rtsme+Rb aAl4mO3,n, wherein m is 3 or 4 and a is = nA(3) - no( 2 ) + no( 4 ); wherein nA(3) is the number of three coordinate aluminum atoms, no( 2 ) is the number of two coordinate oxygen atoms, no(4) is the number of 4 coordinate oxygen atoms, Rt represents a 10 terminal alkyl group, and R represents a bridging alkyl group; wherein R is a linear or branched alkyl having from I to 10 carbon atoms. Thus, aluminoxanes can be represented generally by formulas such as (R-Al O)., R(R-Al-O),AlR 2 , and the like, wherein the R group is typically a linear or branched C1-C 6 alkyl such as methyl, ethyl, propyl, butyl, pentyl, or hexyl wherein n 15 typically represents an integer from 1 to about 50. In one embodiment, the aluminoxane compounds of this invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propyl aluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, 20 iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof. While organoaluminoxancs with different types of R groups arc encompassed by the present invention, methyl aluminoxane (MAO), ethyl aluminoxane, or isobutyl aluminoxane are typical optional cocatalysts used in the catalyst compositions of this invention. These aluminoxanes are prepared from trimethylaluminum, 25 triethylaluminum, or triisobutylaluminum, respectively, and are sometimes referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminum, such as disclosed in U.S. Patent No. 4,794,096, which is herein incorporated by reference in its entirety.
WO 2007/092753 PCT/US2007/061519 51 The present invention contemplates many values of n in the aluminoxane formulas (R-Al-O), and R(R-Al-O).AlR 2 , and typically n is at least about 3. However, depending upon how the organoaluminoxane is prepared, stored, and used, the value of n can be variable within a single sample of aluminoxane, and such a 5 combination of organoaluminoxanes are comprised in the methods and compositions of the present invention. In preparing the catalyst composition of this invention comprising an optional aluminoxane, the molar ratio of the aluminum in the aluminoxane to the metallocene in the composition is usually from about 1:10 to about 100,000:1. In one another 10 aspect, the molar ratio of the aluminum in the aluminoxane to the metallocene in the composition is usually from about 5:1 to about 15,000:1. The amount of optional aluminoxane added to a polymerization zone is an amount within a range of 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 to about 50 mg/L. 15 Organoaluminoxanes can be prepared by various procedures which are well known in the art. Examples of organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, each of which is incorporated by rcfcrence herein, in its entirety. One example of how an aluminoxane can be prepared is as follows. Water, which is dissolved in an inert organic solvent, can be reacted with an 20 aluminum alkyl compound such as AlR 3 to form the desired organoaluminoxane compound. While not intending to be bound by this statement, it is believed that this synthetic method can afford a mixture of both linear and cyclic (R-Al-O)" aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes can be prepared by reacting an aluminum alkyl 25 compound such as AIR 3 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent. Organoboron and Organoborate Activators As provided herein, in one aspect, the present invention provides a catalyst 30 composition comprising, or a catalyst composition comprising the contact product of, at least one ansa-metallocene; optionally, at least one organoaluminum compound; and at least one activator. The activator can be selected independently from: at least WO 2007/092753 PCT/US2007/061519 52 one activator-support as provided herein; at least one organoaluminoxane compound; at least one organoboron or organoborate compound; or any combination thereof. Accordingly, in one aspect of the present invention the at least one activator can be selected from at least one organoboron compound, at least one organoborate compound, 5 or a combination thereof. In a further aspect, the present invention provides a catalyst composition comprising the contact product of at least one ansa-metallocene; at least one organoaluminum compound; at least one activator-support comprising a solid oxide treated with an electron-withdrawing anion; and optionally, an organoboron or 10 organoborate cocatalyst. In another aspect, the present invention provides a catalyst composition comprising the contact product of: at least one ansa-metallocene compound containing a pendant unsaturated moiety; an organoboron or organoborate cocatalyst; an organoaluminum compound; and optionally, an activator-support. In this aspect, the catalyst composition is not required to comprise an activator-support. 15 Any ansa-metallocene compound disclosed herein can be combined with any of the organoboron or organoborate cocatalysts disclosed herein, or any combination of organoboron or organoborate cocatalysts disclosed herein, along with a component that provides an activatable ligand such as an alkyl or hydride ligand to the metallocene, when the metallocene compound does not already comprise such a ligand, such as an 20 organoaluminum compound; to form a catalyst composition. Further, any ansa metallocene compounds disclosed herein can be combined with any an organoboron or organoborate cocatalyst; an organoaluminum compound; optionally, at least one aluminoxane; and optionally, an activator-support; to form a catalyst composition of this invention. However, in one aspect, the catalyst composition of this invention is 25 substantially free of organoboron or organoborate compounds, and in another aspect, the catalyst composition of this invention have polymerization activity in the substantial absence of organoboron or organoborate compounds. In one aspect, as provided herein, the term "organoboron" compound can be used to refer to neutral boron compounds, borate salts, or combinations thereof For 30 example, the organoboron compounds of this invention can comprise a fluoroorgano boron compound, a fluoroorgano borate compound, or a combination thereof Any fluoroorgano boron or fluoroorgano borate compound known in the art can be WO 2007/092753 PCT/US2007/061519 53 utilized. The term fluoroorgano boron compounds has its usual meaning to refer to neutral compounds of the form BY 3 . The term fluoroorgano borate compound also has its usual meaning to refer to the monoanionic salts of a fluoroorgano boron compound of the form [cation]+[BY 4 ]-, where Y represents a fluorinated organic 5 group. For convenience, fluoroorgano boron and fluoroorgano borate compounds are typically referred to collectively by organoboron compounds, or by either name as the context requires. Examples of fluoroorgano borate compounds that can be used as cocatalysts in the present invention include, but are not limited to, fluorinated aryl borates such as, 10 NN-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, NN dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, including mixtures thereof. Examples of fluoroorgano boron compounds that can be used as cocatalysts 15 in the present invention include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, including mixtures thereof. Although not intending to be bound by the following theory, these examples of fluoroorgano borate and fluoroorgano boron compounds, and related compounds, are thought to form "weakly-coordinating" anions when combined with organometal 20 compounds, as disclosed in U.S. Patent 5,919,983. Generally, any amount of organoboron compound can be utilized in this invention. In one aspect, the molar ratio of the organoboron compound to the metallocene compound in the composition is from about 0.1:1 to about 10:1. Typically, the amount of the fluoroorgano boron or fluoroorgano borate compound 25 used as a cocatalyst for the metallocene is in a range of from about 0.5 mole to about 10 moles of boron compound per mole of metallocene compound. In one aspect, the amount of fluoroorgano boron or fluoroorgano borate compound used as a cocatalyst for the metallocene is in a range of from about 0.8 mole to about 5 moles of boron compound per mole of metallocene compound. 30 WO 2007/092753 PCT/US2007/061519 54 The Optional Ionizing Ionic Compound Cocatalyst In one aspect, the present invention provides a catalyst composition comprising, or a catalyst composition comprising the contact product of: 1) at least one tightly-bridged ansa-metallocene compound comprising an olefin-containing 5 moiety bonded to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, as disclosed herein. In another aspect, the present invention provides a catalyst composition as disclosed herein, comprising an optional ionizing ionic compound cocatalyst in addition to these 10 other components. However, in one aspect, the catalyst composition of this invention is substantially free of ionizing ionic compounds, and in another aspect, the catalyst composition of this invention have polymerization activity in the substantial absence of ionizing ionic compounds. In still another aspect, the present invention provides a catalyst composition comprising at least one ansa-metallocene compound as disclosed 15 herein, at least one ionizing ionic compound cocatalyst, optionally at least one activator-support, and optionally at least one organoaluminum compound. Examples of ionizing ionic compound are disclosed in U.S. Patent Numbers 5,576,259 and 5,807,938. An ionizing ionic compound is an ionic compound which can function to 20 enhance activity of the catalyst composition. While not bound by theory, it is believed that the ionizing ionic compound can be capable of reacting with the metallocene compound and converting the metallocene into a cationic metallocene compound. Again, while not intending to be bound by theory, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or 25 partially extracting an anionic ligand, possibly a non- 1 5 -alkadienyl ligand such as
(X
3 ) or (X 4 ), from the metallocene. However, the ionizing ionic compound is an activator regardless of whether it is ionizes the metallocene, abstracts an (X 3 ) or (X 4 ) ligand in a fashion as to form an ion pair, weakens the metal-(X 3 ) or metal-(X 4 ) bond in the metallocene, simply coordinates to an (X 3 ) or (X 4 ) ligand, or any other 30 mechanisms by which activation can occur. Further, it is not necessary that the ionizing ionic compound activate the metallocene only. The activation function of the ionizing ionic compound is evident in the enhanced activity of catalyst composition as WO 2007/092753 PCT/US2007/061519 55 a whole, as compared to a catalyst composition containing catalyst composition that does not comprise any ionizing ionic compound. Examples of ionizing ionic compounds include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl) 5 ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4 dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n butyl)ammonium tetrakis(pentafluorophenyl)borate, NN-dimethylanilinium tetrakis(p-tolyl)borate, NN-dimethylanilinium tetrakis(m-tolyl)borate, N,N 10 dimethylanilinium tetrakis(2,4-dinethylphenyl)borate, NN-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro methyl)phenyl]borate, NN-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, 15 triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoro 20 methyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate, lithium tetrakis(p tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4 dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl) 25 borate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyi)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m tolyl)borate, potassium tetrakis(2,4-dimethylphenyl)borate, potassium tetrakis(3,5 30 dimethylphenyl)borate, potassium tetrafluoroborate, triphenylcarbenium tetrakis(p tolyl)aluminate, triphenylcarbenium tetrakis(m-tolyl)aluminate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbenium tetrakis(3,5- WO 2007/092753 PCT/US2007/061519 56 dimethylphenyl)aluminate, triphenylcarbenium tetrakis(pentafluorophenyl)aluiinate, tropylium tetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate, tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropylium tetrakis(3,5 dimethylphenyl)aluminate, tropylium tetrakis(pentafluorophenyl)aluminate, lithium 5 tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluninate, lithium tetrakis(2,4 dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetrakis(ph enyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m 10 tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5 dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis (3,5 15 dimethylphenyl)aluminate, potassium tetrafluoroaluminate, triphenylcarbenium tris(2,2',2"-nonafluorobiphenyl)fluoroaluminate, silver tetrakis( 1,1,1,3,3,3 hexafluoroisopropanolato)aluminatc, or silver tetrakis(porfluoro-t-butoxy)aluminatc, or any combination thereof. However, these ionizing ionic compound are exemplary, and the ionizing ionic compound is not limited thereto in the present invention. 20 The Olefin Monomer In one aspect of this invention, unsaturated reactants that are useful in the polymerization processes with catalyst compositions and processes of this invention include olefin compounds having from about 2 to about 30 carbon atoms per molecule 25 and having at least one olefinic double bond. This invention encompasses homopolyrnerization processes using a single olefin such as ethylene or propylene, as well as copolymerization reactions with at least one different olefinic compound. In one aspect of a copolymerization reaction of ethylene, copolymers of ethylene comprise a major amount of ethylene (>50 mole percent) and a minor amount of 30 comonomer <50 mole percent), though this is not a requirement. The comonomers that can be copolymerized with ethylene should have from three to about 20 carbon atoms in their molecular chain.
WO 2007/092753 PCT/US2007/061519 57 Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins can be employed in this invention. For example, typical unsaturated compounds that can be polymerized with the catalysts of this invention include, but are not limited to, propylene, 1-butene, 2 5 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-heptcne, the four normal octenes, the four normal nonenes, the five normal decenes, and mixtures of any two or more thereof. Cyclic and bicyclic olefins, including but not limited to, cyclopentene, cyclohexene, norbornylene, norbomadiene, 10 and the like, can also be polymerized as described above. In one aspect, when a copolymer is desired, the monomer ethylene can be copolymerized with a comonomer. In another aspect, examples of the comonomer include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-i-pentene, 4-methyl-1-pentene, 1 15 hexene, 2-hexene, 3-hexene, 3-ethyl-1 -hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes, the four normal nonenes, or the five normal decenes. In another aspect, the comonomer can be 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or styrene. In one aspect, the amount of comonomer introduced into a reactor zone to 20 produce the copolymer is generally from about 0.001 to about 99 weight percent comonomer based on the total weight of the monomer and comonomer. In one aspect, the amount of comonomer introduced into a reactor zone to produce the copolymer is generally from about 0.01 to about 50 weight percent comonomer based on the total weight of the monomer and comonomer. In another aspect, the amount of 25 comonomer introduced into a reactor zone is from about 0.01 to about 10 weight percent comonomer, and in still another aspect, from about 0.1 to about 5 weight percent comonomer based on the total weight of the monomer and comonomer. Alternatively, an amount sufficient to give the above described concentrations by weight, in the copolymer produced can be used. 30 While not intending to be bound by this theory, in the event that branched, substituted, or functionalized olefins are used as reactants, it is believed that steric hindrance can impede and/or slow the polymerization process. Thus, branched and/or WO 2007/092753 PCT/US2007/061519 58 cyclic portion(s) of the olefin removed somewhat from the carbon-carbon double bond would not be expected to hinder the reaction in the way that the same olefin substituents situated more proximate to the carbon-carbon double bond might. In one aspect, at least one reactant for the catalyst compositions of this invention is ethylene, 5 so the polyrnerizations are either homopolymerizations or copolymerizations with a different acyclic, cyclic, terminal, internal, linear, branched, substituted, or unsubstituted olefin. In addition, the catalyst compositions of this invention can be used in polymerization of diolefin compounds, including but are not limited to, 1,3 butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene. 10 Preparation of the Catalyst Composition In one aspect, this invention encompasses a catalyst composition and a method comprising contacting at least one tightly-bridged ansa-metallocene compound, at least one activator, and optionally at least one organoaluminum compound, as 15 disclosed herein. The method disclosed herein encompasses any series of contacting steps that allows contacting each of the components provided, any order of contacting components or mixtures of components. While not intending to be limiting, examples of contacting steps are typically exemplified herein using a treated solid oxide activator-support and an organoaluminum cocatalyst. These exemplary steps can 20 encompass any number of precontacting and postcontacting steps, and can further encompass using an olefin monomer as a contact component in any of these steps. Examples of preparative methods to prepare the catalyst composition of this invention follow. In one aspect of this invention, the ansa-metallocene can be precontacted with 25 an olefinic monomer, not necessarily the olefin monomer to be polymerized, and an organoaluminum cocatalyst for a first period of time prior to contacting this precontacted mixture with the solid oxide activator-support. For example, the first period of time for contact, the precontact time, between the ansa-metallocene, the olefinic monomer, and the organoaluninum cocatalyst can typically range from time 30 about 1 minute to about 24 hours, and from about 0.1 to about 1 hour is typical. Precontact times from about 10 minutes to about 30 minutes are also typical.
WO 2007/092753 PCT/US2007/061519 59 Once the precontacted mixture of ansa-metallocene, olefin monomer, and organoaluminum cocatalyst is contacted with the solid oxide activator, this composition (further comprising the solid oxide activator) is termed the postcontacted mixture. Typically, the postcontacted mixture can be allowed to remain in contact for 5 a second period of time, the postcontact time, prior to being initiating the polymerization process. In one aspect, postcontact times between the solid oxide activator-support and the precontacted mixture typically range from time about 1 minute to about 24 hours, and from 0.1 to about 1 hour is typical. Postcontact times from about 10 minutes to about 30 minutes are also typical. 10 In another aspect of this invention, the various catalyst components (for example, ansa-metallocene, activator-support, organoaluminum cocatalyst, and optionally an unsaturated hydrocarbon) can be contacted in the polymerization reactor simultaneously while the polymerization reaction is proceeding. Alternatively, any two or more of these catalyst components can be "precontacted" in a vessel or tube 15 prior to their entering the reaction zone. This precontacting step can be a continuous process, in which the precontacted product is fed continuously to the reactor, or it can be a stcpwisc or batchwise process in which a batch of prccontactcd product can be added to make a catalyst composition. This precontacting step can be carried out over a time period that can range from a few seconds to as much as several days, or longer. 20 In this aspect, the continuous precontacting step can last typically from about 1 second to about 1 hour. Also in this aspect, the continuous precontacting step can last typically from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes. Alternatively the precontacting process can be carried out in multiple steps, 25 rather than a single step, in which multiple mixtures are prepared, each comprising a different set of catalyst components. For example, at least two catalyst components can be contacted forming a first mixture, followed by contacting the first mixture with at least one other catalyst component forming a second mixture, and so forth. Multiple precontacting steps can be carried out in a single vessel or in multiple 30 vessels. Further, multiple precontacting steps can be carried out in series (sequentially), in parallel, or a combination thereof. For example, a first mixture of two catalyst components can be formed in a first vessel, a second mixture comprising WO 2007/092753 PCT/US2007/061519 60 the first mixture plus one additional catalyst component can be formed in the first vessel or in a second vessel, which is typically placed downstream of the first vessel. In another aspect, one or more of the catalyst components can be split and used in different precontacting treatments. For example, part of a catalyst component 5 can be fed into a first precontacting vessel for precontacting with at least one other catalyst component, while the remainder of that same catalyst component can be fed into a second precontacting vessel for precontacting with at least one other catalyst component, or can be fed directly into the reactor, or a combination thereof. The precontacting can be carried out in any suitable equipment, such as tanks, stirred mix 10 tanks, various static mixing devices, a tube, a flask, a vessel of any type, or any combination thereof. In one aspect, for example, a catalyst composition of this invention is prepared by contacting 1-hexene, triisobutylaluminum or tri-n-butylaluminum, and an ansa metallocene for at least about 30 minutes, followed by contacting this precontacted 15 mixture with a sulfated alumina activator-support for at least about 10 minutes up to one hour to form the active catalyst. The precontacting step typically increases the productivity of the polymer as compared to the same catalyst composition that is prepared without this precontacting step. The enhanced activity catalyst composition of this invention can be used for 20 homopolymerization of an a-olefin monomer such as ethylene or copolymerization of an at-olefin and a comonomer. However, neither a precontacting step nor a postcontacting step are required for this invention. The postcontacted mixture can be heated at a temperature and for a duration sufficient to allow adsorption, impregnation, or interaction of precontacted mixture 25 and the solid oxide activator-support, such that a portion of the components of the precontacted mixture is immobilized, adsorbed, or deposited thereon. For example, the postcontacted mixture can be heated from between about 04F to about 1501F. Temperatures between about 40'F to about 95*F are typical if the mixture is heated at all. 30 In one aspect, the molar ratio of the ansa-metallocene compound to the organoaluminum compound can be from about 1:1 to about 1:10,000. In another aspect, the molar ratio of the ansa-metallocene compound to the organoaluminum WO 2007/092753 PCT/US2007/061519 61 compound can be from about 1:1 to about 1:1,000, and in another aspect, from about 1:1 to about 1:100. These molar ratios reflect the ratio of ansa-metallocene compound to the total amount of organoaluminum compound in both the precontacted mixture and the posteontacted mixture combined. 5 When a precontacting step is used, generally, the molar ratio of olefin monomer to ansa-metallocene compound in the precontacted mixture can be from about 1:10 to about 100,000:1, or from about 10:1 to about 1,000:1. In another aspect of this invention, the weight ratio of the solid oxide activator to the organoaluminum compound can range from about 1:5 to about 1,000:1. In 10 another aspect, the weight ratio of the solid oxide activator to the organoaluminum compound can be from about 1:3 to about 100:1, and in yet another aspect, from about 1:1 to about 50:1. In a further aspect of this invention, the weight ratio of the ansa-metallocene to solid oxide activator-support can be from about 1:1 to about 1:1,000,000. Yet 15 another aspect of this invention is the weight ratio of the ansa-metallocene to solid oxide activator-support which can be from about 1:10 to about 1:100,000, and in another aspect, from about 1:20 to about 1:1000. One aspect of this invention is that aluminoxane is not required to form the catalyst composition disclosed herein, a feature that allows lower polymer production 20 costs. Accordingly, in one aspect, the present invention can use AlR 3 -type organoaluminum compounds and an activator-support in the absence of aluminoxanes. While not intending to be bound by theory, it is believed that the organoaluminum compounds likely do not activate the metallocene catalysts in the same manner as an organoaluminoxane. 25 Additionally, no expensive borate compounds or MgCl 2 are required to form the catalyst composition of this invention, although aluminoxane, borate compounds, MgC 12, or any combination thereof can be used optionally in the catalyst composition of this invention. Further, in one aspect, cocatalysts such as aluminoxanes, organoboron compounds, ionizing ionic compounds, or any combination thereof can 30 be used as cocatalysts with the ansa-metallocene, either in the presence or absence of the activator support. Further, cocatalysts such as aluminoxanes, organoboron compounds, ionizing ionic compounds, or any combination thereof can be used as WO 2007/092753 PCT/US2007/061519 62 with the ansa-metallocene, either and in the presence or absence of an organoaluminum compound, as specified herein. Thus, the at least one organoaluminurn compound is optional when at least one ligand on the metallocene is a hydrocarbyl group, H, or BH4; when the at least one activator comprises an 5 organoaluminoxane compound; or both these conditions are present. However, the catalyst compositions of the present invention are active in the substantial absence of cocatalysts such as aluminoxanes, organoboron compounds, ionizing ionic compounds, or any combination thereof. Thus, in one aspect, this invention provides a process to produce a catalyst 10 composition, comprising: contacting at least one ansa-metallocene, at least one olefin, and at least one organoaluminum compound for a first period of time to form a precontacted mixture comprising at least one precontacted ansa-metallocene, at least one precontacted organoaluminum compound, and at least one precontacted olefin; and 15 contacting the precontacted mixture with at least one activator-support and optionally additional organoaluminum compound for a second period of time to form a postcontacted mixture comprising at Icast one postcontacted ansa-metallocene, at least one postcontacted organoaluminum compound, at least one postcontacted olefin, and at least one postcontacted activator-support. In one aspect, the at least one 20 ansa-metallocene can comprise a compound having the formula:
(XI)(X
2
)(X
3
)(X
4 )Ml, wherein M' is titanium, zirconium, or hafnium;
(X
1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; 25 one substituent on (X') and (X 2 ) is a bridging group having the formula
ER'R
2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X') and (X 2 ), and wherein R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R' and R 2 is an aryl group; 30 at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; WO 2007/092753 PCT/US2007/061519 63
(X
3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any 5 of which having up to 12 carbon atoms; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a 10 phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen. In one aspect, the catalytic activity of the catalyst of this invention is typically greater than or equal to about 100 grams polyethylene per gram of chemically treated solid oxide per hour (abbreviated gP/(gCTSO-hr)). In another aspect, the catalyst of 15 this invention can be characterized by an activity of greater than or equal to about 250 gP/(gCTSO-hr), and in another aspect, an activity of greater than or equal to about 500 gP/(gCTSO-hr). In still another aspect, the catalyst of this invention can be characterized by an activity of greater than or equal to about 1000 gP/(gCTSO-hr), and in another aspect, an activity of greater than or equal to about 2000 20 gP/(gCTSO-hr). In one aspect, this activity is typically measured under slurry polymerization conditions using isobutane as the diluent, with a polymerization temperature of about 90 'C, and an ethylene pressure of about 550 psig. In another aspect, this activity is measured under slurry polymerization conditions using isobutane as the diluent, with a polymerization temperature from about 80 'C to about 25 105 'C, and an ethylene pressure from about 450 psig to about 550 psig. The reactor should have substantially no indication of any wall scale, coating or other forms of fouling upon making these measurements. Utility of the Catalyst Composition in Polymerization Processes 30 The catalysts of the present invention are intended for any olefin polymerization method known in the art, using various types of polymerization WO 2007/092753 PCT/US2007/061519 64 reactors. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing olefin monomers to produce homopolymers or copolymers. Such homopolymers and copolymers are referred to as resins or polymers. The various types of reactors include those that may be referred to as 5 batch, slurry, gas-phase, solution, high pressure, tubular or autoclave reactors. Gas phase reactors may comprise fluidized bed reactors or staged horizontal reactors. Slurry reactors may comprise vertical or horizontal loops. High pressure reactors may comprise autoclave or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes could use intermittent or continuous product 10 discharge. Processes may also include partial or full direct recycle of un-reacted monomer, un-reacted comonomer, and/or diluent. Polymerization reactor systems of the present invention may comprise one type of reactor in a system or multiple reactors of the same or different type. Production of polymers in multiple reactors may include several stages in at least two 15 separate polymerization reactors interconnected by a transfer device making it possible to transfer the polymers resulting from the first polymerization reactor into the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from 20 one reactor to subsequent reactors for continued polymerization. Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas reactors, a combination of loop and gas reactors, multiple high pressure reactors or a combination of high pressure with loop and/or gas reactors. The multiple reactors may be operated in series or in parallel. 25 According to one aspect of the invention, the polymerization reactor system may comprise at least one loop slurry reactor. Such reactors are known in the art and may comprise vertical or horizontal loops. Monomer, diluent, catalyst and optionally any comonomer may be continuously fed to a loop reactor where polymerization occurs. Generally, continuous processes may comprise the continuous introduction of 30 a monomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent. Reactor effluent may be flashed to remove the solid polymer from the liquids WO 2007/092753 PCT/US2007/061519 65 that comprise the diluent, monomer and/or comonomer. Various technologies may be used for this separation step including but not limited to, flashing that may include any combination of heat addition and pressure reduction; separation by cyclonic action in either a cyclone or hydrocyclone; or separation by centrifugation. 5 A typical slurry polymerization process (also known as the particle form process), which is well known in the art 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 by reference in its entirety herein. Suitable diluents used in slurry polymerization are well known in the art and 10 include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquids under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions can occur under bulk conditions where no diluent is used. An example is 15 polymerization of propylene monomer as disclosed in U.S. Patent Nos. 5,455,314, which is incorporated by reference herein in its entirety. According to yet another aspect of this invention, the polymerization reactor may comprise at least one gas phase reactor. Such systems are known in the art and may employ a continuous recycle stream containing one or more monomers 20 continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream may be withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product may be withdrawn from the reactor and new or fresh monomer may be added to replace the polymerized monomer. Such gas phase reactors may comprise a process for multi 25 step gas-phase polymerization of olefins, in which olefins are polymerized in the gaseous phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in U.S. Patent Nos. 5,352,749, 4588,790 and 5,436,304, each of which is incorporated by reference 30 in its entirety herein. According to still another aspect of the invention, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor, both of WO 2007/092753 PCT/US2007/061519 66 which are known in the art. Tubular reactors may have several zones where fresh monomer, initiators, or catalysts are added. Monomer may be entrained in an inert gaseous stream and introduced at one zone of the reactor. Initiators, catalysts, and/or catalyst components may be entrained in a gaseous stream and introduced at another 5 zone of the reactor. The gas streams may be intermixed for polymerization. Heat and pressure may be employed appropriately to obtain optimal polymerization reaction conditions. According to yet another aspect of the invention, the polymerization reactor may comprise a solution polymerization reactor wherein the monomer is contacted 10 with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer may be employed. If desired, the monomer may be brought in the vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a 15 solution of the polymer in a reaction medium. Agitation may be employed to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Adequate means are utilized for dissipating the exothermic heat of polymerization. These reactors are known in the art. Polymerization reactors suitable for the present invention may further 20 comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components, and/or at least one polymer recovery system. Suitable reactor systems for the present invention may further comprise systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycle, storage, loadout, laboratory 25 analysis, and process control. Conditions that are controlled for polymerization efficiency and to provide resin properties include temperature, pressure and the concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. Suitable polymerization 30 temperature may be any temperature below the de-polymerization temperature according to the Gibbs Free energy equation. Typically this includes from about 60 0
C
WO 2007/092753 PCT/US2007/061519 67 to about 280'C, for example, and from about 70'C to about 110 C, depending upon the type of polymerization reactor. Suitable pressures will also vary according to the reactor and polymerization type. The pressure for liquid phase polymerizations in a loop reactor is typically less 5 than 1000 psig. Pressure for gas phase polymerization is usually at about 200 - 500 psig. High pressure polymerization in tubular or autoclave reactors is generally run at about 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region occurring at generally higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical 10 phase) may offer advantages. The concentration of various reactants can be controlled to produce resins with certain physical and mechanical properties. The proposed end-use product that will be formed by the resin and the method of forming that product determines the desired resin properties. Mechanical properties include tensile, flexural, impact, creep, stress 15 relaxation and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, temperature melt of crystallization, density, stereoregularity, crack growth, long chain branching and rheological measurements. The concentrations of monomer, co-monomer, hydrogen, co-catalyst, 20 modifiers, and electron donors are important in producing these resin properties. Comonomer is used to control product density. Hydrogen is used to control product molecular weight. Co-catalysts can be used to alkylate, scavenge poisons and control molecular weight. Modifiers can be used to control product properties and electron donors affect stercoregularity. In addition, the concentration of poisons must be 25 minimized since they impact the reactions and product properties. The polymer or resin may be formed into various articles, including, but not limited to, bottles, drums, toys, household containers, utensils, film products, drums, fuel tanks, pipes, geomembranes, and liners. Various processes may be used to form these articles, including, but not limited to, blow molding, extrusion molding, 30 rotational molding, thermoforming, cast molding and the like. After polymerization, additives and modifiers can be added to the polymer to provide better processing during manufacturing and for desired properties in the end product. Additives include WO 2007/092753 PCT/US2007/061519 68 surface modifiers such as slip agents, antiblocks, tackifiers; antioxidants such as primary and secondary antioxidants; pigments; processing aids such as waxes/oils and fluoroelastomers; and special additives such as fire retardants, antistats, scavengers, absorbers, odor enhancers, and degradation agents. 5 Ethylene Polymers Prepared According to this Invention In one aspect, the ethylene polymer produced using the catalyst composition of this invention is typically characterized by lower levels of long chain branching (LCB) than are typically observed when using a tightly-bridged ansa-metallocene 10 compound without an olefin-containing moiety bonded to a cyclopentadienyl-type ligand, even when the comparative metallocene comprises at least one aryl group bonded to the bridging atom of the bridging ligand. In a further aspect, the ethylene polymer produced using the catalyst composition of this invention is typically characterized by higher molecular weights than are typically observed when using a 15 tightly-bridged ansa-metallocene compound without at least one aryl group bonded to the bridging atom of the bridging ligand, even when the comparative metallocene comprises an olcfin-containing moiety bonded to a cyclopentadienyl-type ligand. Figures 3 through 8 illustrate various aspects of olefin homopolymer produced according to this invention. 20 The combination of size exclusion chromatography (SEC) and multiangle light scattering (MALS) detection was used to detect and characterize polymer branching. As illustrated in Figures 3-5, diagrams obtained from SEC-MALS analysis plotting the radius of gyration (Rg), one measurement of molecular size, versus Mw, of the ethylene homopolymer produced in Examples 1-7 and Examples 25 10-11, demonstrate one aspect of the invention's utility in reducing LCB. Deviation of the radius of gyration (Rg) from a known linear control (in this instance, HiD9640) indicates branching. Thus, the data from Figures 3-5 demonstrate that the polymers prepared using the catalyst compositions according to this invention are only very slightly deviated from the linear standard, HiD9640, at high molecular weight end in 30 the plot of Rg vs. Mw. Figures 6 and 7 illustrate plots of log(rqo) versus log (Mw) for polymers prepared according to inventive Examples 1-11 and comparative Examples 14-16, WO 2007/092753 PCT/US2007/061519 69 respectively, and further illustrate how reduced LCB levels are manifested (see: Table 1). Linear polyethylene polymers are observed to follow a power law relationship between their zero shear viscosity, 7o, and their weight average molecular weight, Mw, with a power very close to 3.4. This relationship is shown by a 5 straight line with a slope of 3.4 when the logarithm of 7o is plotted versus the logarithm of Mw. Deviations from this linear polymer line are generally accepted as being caused by the presence of long-chain branching (LCB). Janzen and Colby presented a model that predicts the expected deviation from the linear plot of log(77o) vs. log(Mw) for given frequencies of LCB as a function of the weight average 10 molecular weight of the polymer. See: ["Diagnosing long-chain branching in polyethylenes," J. Mol. Struct. 485-486, 569-584 (1999)], which is incorporated herein by reference, in its entirety. Thus, Figures 6 and 7 plot the logarithm of qo versus the logarithm of M, for polymers prepared according to this invention, illustrating the dependence of zero 15 shear melt viscosity on weight average molecular weight (M. ), and demonstrating that these polymers are only very slightly deviated from the well-know 3.4 power law "Arnett line" which is used as an indication of a linear polymer (J. Phys. Chem. 1980, 84, 649). Consistent with this observation, both SEC-MALS and rheology data indicate that the inventive metallocenes produce very low LCB in ethylene 20 polymerization, as illustrated in Figure 6 for Examples 1-11. In contrast, polymers made according to the comparative Examples 14-16 had much lower M, relative to polymers prepared according to this invention, Examples 1-11. Typically, these polymers also had similar or slightly higher levels of LCB, as illustrated in Figure 7. Figure 8 demonstrates a comparison of gcl-permcation chromatography (GPC) 25 runs for the polymers produced according to Examples 1-11 and Examples 14-16, of this invention. These GPC results (Table 1 and Figure 8) indicate that the polyethylenes (PE) produced according to this invention generally have high molecular weights. While the polymers made according to comparative Examples 14 16 were characterized by low levels of LCB (Figure 8), these comparative polymers 30 had relatively lower M, as compared to the polymers prepared according to this invention. Comparative Examples 12 and 13 also demonstrate that the catalyst prepared using comparative metallocene C-I exhibited poor activity (Table 1).
WO 2007/092753 PCT/US2007/061519 70 Further, a considerable amount of insoluble polymers (about 50 wt%) were observed in the polymeric samples prepared according to Comparative Examples 12 and 13 during the process of preparing the GPC and SEC-MALS samples of these materials. Thus, using polymeric samples prepared according to Comparative Examples 12 and 5 13, 25 mg to 28 ng of polymer was mixed in 25 nL of 1,2,4-trichlorobenzene, and agitated for 5 hours, while maintaining this mixture at 150*C. Visual examination of the sample vial containing the sample prepared as described revealed that a precipitate formed on the sides of the sample vial. This observation indicates that the polymers prepared according to Examples 12 and 13, using metallocene C-1, were non-linear 10 polymers. No insoluble polymers were observed in polymers prepared according to any other Example. Definitions In order to more clearly define the terms used herein, the following definitions 15 are provided. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls. The term "polymer" is used herein to mean homopolymers comprising ethylene and/or copolymers of ethylene and another olefinic comonomer. "Polymer" 20 is also used herein to mean homopolymers and copolymers of any other polymerizable monomer disclosed herein. The term "cocatalyst" is generally used herein to refer to the organoaluminum compounds that can constitute one component of the catalyst composition, but also refers to the optional components of the catalyst composition including, but not 25 limited to, aluminoxanes, organoboron compounds, organoborate compounds, or ionizing ionic compounds, as disclosed herein. In one aspect, cocatalysts can be organoaluminum compounds of the formula Al(X 5
)(X
6
)
3 ,, wherein (X 5 ) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X 6 ) is alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and n is a 30 number from 1 to 3, inclusive. The term cocatalyst can be used regardless of the actual function of the compound or any chemical mechanism by which the compound might operate.
WO 2007/092753 PCT/US2007/061519 71 The term "precontacted" mixture is used herein to describe a first mixture of catalyst components that are contacted for a first period of time prior to the first mixture being used to form a "postcontacted" or second mixture of catalyst components that are contacted for a second period of time. Typically, the 5 precontacted mixture describes a mixture of metallocene, olefin monomer, and organoaluminurn compound, before this mixture is contacted with the acidic activator-support and optionally an organoaluminum compound. Thus, "precontacted" describes components that are used to contact each other, but prior to contacting the components in the second, postcontacted mixture. Accordingly, this 10 invention may occasionally distinguish between a component used to prepare the precontacted mixture and that component after the mixture has been prepared. For example, according to this description, it is possible for the precontacted organoaluminum compound, once it is contacted with the metallocene and the olefin monomer, to have reacted to form at least one different chemical compound, 15 formulation, or structure from the distinct organoaluminum compound used to prepare the precontacted mixture. In this case, the precontacted organoaluminum compound or component is described as comprising an organoaluminum compound that was used to prepare the precontacted mixture. Similarly, the term "postcontacted" mixture is used herein to describe a second 20 mixture of catalyst components that are contacted for a second period of time, and one constituent of which is the "precontacted" or first mixture of catalyst components that were contacted for a first period of time. Typically, the term "postcontacted" mixture is used herein to describe the mixture of metallocene, olefin monomer, organoaluminum compound, and acidic activator-support, formed from contacting the 25 precontacted mixture of a portion of these components with the any additional components added to make up the postcontacted mixture. Generally, the additional component added to make up the postcontacted mixture is the solid oxide activator, and optionally can include an organoaluminum compound the same or different from the organoaluminum compound used to prepare the precontacted mixture, as 30 described herein. Accordingly, this invention may also occasionally distinguish between a component used to prepare the postcontacted mixture and that component after the mixture has been prepared.
WO 2007/092753 PCT/US2007/061519 72 The term tightly-bridged ansa-metallocene describes a metallocene compound in which the two 5 -cycloalkadienyl-type ligands in the molecule are linked by a bridging moiety, wherein the shortest link between the two ii 5 -cycloalkadienyl-type ligands comprises one atom. Thus, the length of the bridge or the chain between the 5 two cyclopentadienyl-type ligands is a single atom, although this bridging atom is substituted. Thus, the metallocenes of this invention are bridged bis(i 5 cycloalkadienyl)-type compounds, wherein the 'n 5 -cycloalkadienyl portions include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including substituted analogs and partially saturated analogs thereof. Possible substituents on 10 these ligands include hydrogen, therefore the description "substituted derivatives thereof' in this invention includes partially saturated ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, the 15 metallocene is referred to simply as the "catalyst", in much the same way the term "cocatalyst" is used herein to refer to the organoaluminum compound. The terms "catalyst composition," "catalyst mixture," and the like do not depend upon the actual product of the reaction of the components of the mixtures, the nature of the active catalytic site, or the fate of the aluminum cocatalyst, ansa 20 metallocene, any olefin monomer used to prepare a precontacted mixture, or the solid oxide activator after combining these components. Therefore, the terms catalyst composition, catalyst mixture, and the like include both heterogeneous compositions and homogenous compositions. The term "hydrocarbyl" is used to specify a hydrocarbon radical group that 25 includes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like, and includes all substituted, unsubstituted, branched, linear, heteroatom substituted derivatives thereof. Unless otherwise specified, the hydrocarbyl groups of this invention typically comprise up to about 20 carbon atoms. In one aspect, hydrocarbyl groups 30 can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms. The term "hydrocarbyloxide" group is used generically to refer collectively to both alkoxide and aryloxide groups. Unless otherwise specified, the hydrocarbyl WO 2007/092753 PCT/US2007/061519 73 oxide groups of this invention typically comprise up to about 20 carbon atoms. In one aspect, hydrocarbyloxide groups can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms. The term "hydrocarbylamino" group is used generically to refer collectively to 5 alkylamino (NHR), arylamino (NHAr), dialkylamino (NR 2 ), and diarylamino (NAr 2 ) groups. Unless otherwise specified, the hydrocarbyl amino groups of this invention typically comprise up to about 20 carbon atoms. In one aspect, hydrocarbylamino groups can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms. 10 The term "alkenyl" is used broadly to specify a hydrocarbyl group that comprises an alkene moiety, regardless of the particular regiochemistry of the alkene moiety and encompassing all stereochemical isomers. Thus, for example, the term alkenyl is intended to include any CH=CH 2 -substituted or CH=CMe 2 -substituted alkyl group, regardless of where the substitution occurs within the alkyl group. Terms such 15 as olefin-containing hydrocarbyl group or olefin-containing pendant group are typically used interchangeably with alkenyl group, again illustrating that these terms arc not intended to be bound by the particular location of the C=C double bond within the group. Unless otherwise specified, the alkenyl groups of this invention typically comprise up to about 20 carbon atoms. In one aspect, alkenyl groups can have up to 20 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms. The terms solid oxide activator-support, acidic activator-support, activator support, treated solid oxide, treated solid oxide compound, and the like are used herein to indicate a treated, solid, inorganic oxide of relatively high porosity, which exhibits Lewis acidic or Bronsted acidic behavior, and which has been treated with an 25 electron-withdrawing component, typically an anion, and which is calcined. The electron-withdrawing component is typically an electron-withdrawing anion source compound. Thus, the treated solid oxide compound comprises the calcined contact product of at least one solid oxide compound with at least one electron-withdrawing anion source compound. Typically, the activator-support or "treated solid oxide 30 compound" comprises at least one ionizing, acidic solid oxide compound. The terms support or activator-support are not used to imply these components are inert, and this component should not be construed as an inert component of the catalyst composition.
WO 2007/092753 PCT/US2007/061519 74 The term "activator," as used herein, refers generally to a substance that is capable of converting the contact product of: 1) a metallocene component; and 2) a component that provides an activatable ligand such as an alkyl or hydride ligand to the metallocene, when the metallocene compound does not already comprise such a ligand; 5 into a catalyst that can polymerize olefins. This term is used regardless of whether an activator ionizes the metallocene, abstracts an anionic ligand to form an ion pair, weakens a metal-ligand bond in the metallocene, simply coordinates to an anionic ligand, or any other mechanism. As disclosed herein, the contact product comprises at least one activator, which can be selected independently from: i) an activator 10 support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator-support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron or an organoborate compound; or iv) any combination of these components. The term "clay" is used herein to refer to that component of the catalyst 15 composition, a substantial portion of which constitutes a clay mineral or a mixture of clay minerals that have been pretreated by either exchanging cations, pillaring or simply wetting, that can be used as a activator-support in the catalyst composition described herein. The transition metal compound and organometal cocatalyst are reacted with the clay activator-support to form the active catalyst. While not 20 intending to be bound by the following statement, the clay component of the catalyst composition of this invention probably functions as a activator-support for the transition metal compound, as well as a cocatalyst from the standpoint that it is in intimate physical chemical contact with the transition metal component. As used herein, the collective term "clay mineral" is used herein to describe 25 the large group of finely-crystalline, sheet like clay minerals that are found in nature in fine-grained sediments, sedimentary rocks, and the like. Clay minerals are a class of hydrous silicate and aluminosilicate minerals with sheet-like structures and very high surface areas. This term is also used to describe hydrous magnesium silicates with a phyllosilicate structure. Many common clay minerals belong to the kaolinite, 30 montmorillonite, or illite groups of clays. Thus, the term "clay mineral" is not used herein to refer to the fine-grained soil consisting of mineral particles, not necessarily clay minerals, that are less than about 0.002 mm in size.
WO 2007/092753 PCT/US2007/061519 75 The term "pillared clay" is used herein to refer to a component of the catalyst composition comprising clay minerals, typically of the of the smectite group and other phylosilicates in addition to sepiolites and palygorskites, that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations. 5 Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometallates, and other large ions. Thus, the term pillaring refers to a simple exchange reaction in which the exchangeable cations of a clay material are replaced with large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the interlayers of the clay and 10 when calcined are converted to metal oxide "pillars," effectively supporting the clay layers as column-like structures. Examples of pillaring and pillared clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent 15 No. 4,060,480; each of which is incorporated herein in its entirety. Although any methods, devices, and materials similar or equivalent to those described hercin can be used in the practice or testing of the invention, the typical methods, devices and materials are herein described. All publications and patents mentioned herein are incorporated herein by 20 reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. The publications discussed above and throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the 25 inventors are not entitled to antedate such disclosure by virtue of prior invention. For any particular compound disclosed herein, any general structure presented also encompasses all conformational isomers, regioisomers, stereoisomers, and the like, that can arise from a particular set of substituents. The general structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in 30 enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context requires.
WO 2007/092753 PCT/US2007/061519 76 The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort can be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the 5 description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims. In the following examples, unless otherwise specified, the syntheses and preparations described herein were carried out under an inert atmosphere such as nitrogen and/or argon. Solvents were purchased from commercial sources and were 10 typically dried over activated alumina prior to use. Unless otherwise specified, reagents were obtained from commercial sources. General testing procedures, characterization, and synthetic procedures are provided herein. Synthetic methods to prepare the metallocenes, treated solid oxides, and other reagents of this invention are also provided herein. 15 General Testing Procedures Melt index (MI, g/10 min) was determined in accordance with ASTM D1238 condition F at 190'C with a 2,160 gram weight. High load melt index (HLMI, g/10 min) was determined in accordance with 20 ASTM D1238 condition E at 190'C with a 21,600 gram weight. Polymer density was determined in grams per cubic centimeter (g/cc) on a compression molded sample, cooled at about 15*C per hour, and conditioned for about 40 hours at room temperature in accordance with ASTM D1505 and ASTM D1928, procedure C. 25 Molecular weight and molecular weight distributions were obtained using a PL-GPC 220 (Polymer Labs, UK) system equipped with a differential refractive index detector and three 7.5 mm x 300 mm 20 um Mixed A-LS columns (Polymer Labs) running at 145 'C. The flow rate of the mobile phase, 1,2,4-trichlorobenzene (TCB) containing 0.5 g/L 2,6-di-t-butyl-4-methylphenol (BHT), was set at 1 mL/min and the 30 concentration of polymer solutions was generally kept in the range of 1.0-1.5 mg/mL, depending on the molecular weights. Sample preparation was conducted at 150 'C for 4 h with occasional and gentle agitation before the solutions being transferred to WO 2007/092753 PCT/US2007/061519 77 sample vials for injection. In order to minimize unbalanced solvent peak, solvent with the same composition as the mobile phase was used for solution preparation. The integral calibration method was employed to deduce molecular weights and molecular weight distributions using a Chevron Phillips Chemicals Company's broad 5 linear polyethylene, Marlex BHB5003, as the broad standard. The integral table of the broad standard was pre-determined in a separate experiment with SEC-MALS. Melt viscosity measurements to determine shear viscosity characteristics Small-strain oscillatory shear measurements were performed on an ARES 10 oscillatory rheometer using parallel-plate geometry (TA Instruments, formerly Rheometrics Inc.). Data were typically obtained over an angular frequency range of 0.03 to 100 rad/s at a temperature of 190 'C. Fluff samples were stabilized with 0.1 wt% BHT dispersed in acetone and then vacuum dried before molding. Samples were compression molded at 184 'C for 15 a total of three minutes. The samples were allowed to melt at a relatively low pressure for one minute and then subjected to a high molding pressure for an additional two minutes. The molded samples were then quenched in a cold (room temperature) press. Disks having the size 2 mm x 25.4 mm diameter were stamped out of the molded slabs for rheological characterization. 20 The test chamber of the rheometer was blanketed in nitrogen in order to minimize polymer degradation. The rheometer was preheated to the initial temperature of the study. Upon sample loading and after oven thermal equilibration, the specimens were squeezed between the plates to a 1.6 mm thickness and the excess was trimmed. 25 Strains were generally maintained at a single value throughout a frequency sweep but larger strain values were used for low viscosity samples to maintain a measurable torque. Smaller strain values were used for high viscosity samples to avoid overloading the torque transducer and to keep within the linear viscoelastic limits of the sample. The instrument automatically reduces the strain at high 30 frequencies if necessary to keep from overloading the torque transducer. Viscosity data were fit with a modified Carreau-Yasuda model [R. Byron Bird, Robert C. Armstrong, and Ole Hassager, Dynamics of Polymeric Liquids, WO 2007/092753 PCT/US2007/061519 78 Volume 1, Fluid Mechanics, (John Wiley & Sons, New York, 1987), p 171-172], which is incorporated by reference herein to obtain estimates of the zero shear viscosity, viscous relaxation time, and a breadth parameter, as indicated below. 5 |9*1 = //[1 + (ov 1 ) "I nya wherein: I q*l = magnitude of the complex viscosity in Pa-s co = angular frequency in rad/s qo = zero shear viscosity in Pa-s 10 - = viscous relaxation time in s a = breadth parameter n = power law parameter, fixed at 0.1818. Absolute Molecular Weight as Determined by Light Scattering 15 Molecular weight data were determined using SEC-MALS, which combines the methods of size exclusion chromatography (SEC) with multi-angle light scattering (MALS) detection. A DAWN EOS 18-angle light scattering photometer (Wyatt Technology, Santa Barbara, CA) was attached to a PL-210 SEC system (Polymer Labs, UK) or a Waters 150 CV Plus system (Milford, MA) through a hot transfer line, 20 thermally controlled at the same temperature as the SEC columns and its differential refractive index (DRI) detector (145 'C). At a flow rate setting of 0.7 mL/min, the mobile phase, 1,2,4-trichlorobenzene (TCB), was eluted through three, 7.5 mm x 300 mm, 20 pm Mixed A-LS columns (Polymer Labs). Polyethylene (PE) solutions with concentrations of~1.2 mg/nL, depending on samples, were prepared at 150 'C for 4 25 h before being transferred to the SEC injection vials sitting in a carousel heated at 145 'C. For polymers of higher molecular weight, longer heating times were necessary in order to obtain true homogeneous solutions. In addition to acquiring a concentration chromatogram, seventeen light-scattering chromatograms at different angles were also acquired for each injection using Wyatt's Astra@ software. At each chromatographic 30 slice, both the absolute molecular weight (M) and root mean square (RMS) radius, also known as radius of gyration (Rg) were obtained from a Debye plot's intercept and WO 2007/092753 PCT/US2007/061519 79 slope, respectively. Methods for this process are detailed in Wyatt, P.J., Anal. Chim. Acta, 272, 1 (1993), which is hereby incorporated herein by reference in its entirety. The linear PE control employed was a linear, high-density broad molecular weight distribution (MWD) polyethylene sample (Chevron Phillips Chemical Co.). The 5 weight average molecular weight (Mw), number average molecular weight (A4f,), z average molecular weight (Mz) and molecular weight distribution (M,/M,) were computed from these data, and are presented in various Tables. The Zimm-Stockmayer approach was used to determine the amount of LCB in ethylene polymers. Since SEC-MALS measures Al and Rg at each slice of a 10 chromatogram simultaneously, the branching indices, gm, as a function of M could be determined at each slice directly by determining the ratio of the mean square R. of branched molecules to that of linear ones, at the same M, as shown in equation 1: "Rg)2~(1 9M R - ( br() ( !lin where the subscripts br and lin represent branched and linear polymers, respectively. 15 At a given gm, the weight-averaged number of LCB per molecule (B 3 ,.) was computed using Zimm-Stockmayer's equation, shown in equation 2, where the branches were assumed to be trifunctional, or Y-shaped. gM= 6 1_ (2 + B±2 +(B 3 w)1 - 1 (2)
B
3w 2 B3w ) (2 + B 3
-(B
3 )1/2 LCB frequency (LCBM ), the number of LCB per 1 000 C, of the ith slice was then 20 computed straightforwardly using equation 3: LCBmi = 1 000*14*B 3 w/M (3) where Mi is the MW of the ith slice. The LCB distribution (LCBD) across the molecular weight distribution (MWD) was thus established for a full polymer. A Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument was 25 used to determine specific surface area ("surface area") and specific pore volume ("pore volume"). This instrument was acquired from the Quantachrome Corporation, Syosset, N.Y.
WO 2007/092753 PCT/US2007/061519 80 Preparation of a Fluorided Silica-Alumina Activator-Support The silica-alumina used to prepare the fluorided silica-alumina acidic activator-support in this Example was typically Davison silica-alumina obtained from W.R. Grace as Grade MS 13-110, containing 13% alumina, having a pore volume of 5 about 1.2 cc/g and a surface area of about 400 m 2 /g. This material was fluorided by impregnation to incipient wetness with a solution containing ammonium bifluoride in an amount sufficient to equal 10 wt % of the weight of the silica-alumina. This impregnated material was then dried in a vacuum oven for 8 hours at 100'C. The thus-fluorided silica-alumina samples were then calcined as follows. About 10 grams 10 of the alumina were placed in a 1.75-inch quartz tube fitted with a sintered quartz disk at the bottom. While the silica was supported on the disk, dry air was blown up through the disk at the linear rate of about 1.6 to 1.8 standard cubic feet per hour. An electric furnace around the quartz tube was used to increase the temperature of the tube at the rate of about 400'C per hour to a final temperature of about 500'C. At this 15 temperature, the silica-alumina was allowed to fluidize for about three hours in the dry air. Afterward, the silica-alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere. Preparation of a Sulfated Alumina Activator-Support 20 Sulfated alumina was formed by a process wherein alumina was chemically treated with a sulfate or bisulfate source, typically selected from, but not limited to, sulfuric acid, ammonium sulfate, or ammonium bisulfate. One example follows. A commercial alumina sold as W.R. Grace Alumina A was sulfated by impregnation with an aqueous solution containing about 15-20% (NH 4
)
2
SO
4 or 25 H2SO 4 . This sulfated alumina was calcined at 550 "C in air (240 'C/h ramp rate), with a 3 h hold period at this temperature. Afterward, the alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere. Metallocene Preparations 30 Unless specified otherwise, reagents were obtained from Aldrich Chemical Company and were used as received. 2,7-Di-tert-butylfluorene was purchased from Degussa. The Grignard reagent CpMgCl (IM in THF) was purchased from Boulder WO 2007/092753 PCT/US2007/061519 81 Scientific Company. Hafnium(IV) chloride was purchased from Strem. The solvent THF was distilled from potassium, while anhydrous diethyl ether, methylene chloride, pentane, and toluene were purchased from Fisher Scientific Company and stored over activated alumina. All solvents were degassed and stored under nitrogen. Reaction 5 products were analyzed by 1H NMR spectroscopy (300 MHz, CDC1 3 referenced against either the residual proton peak at 7.24 ppm for CHC1 3 or TMS at 0 ppm) or 13 C NMR (75 MHz, CDCl 3 , referenced against central line of CDCl 3 at 77.00 ppm). Reported preparations were not optimized. The following fuilvenes, F-I through F-5, were prepared as disclosed herein 10 and used to prepare the ligands L-1 through L-5 provided herein. 32 2 2-(pent-4-enyl)-6,6- 2-(but-3-enyl)-6,6- 2-(1,1-dimethylpent-4-eny1) diphenylpentafulvene diphenylpentafulvene 6,6-diphenylpentafulvene F-iF-2 F-3 / 3 6,6-diphenylpentafulvene 2-(pent-4-eny1)-6,6 dibutylpentafulvene F-4 F-5 WO 2007/092753 PCT/US2007/061519 82 The following ligands L-1 through L-5 were prepared as disclosed herein. t-B -Bu t-Bu -Bu t-B -Bu Phh, Ph Ph, Ph P Ih Ph Mixture of isomers Mixture ofisomers Mixture ofisomers L-IL-2 L-3 t-B t-Bu t-B / Bu Ph-- C4H>
C
4
H
Mixture of isomers Mixture of isomers L-4 L-5 Synthesis of 2-(pent-4-enyl)-6,6-diphenylpentafulvene (F-1). 5 To 5-bromo-1-pentene (100 g of 95 wt%, 0.637 mol) was added cyclopentadienyl magnesium chloride (700 mL of 1 M solution in THF, 0.7 mol) at 0 'C in an hour. After stirring for an additional 30 minutes at 0 'C, the mixture was warmed to room temperature. After stirring overnight, the reaction was quenched with a mixture of ice and water. The mixture was extracted with pentane. The 10 organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent under vacuum at room temperature gave a yellow-brown liquid (98 g, crude pent-4-enylcyclopentadiene). To the crude pent-4 enylcyclopentadiene (89 g) dissolved in THF (500 mL) was added n-BuLi (60 mL of 10 M in hexanes, 0.6 mol) at -78 'C. The mixture was warmed up to room 15 temperature and stirred overnight. The anion solution was added to benzophenone (110 g, 0.604 mol) dissolved in THF (500 mL) at 0 "C in 25 minutes. The mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% HCl aqueous solution. The mixture was extracted with pentanc. The organic layer was washed with water and dried over anhydrous sodium 20 sulfate. Removal of the solvent under vacuum at 40 'C gave a dark red viscous oil. The oil was dissolved in heptane and filtered through silica gel. The product was collected by washing the silica gel with 5-10% CH 2 C1 2 in heptane. Removal of the WO 2007/092753 PCT/US2007/061519 83 solvent gave the desired product (145 g, 84% yield based on 5-bromo-1-pentene) as a dark red viscous oil. 'H NMR (300 MHz, CDC1 3 ) 8 7.41-7.48 (m, 1OH), 6.59-6.62 (dd, J= 5.1 Hz, 1.4 Hz, 1H), 6.40-6.42 (dd, J= 5.1 Hz, 1.4 Hz, 1H), 6.12-6.15 (in, 1H), 5.86-6.02 (m, 1H), 5.08-5.20 (m, 2H), 2.55-2.60 (t, J= 7.2 Hz, 2H), 2.22-2.30 5 (m, 2H), 1.76-1.88 (quin, J= 7.2 Hz, 2H); ' 3 C NMR (75 MHz, CDCl 3 ) 3 148.28, 148.13, 143.28, 140.85, 140.76, 138.01, 133.51, 131.34, 131.29, 127.76, 127.74, 127.13, 127.08, 124.74, 118.24, 114.24, 33.95, 30.13, 28.46. Synthesis of 1-(3-(pent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl) 10 1,1-diphenylmethane (L-1) To 2,7-di-tert-butylfluorene (125.1 g, 0.45 mol) dissolved in Et 2 O (700 mL) was added n-BuLi (47 mL of 10 M in hexanes, 0.47 mol) at 0 *C. The mixture was warmed to room temperature and stirred overnight. The anion solution was added to 2-(pent-4-enyl)-6,6-diphenylpentafulvene (F-1) (145 g, 0.487 mol) dissolved in Et 2 O 15 (300 mL) at -78 *C in 10 minutes. The mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% HCI aqueous solution. The mixture was extracted with Et 2 0. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent under vacuum gave a pale brown solid. The solid was washed with heptane and dried 20 under vacuum. A mixture of isomers for the desired product (191.7 g, 74% yield) was obtained as a white solid. Synthesis of 2-(but-3-enyl)-6,6-diphenylpentafulvene (F-2) To 4-bromo-1-butene (100 g of 97 wt%, 0.719 mol) was addcd 25 cyclopentadienyl magnesium chloride (800 mL of 1 M solution in THF, 0.8 mol) at 0 *C in 50 minutes. After stirring for an additional 15 minutes at 0 'C, the mixture was warmed to room temperature. After stirring overnight, the reaction was quenched with a mixture of ice and water. The mixture was extracted with pentane. The organic layer was washed with water and dried over anhydrous sodium sulfate. 30 Removal of the solvent under vacuum at room temperature gave a brown liquid (94.2 g, crude but-3-enylcyclopentadicnc). To the crude but-3-cnylcyclopentadienc (94.2 g) WO 2007/092753 PCT/US2007/061519 84 dissolved in THF (500 mL) was added n-BuLi (70 mL of 10 M in hexanes, 0.7 mol at -78 'C. The mixture was warmed up to room temperature and stirred overnight. The anion solution was added to benzophenone (133.8 g, 0.735 mol) dissolved in THF (400 mL) at 0 *C in 35 minutes. The mixture was warmed to room temperature and 5 stirred overnight. The reaction was quenched with a mixture of ice and 10% HCl aqueous solution. The mixture was extracted with pentane. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent under vacuum at 40 'C gave a dark red viscous oil. The oil was dissolved in heptane and filtered through silica gel. The product was collected by washing the silica gel 10 with 5-10% CH 2 Cl 2 in heptane. Removal of the solvent gave the desired product (152g, 74.4% yield based on 4-bromo-l-butene) as a dark red viscous oil. 'H NMR (300 MHz, CDC1 3 ) 3 7.29-7.41 (m, 10H), 6.50-6.53 (dd, .1 = 5.2 Hz, 1.4 Hz, 1H), 6.29-6.31 (dd, J= 5.2 Hz, 1.4 Hz, 1H), 6.02-6.05 (m, IH), 5.82-5.98 (m, 1H), 4.94 5.16 (m, 2H), 2.53-2.60 (in, 2H), 2.33-2.43 (m, 2H); ' 3 C NMR (75 MHz, CDCl 3 ) 3 15 148.59, 147.67, 143.18, 140.86, 140.78, 137.85, 133.48, 131.38, 131.36, 127.85, 127.82, 127.18, 127.13, 124.75, 118.35, 114.29, 33.36, 30.20. Synthesis of 1-(3-(but-3-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1 diphenylmethane (L-2) 20 To 2,7-di-tert-butylfluorene (91.7 g, 0.33 mol) dissolved in Et 2 O (500 mL) was added n-BuLi (35 mL of 10 M in hexanes, 0.35 mol) at 0 'C. The mixture was warmed to room temperature and stirred overnight. The anion solution was added to 2-(but-3-enyl)-6,6-diphenylpentafulvene (compound F-2) (104 g, 0.366 mol) dissolved in Et 2 O (200 mL) at 0 'C in 35 minutes. After stirring for an additional 30 25 minutes at 0 *C, the mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% HCI aqueous solution. The mixture was extracted with CH 2 Cl 2 . The organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent under vacuum gave a pale brown solid. The solid was washed with heptane and dried under vacuum. A 30 mixture of isomers for the desired product (142 g, 76.5% yield) was obtained as a white solid.
WO 2007/092753 PCT/US2007/061519 85 Synthesis of 2-(1,1-dimethylpent-4-enyl)-6,6-diphenylpentafulvene (F-3) To a solution of 6-butenyl-6-methylpentafulvene (17.8 g, 122 mmol) (prepared by the method of K. J. Stone and R. D. Little, J. Org. Chem., 1984, 49(11), 5 1849-1853) in dry THF (50 mL) was added a solution of methyllithium (75 mL of 1.6 M in ether, 120 mmol) while cooling in dry ice. After stirring for 20 hours and warming to room temperature, the yellow solution was gradually added to a solution of benzophenone (21.87 g, 120 mmol) in THF (50 mL) while cooling in ice. A red color formed immediately and after 4 hours analysis of an aliquot showed that the 10 reaction was nearly complete. After an additional hour, the mixture was cooled while a solution of concentrated hydrochloric acid (20 mL) in water (200 mL) was added. Following addition of pentane (150 mL), the organic layer was washed with water and dried over sodium sulfate. The solvent was removed under vacuum and the red liquid was cooled to - 15 'C overnight. The red crystalline product was washed with cold 15 methanol and dried under vacuum to a red solid (32.8 g, 84% yield). 1H NMR (300 MHz, CDCl 3 ) 8 7.22-7.40 (in, IH), 6.56-6.58 (dd, J= 5.1 Hz, 1.8 Hz, IH), 6.24-6.26 (dd, J= 5.1 Hz, 1.8 Hz, 1H), 5.91-5.93 (t, J= 1.8 Hz, 1H), 5.70-5.85 (m, 1H), 4.84 5.00 (m, 2H), 1.88-2.00 (m, 2H), 1.52-1.60 (m, 2H), 1.17 (s, 6H); "C NMR (75 MHz, CDCl 3 ) 5 156.16, 148.39, 143.20, 140.96, 140,92, 138.98, 131.61, 131.43, 131.39, 20 127.81, 127.77, 127.24, 127.14, 124.88, 116.30, 113.45, 41.96, 35.86, 29.90, 27.90. Synthesis of 1-(3-(1,1-dimethylpent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert butylfluorenyl)-11,1-diphenylmethane (L-3) A solution of 2,7-di-tert-butylfluorene (27.8 g, 100 mmol) in Et 2 O (200 mL) 25 was cooled in dry ice and n-BuLi (68 mL of 1.6 M in hexanes, 0109 mmol) was added dropwise. The slurry was warmed to room temperature and stirred for 24 hours. The dark solution was cooled in dry ice and a solution of 2-(1,1-dimethylpent 4 -enyl)-6,6-diphenylpentafulvene (compound F-3) (32.8 g, 54.3 mmol) in Et 2 O (100 mL) was then added rapidly. The mixture was warmed to room temperature and 30 stirred for 20 hours. After cooling in ice, a solution of concentrated hydrochloric acid (20 mL) in water (200 mL) was added. Following addition of pentane (100 mL), the organic layer was separated and washed with water. After drying over sodium sulfate WO 2007/092753 PCT/US2007/061519 86 and filtering, the solvent was removed under vacuum leaving a glassy solid. The solid was heated with methanol (100 mL) and the hot methanol solution was poured off. This process was repeated four times. The solid was then dissolved in hot pentane, which was then removed under vacuum while heating. The solid was broken up, 5 dried under vacuum, and then heated with ethanol (70 mL). After cooling, the solid was filtered and dried. A mixture of isomers for the desired product (18.1 g, 30% yield) was obtained as a white solid. Synthesis of 6,6-diphenylpentafulvene (F-4) 10 Benzophenone (63.8 g, 350 mmol) was dissolved in anhydrous 1,2 dimethoxyethane (DME) (150 mL) under nitrogen. In a one-liter flask, ground potassium hydroxide (30 g, 535 mmol) was slurried in DME (200 mL). The slurry was cooled in an ice bath and freshly cracked cyclopentadiene (35 mL, 430 mmol) were added. After 30 minutes, the solution of benzophenone was added over 15 15 minutes. The flask was stirred in a refrigerator for 90 hours and then, while cooling in ice, 3M HCI (450 mL) were added. The mixture was diluted with pentane (500 mL) and separated. The organic layer was washed with water (2 X 200 mL) and dried over sodium sulfate. The solution was filtered and taken to dryness under vacuum. The solid was dissolved in boiling pentane (600 mL) and then concentrated to 400 20 mL. Cooling to -15 'C for 40 hours gave a red solid (69.5 g, 86.3% yield). 'H NMR (300 MHz, CDCl 3 ) 6 7.24-7.38 (m, 10H), 6.53-6.59 (m, 2H), 6.24-6.30 (rn, 2H); 13 C NMR (75 MHz, CDC1 3 ) 8 151.24, 143.20, 140.65, 131.73, 131.55, 128.16, 127.20, 123.89. 25 Synthesis of 1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenyl methane (L-4) To a solution of 2,7-di-tert-butylfluorenc (29.8 g, 107 mmol) in dry THF (100 mL), cooled in dry ice, was added n-BuLi (43.0 mL of 2.5 M in hexanes, 107.5 mmol). The bath was removed and the dark solution was stirred for 2 hours. This 30 solution was then added dropwise to a solution of 6,6-diphenylpentafulvene (compound F-4) (26.0 g, 113 mmol) in THF (100 mL), while cooling in ice. The reaction mixture was stirred at room temperature for 86 hours and then cooled in ice.
WO 2007/092753 PCT/US2007/061519 87 IM HCl solution, (100 mL) was added. The mixture was diluted with chloroform (100 mL) and separated. The chloroform layer was washed with water (3 X 100 mL) and dried over sodium sulfate. The solution was filtered and evaporated to a light orange solid. The solid was dissolved in boiling chloroform (150 mL) and methanol 5 (150 mL) was slowly added. After cooling for two days to -15 'C, the solid was filtered off, ground, and dried under vacuum. A mixture of isomers for the desired product (25.4 g, 46.7% yield) was obtained as an off white solid. Synthesis of 5 -(3-(pent-4-enyl)cyclopentadienyl)-5-(2,7-di-tert-butyl 10 fluorenyl)nonane (L-5) A flask was charged with 2,7-di-tert-butylflourene (10 g, 36 mmol), Et 2 O (150 mL), cooled to -78 0 C under N 2 and stirred as n-BuLi (4.3 mL of 10 M in hexanes, 43 mmol) was added via syringe. The reaction mixture was warmed to room temperature, stirred overnight, cooled to -78 "C, and 2-(pent-4-enyl)-6,6 15 dibutylpentafulvene (compound F-5) (13 g, 50 mmol) (prepared by the method of K.J. Stone and R.D. Little, J. Org. Chem., (1984), 49(11), 1849-1853) quickly added. The reaction mixture was warmed to room temperature and stirred overnight. The reaction was quenched with saturated. NH 4 Cl solution. The organic layer was extracted with Et 2 O, washed with water and dried over anhydrous Na 2
SO
4 . Removal 20 of the solvent under vacuum gave a yellow oil. Elution of the oil through a silica-gel column using heptane afforded a mixture of isomers for the desired product (12.8 g, 66% yield) as an oil. Synthesis of diphenylmethylidene{a 5 -[3-(pent-4-enyl)cyclopentadien-1 25 ylidene] }[1-(2,7-di-tert-butylfluoren-9-ylidene)]hafnium dichloride (I-1) To 1-(3-(pent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1 diphenylmethanc (compound L-1) (45.3 g, 78.6 mmol) dissolved in Et 2 O (400 mL) was slowly added n-BuLi (68.5 mL of 2.5 M in hexanes, 171.3 mmol) at 0 0 C. The mixture was warmed to room temperature, stirred overnight, and then added via 30 cannula to HfCl 4 (26.8 g, 83.6 mmol) suspended in a mixture of pentane (450 mL) and Et 2 O (30 mL) at 0 'C in 30 minutes. The mixture was warmed to room temperature and stirred for two days. The slurry was concentrated and centrifuged.
WO 2007/092753 PCT/US2007/061519 88 The liquid was decanted off. The remaining solid was washed a second time with pentane (100 nL), then extracted with methylene chloride and centrifuged. The solution was taken to dryness under vacuum to give a yellow solid (46.4 g, 71.7%). 'H NMR (300 MHz, CDC13) 6 7.88-7.98 (n, 3H), 7.78-7.88 (m, 3H), 7.40-7.50 (m, 5 2H), 7.29-7.38 (broad t, J = 7.2 Hz, 2H), 7.11-7.28 (m, 4H), 6.28 (broad s, 1H), 6.24 (broad s, 1H), 5.87-5.93 (t, J= 2.7 Hz, 1H), 5.61-5.78 (m, 1H), 5.44-5.50 (t, J= 2.7 Hz , 1H), 5.19-5.25 (t, J= 2.7 Hz, IH), 4.82-4.96 (m, 2H), 2.28-2.48 (m, 2H), 1.94 2.05 (m, 2H), 1.46-1.60 (m, 2H), 0.98 (s, 18H); 1 3 C NMR (75 MHz, CDCl 3 ) 8 149.41, 149.21, 144.47, 144.24, 137.71, 132.69, 129.08, 128.83, 128.45, 128.39, 128.22, 10 126.50, 126.46, 126.13, 125.97, 123.70, 123.46, 123.40, 123.34, 119.89, 119.66, 119.01, 118.86, 118.82, 118.53, 114.75, 114.39, 111.11, 100.92, 100.69, 76.88, 57.88, 35.29, 35.27, 33.75, 31.04, 31.02, 29.48, 29.31. Synthesis of diphenylmethylidene{j 5 -[3-(but-3-enyl)cyclopentadien-l 15 ylidenel}{(rl-(2,7-di-tert-butylfluoren-9-ylidene)]hafnium dichloride (1-2) To 1-(3-(but-3-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1 diphenylmethane (compound L-2) (3.2 g, 5.7 mmol) dissolved in Et 2 O (30 mL) was slowly added n-BuLi (5.2 mL of 2.5 M in hexanes, 13 mmol) at 0 *C. The mixture was warmed to room temperature, stirred overnight, and then added via cannula to 20 HfCI 4 (2.1 g, 6.5 umol) suspended in a mixture of pentane (30 mL) and Et 2 O (5 mL) at 0 'C in 10 minutes. The mixture was warmed to room temperature and stirred for two days. The slurry was concentrated and centrifuged. The liquid was decanted off. The remaining solid was washed a second time with pentane (80 mL), then extracted with methylene chloride and centrifuged. The solution was taken to dryness under 25 vacuum to give a yellow solid (3.1 g, 67.4% yield). 1H NMR (300 MHz, CDC1 3 ) 8 7.87-7.98 (m, 3H), 7.79-7.86 (m, 3H), 7.43-7.49 (m, 2H), 7.30-7.38 (dt, J= 7.5 Hz, 1.4 Hz, 2H), 7.14-7.29 (m, 4H), 6.24-6.27 (d, J= 0.6 Hz, 1H), 6.20-6.24 (d, J= 0.6 Hz, 1H), 5.87-5.92 (t, J= 2.7 Hz, 1H), 5.62-5.77 (m, 1H), 5.42-5.47 (t, J= 2.7 Hz, 1H), 5.18-5.23 (t, J= 2.7 Hz, 1H), 4.85-4.98 (m, 2H), 2.35-2.55 (m, 2H), 2.13-2.22 30 (in, 2H), 0.96 (s, 18H); 1 3 C NMR (75 MHz, CDCl 3 ) 8 149.52, 149.33, 144.51, 144.30, 137.33, 132.16, 129.13, 128.89, 128.51, 128.45, 128.30, 128.26, 126.58, 126.53, WO 2007/092753 PCT/US2007/061519 89 126.24, 126.06, 123.77, 123.54, 123.42, 123.36, 119.97, 119.75, 119.08, 118.90, 118.58, 114.94, 114.83, 111.14, 101.01, 100.68, 76.93, 57.94, 35.36, 35.35, 34.11, 31.08, 31.05, 29.42. 5 Synthesis of diphenylmethylidene{rj 5 -[3-(but-3-enyl)cyclopentadien-1 ylidene] } [l 5 -(2,7-di-tert-butylfluoren-9-ylidene)] zirconium dichloride (1-3) To 1-(3-(but-3-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1 diphenylmethane (compound L-2) (40.5 g, 72.1 mmol) suspended in Et 2 O (400 mL) was slowly added n-BuLi (15.2 mL of 10 M in hexanes, 152 mmol) at 0 'C. The 10 mixture was warmed to room temperature, stirred overnight, and then added via cannula to ZrC1 4 (18.5 g, 79.4 mmol) suspended in a mixture of pentane (400 mL) and Et 2 O (30 mL) at 0 *C in 15 minutes. The mixture was warmed to room temperature, stirred for one day, and evacuated to dryness. The residue was stirred in pentane (300mL) and centrifuged. The supernatant was discarded. The remaining solid was 15 washed a second time with pentane (100 mL), then extracted with methylene chloride and centrifuged. The solution was taken to dryness under vacuum to give a red solid (38.1 g, 73.3% yield). 'H NMR (300 MHz, CDCl 3 ) 6 7.88-8.02 (m, 3H), 7.77-7.88 (m, 3H), 7.46-7.54 (m, 2H), 7.31-7.40 (broad t, J= 7.5 Hz, 2H), 7.14-7.32 (m, 4H), 6.24 (s, 1H), 6.20 (s, 1H), 5.96-6.02 (unresolved t, 1H), 5.63-5.79 (m, 1H), 5.50-5.55 20 (unresolved t, 1H), 5.25-5.31 (unresolved t, 1H), 4.87-5.01 (m, 2H), 2.33-2.53 (m, 2H), 2.15-2.27 (m, 2H), 0.97 (s, 18H); '-C NMR (75 MHz, CDC 3 ) 8 149.85, 149.65, 144.23, 144.01, 137.27, 133.51, 129.08, 128.84, 128.50, 128.45, 128.33, 128.30, 126.58, 126.54, 126.18, 126.01, 124.04, 123.81, 123.55, 123.48, 121.08, 120.89, 120.31, 120.03, 119.43, 119.24, 115.71, 114.86, 108.44, 103.37, 103.18, 76.66, 58.10, 25 35.38, 35.36, 33.98, 31.05, 31.02, 29.46. Synthesis of diphenylmethylidene{l 5 -[3-(pent-4-enyl)cyclopentadien-1 ylidene]} I[n 5 -(2,7-di-tert-butylfluoren-9-ylidene)] zirconium dichloride (1-4) To 1-(3-(pent-4-enyl)cyclopentadieny)-1-(2,7-di-tert-butylfluorenyl)-1,1 30 diphenylmethane (compound L-1) (34.7 g, 60.2 mmol) dissolved in Et 2 O (300 mL) was slowly added n-BuLi (52 mL of 2.5 M in hexanes, 130 mmol) at 0 *C. The WO 2007/092753 PCT/US2007/061519 90 mixture was warmed to room temperature, stirred overnight, and then added via cannula to ZrCl 4 (14.7 g, 63.1 mmol) suspended in a mixture of pentane (250 mL) and Et 2 O (20 mL) at 0 *C in 30 minutes. The mixture was warmed to room temperature, stirred for one day, and evacuated to dryness. The residue was stirred in pentane 5 (200mL) and centrifuged. The supernatant was discarded. The remaining solid was washed a second time with pentane (50 mL), then extracted with methylene chloride and centrifuged. The solution was taken to dryness under vacuum to give a red solid (33.5 g, 75.6%). 'H NMR (300 MHz, CDC 3 ) 5 7.94-7.99 (m, 2H)], 7.89-7.94 (m, 1H), 7.77-7.87 (m, 3H), 7.47-7.53 (m, 2H), 7.32-7.39 (dt, J= 7.2 Hz, 1.2 Hz, 2H), 10 7.15-7.29 (m, 4H), 6.23 (broad s, 1H), 6.19 (broad s, 1H), 5.94-5.98 (t, J= 2.7 Hz, 1H), 5.62-5.76 (m, 1H), 5.50-5.54 (t, J= 2.7 Hz, 1H), 5.24-5.29 (t, J= 2.7 Hz, 1H), 4.82-4.96 (m, 2H), 2.23-2.43 (n, 2H), 1.97-2.05 (m, 2H), 1.48-1.61 (m, 2H), 0.97 (s, 18H); "C NMR (75 MHz, CDC1 3 ) 3 149.85, 149.65, 144.27, 144.03, 137.79, 134.18, 129.11, 128.85, 128.51, 128.46, 128.34, 126.59, 126.55, 126.18, 126.03, 124.04, 15 123.79, 123.54, 123.47, 121.09, 120.89, 120.32, 120.06, 119.46, 119.26, 115.61, 114.44, 108.51, 103.36, 103.29, 76.69, 58.13, 35.39, 35.37, 33.78, 31.06, 31.03, 29.61, 29.33, Synthesis of diphenylmethylidene{rj-[3-(1,1-dimethylpent-4-enyl)cyclo 20 pentadien-1-ylidenel } [I 5 -(2,7-di-tert-butylfluoren-9-ylidene)]zirconium dichloride (1-5) A slurry of 1-(3-(1,1-dimethylpent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert butylfluorenyl)-1,1-diphenylmethane (compound L-3) (10.8 g, 17.9 mmol) in Et 2 O (50 mL) was cooled in dry ice and n-BuLi (22.2 mL of 1.6 M in hcxanes, 35.5 mmol) 25 was added dropwise. After 1 hour, the bath was removed and the mixture was stirred for 48 hours at room temperature. The mixture was added to ZrCl 4 (4.37 g, 18.8 mmol) suspended in pentane (50 mL) while cooling in ice. The slurry was stirred for 65 hours at room temperature. The slurry was concentrated until thick and pentane (70 mL) was added. The slurry was stirred overnight and the liquid was decanted, off. 30 The solid was washed a second time with pentane and then extracted with methylene chloride and centrifuged. The solution was taken to dryness under vacuum to give a WO 2007/092753 PCT/US2007/061519 91 red solid (11.65 g, 85.2% yield). 1 H NMR (300 MHz, CDCl 3 ) 8 7.93-8.02 (m, 3H), 7.80-7.91 (m, 3H), 7.52-7.60 (dt, J= 8.7 Hz, 1.5 Hz, 2H), 7.38-7.47 (m, 2H), 7.20 7.35 (m, 4H), 6.27 (broad s, 2H), 6.14-6.18 (t, J = 3.0 Hz, 1H), 5.67-5.83 (m, 1H), 5.61-5.64 (t, J= 3.0 Hz, 1H), 5.48-5.52 (t, J= 3.0 Hz, IH), 4.88-5.04 (m, 2H), 1.76 5 2.10 (m, 2H), 1.44-1.53 (m, 2H), 1.26 (s, 3H), 1.07 (s, 3H), 1.02 (s, 18H); 1 3 C NMR (75 MHz, CDC13) 6 149.67, 149.60, 144.31, 144.13, 143.46, 138.49, 129.15, 128.89, 128.51, 128.48, 128.39, 128.33, 126.58, 126.52, 126.11, 125.97, 124.18, 124.10, 123.73, 123.36, 121.09, 120.78, 120.20, 119.75, 118.88, 114.16, 113.84, 108.10, 104.30, 100.60, 77.19, 57.65, 46.43, 36.32, 35.38, 35.36, 31.06, 31.03, 29.47, 26.99, 10 24.19. Synthesis of Diphenylmethylidenelr1 5 -(cyclopentadien-1-ylidene)][q 5 -(2,7-di-tert butylfluoren-9-ylidene)]zirconium dichloride (C-1) Under nitrogen, 1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)-1,1 15 diphenylmethane (compound L-4) (15.26 g, 30.0 mmol) was suspended in dry Et 2 O (250 mL). While cooling in dry ice, n-BuLi (24.0 mL of 2.5 M in hexanes, 60 mmol) were added dropwise. The bath was then removed and the mixture was stirred for 24 hours. The solution was gradually added to zirconium tetrachloride (7.38 g, 31.7 mmol) suspended in pentane (50 mL) and cooled in ice. The orange slurry was stirred 20 for 90 hours and allowed to warm to room temperature. The resulting slurry was centrifuged and the solid was mixed with dry methylene chloride (120 mL). The mixture was centrifuged and the solution was removed and taken to dryness under vacuum. The desired product (9.63 g, 48% yield) was obtained as an orange solid. 'H NMR (300 MHz, CDCI 3 ) 8 7.98-8.04 (d, J= 9 Hz, 2H), 7.91-7.96 (m, 2H), 7.83 25 7.89 (m, 2H), 7.55-7.60 (dd, J= 9 Hz, 1.8 Hz, 2H), 7.38-7.45 (dt, J= 7.5 Hz, 1.8 Hz, 2H), 7.21-7.36(m, 4H), 6.30-6.34 (m, 4H), 5.64-5.67 (t, J = 2.7 Hz, 2H), 1.03 (s, 18H); '-C NMR (75 MHz, CDCl 3 ) 8 149.98, 144.00, 128.93, 128.50, 128.41, 126.64, 126.08, 124.16, 123.56, 121.12, 120.30, 119.41, 117.92, 109.92, 102.40, 77.72, 58.36, 35.40, 31.01. 30 WO 2007/092753 PCT/US2007/061519 92 Synthesis of dibutylmethylidene {r-[3-(pent-4-enyl)cyclopentadien-1 ylidene }} [i 5 -(2,7-di-tert-butylfluoren-9-ylidene)] zirconium dichloride (C-2) A flask was charged with 5-(3-(pent-4-enyl)cyclopentadienyl)-5-(2,7-di-tert butylfluorenyl)nonane (compound L-5) (12.8 g, 23.8 mmol), Et 2 O (200 mL), stir bar 5 and cooled to -78 *C as n-BuLi (5.3 mL of 10 M in hexanes, 53 mmol) was slowly added. The mixture was warmed to room temperature, stirred overnight, and then added via cannula to ZrC1 4 (5.5 g, 23.6 mmol) stirring in pentane at 0 'C. The mixture was warmed to room temperature, stirred for 7 days, and evacuated to dryness. The residue was extracted with pentane, filtered, and the filtrate discarded. 10 The remaining solid was extracted with CH 2 C1 2 , filtered and the filtrate evacuated to dryness affording a red solid (7.8 g, 47% yield). %). 1H NMR (300 MHz, CDC1 3 ) 8 7.88-7.94 (m, 2H), 7.63 (broad s, 1H), 7.55 (broad s, 1H), 7.47-7.53 (m, 2H), 5.87 5.90 (t, J= 2.7 Hz, iH), 5.58-5.73 (m, 1H), 5.46-5.49 (t, J= 2.7 Hz, 1H), 5.23-5.27 (t, J= 2.7 Hz, 1H), 4.80-4.92 (in, 2H), 2.55-2.75 (m, 4H), 2.20-2.40 (m, 2H), 1.90-2.00 15 (m, 2H), 1.40-1.80 (m, 1OH), 1.15 (s, 18H), 1.00 (t, J= 6.9 Hz, 3H), 0.97 (t, J= 6.9 Hz, 3H); 1 3 C NMR (75 MHz, CDCl 3 ) 5 150.92, 150.64, 137.78, 134.97, 123.74, 123.51, 123.48, 123.44, 123.12, 122.48, 120.96, 120.56, 118.73, 118.36, 116.13, 114.32, 112.59, 102.07, 101.93, 76.73, 48.76, 35.79, 35.76, 34.81, 34.68, 33.75, 31.49, 31.48, 29.59, 29.24, 26.35, 26.18, 24.07, 24.04, 14.81, 14.78. 20 Synthesis of dibutylmethylidene{" 5 -[3-(pent-4-enyI)cyclopentadien-1 ylidenel} [r1 5 -(2,7-di-tert-butylfluoren-9-ylidene)]hafnium dichloride (C-3) To 5-(3-(pent-4-enyl)cyclopentadienyl)-5-(2,7-di-tert-butylfluorenyl)nonane (compound L-5) (14.6 g, 27.2 mmol) dissolved in Et 2 O (150 mL) was slowly added 25 n-BuLi (26 mL of 2.5 M in hexanes, 65 mmol) at 0 'C. The mixture was warmed to room temperature, stirred overnight, and then added via cannula to HfCl4 (9.2 g, 28.7 mmol) suspended in a mixture of pentane (150 mL) and Et 2 O (20 mL) at -78 *C in 15 minutes. The mixture was warmed to room temperature, stirred for two days and evacuated to dryness. The residue was stirred in pentane (150 mL) and centrifuged. 30 The supernatant was discarded. The remaining solid was extracted with methylene chloride and centrifuged. The solution was taken to dryness under vacuum to give a WO 2007/092753 PCT/US2007/061519 93 yellow solid (6.6 g, 31% yield). 1 H NMR (300 MHz, CDCl 3 ) 6 7.88-7.91 (m, 2H)], 7.64 (broad s, 1H), 7.56 (broad s, 1H), 7.42-7.48 (m, 2H), 5.80-5.84 (t, J= 2.7 Hz, IH), 5.58-5.73 (m, IH), 5.39-5.43 (t, J= 2.7 Hz, 1H), 5.18-5.23 (t, J= 2.7 Hz, 1H), 4.78-4.91 (m, 2H), 2.55-2.75 (m, 411), 2.22-2.42 (m, 2H), 1.88-1.97 (m, 2H), 1.40 5 1.80 (m, 10H), 1.27 (s, 18H), 0.99 (t, J= 6.9 Hz, 3H), 0.97 (t, J= 6.9 Hz, 3H); ' 3 C NMR (75 MHz, CDCl 3 ) 8 150.63, 150.32, 137.78, 133.55, 123.42, 123.40, 123.36, 123.15, 121.99, 121.30, 119.48, 119.02, 118.30, 117.97, 115.26, 115,07, 114.30, 99.44, 99.39, 76.79, 48.73, 35.74, 35.72, 35.01, 34.89, 33.78, 31.52, 31.49, 29.53, 29.30, 26.46, 26.30, 24.09, 24.05, 14.83, 14.79. 10 EXAMPLES 1-16 Catalytic Runs Varying the Metallocene, Activator-Support, and Conditions Examples 1-16 in Table I illustrate ethylene polymerization runs performed in a one-gallon (3.785 liter) stainless steel autoclave reactor at various temperatures, 15 using two liters of isobutane diluent and an aluminum alkyl cocatalyst and scavenger. No hydrogen or comonomer was added. Metallocene solutions (2mg/mL) were typically prepared by dissolving 30 mg of the metallocene in 15 mL of toluene. A typical polymerization procedure is as follows. The aluminum alkyl compound, treated solid oxide, and the metallocene solution were added through a charge port, 20 typically in that order, while venting isobutane vapor. The charge port was closed and two liters of isobutane were added. The contents of the reactor were stirred and heated to the desired run temperature (Table 1). Ethylene was fed on demand to maintain the specified pressure for the specified length of the polymerization run. The reactor was maintained at the desired run temperature through the run by an 25 automated heating and cooling system. After the allotted polymerization time, the ethylene flow was stopped, and the reactor slowly depressurized and opened to recover a granular polymer. In all cases, the reactor was clean with no indication of any wall scale, coating or other forms of fouling. The polymer was then removed and weighed (Table 1). 30 WO 2007/092753 PCT/US2007/061519 94 - 10 ON m~ 'n _n a, w0 en en) Nq N1 N q N CN .* Z 00 r- 'n C7 o NC 00 N~ N1 r- N ) a, r- N 00 - 1 - W - r- -0 O ~ 1 C, 0 n N ~, ~ 0 - 0 N n en -q 10 Nn CDV , 0 c" 11 nc 0 ~ e en m C14 00ell 0 m - - I gc d 0)' 0 0 0> C, 0- 0 0 r 0 0 0 0 : cl >~ .4 C, C, '-4 1 4 c4 c 0' 2 -I 0)0 o9 .2_ ~ ~ .~ o4 C, C~ ml C>Cl 'n __ __n - -n - - - In -4 C14 m 0 Inr- 0 WO 2007/092753 PCT/US2007/061519 95 .fl 00 00 04 00 4 m' C) clq en e ')4-) C) 0 C, C, 04 I4 04V

权利要求:
Claims (31)
[1] 1. A catalyst composition comprising the contact product of: 1) at least one ansa-metallocene; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: (XI)(X 2 )(X 3 )(X 4 )MI, wherein M1 is titanium, zirconium, or hafnium; (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula ERR 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least onc of R1 and R 2 is an aryl group; at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; b) the at least one organoaluminum compound comprises a compound having the formula: WO 2007/092753 PCT/US2007/061519 97 Al .(X 6)3 wherein (X 5 ) is a hydrocarbyl having from 1 to 20 carbon atoms; (X 6 ) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive; and c) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron compound or an organoborate compound; or iv) any combination thereof; wherein the at least one organoaluminum compound is optional when: 1) at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 2) the at least one activator comprises an organoaluminoxane compound; or 3) both conditions 1 and 2 are present.
[2] 2. The catalyst composition of Claim 1, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: R4A: Q R 4 B RA R 3 B (I), wherein M1 is zirconium or hafnium; X is, independently, F, Cl, Br, or I; E is C or Si; R' and R2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R' or R 2 is an aryl group; WO 2007/092753 PCT/US2007/061519 98 R 3 A and R 3 D are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and R 4 A and RB are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof, and c) the at least one activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflatc, bisulfate, sulfate, fluoroboratc, fluorosulfate, trifluoroacctate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof.
[3] 3. The catalyst composition of Claim 1, wherein the at least one activator is an activator-support further comprising a metal or metal ion such as zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.
[4] 4. The catalyst composition of Claim 1, wherein the at least one activator is an activator-support selected from a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non layered silicate mineral, a layered aluminosilicate mineral, a non-layered aluminosilicate mineral, or any combination thereof. WO 2007/092753 PCT/US2007/061519 99
[5] 5. The catalyst composition of Claim 4, wherein the clay mineral comprises an allophone, a smectite, a montmorillonite, a nontronite, a hectorite, a laponite, a halloysite, a vermiculite, a mica, a fluoromica, a chlorite, a mixed-layer clay, a fiberous clay, a sepiolite, an attapulgite, a palygorskite, a serpentine clay, an illite, a saponite, or any combination thereof.
[6] 6. The catalyst composition of Claim 1, wherein the at least one ansa metallocene comprises a compound having the formula: R4A R 4 B R2v6E X R3A R3B (11), wherein M 1 is zirconium or hafnium; X is F, Cl, Br, or I; E is C or Si; R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group; R 3 A and R 3 B are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl; n is an integer from 1 to 6, inclusive; and R4 and R4B are independently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen. WO 2007/092753 PCT/US2007/061519 100
[7] 7. The catalyst composition of Claim 1, wherein the at least one ansa metallocene comprises a compound having the formula: R4A / R 4 B R2rE M R 3 A R 3 B (111), wherein M 1 is zirconium or hafnium; X is Cl, Br, or 1; E is C or Si; R' and R 2 are independently methyl or phenyl, wherein at least one of R1 or R 2 is phenyl; R 3 A and R 3 B are independently H or methyl; n is I or 2; and R 4 A and RB are independently H or t-butyl.
[8] 8. The catalyst composition of Claim 1, wherein the at least one ansa t-Bu t-Bu t-Bu t-Bu Ph&a,, ,,,-lCI Phi,. 2 an"MCI Ph, Zr CI~ ~ Ph- Zr*C" metallocene is selected from t u- t u - t-Bu t-Bu t-Bu t- Q u t-Bu / t-Bu Ph "MPhi,,,,,MCI C K h,,,, f"" 0 Ph--' Ph* ' C Ph'~~smC WO 2007/092753 PCT/US2007/061519 101 t-Bu t-Bu -Bu t-Bu Ph /z -B Ph#,. / tB Phll. j OIICI Ph r Hf eeC hn.. g.uC' Ph" C Ph-C' Ph- CI ,or any combination thereof.
[9] 9. The catalyst composition of Claim 1, wherein (6) is fluoride, chloride, bromide, methoxide, ethoxide, or hydride.
[10] 10. The catalyst composition of Claim 1, wherein Al(X 5 )n(X 6 ) 3 - is trimethyl aluminum, triethylaluminum, tri-n-propylaluminum, tri-i -propyl aluminum, tri-n-butylaluminum, tri-sec-butylaluminum, triisobutylaluminum, tri-n hexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.
[11] 11. The catalyst composition of Claim 1, wherein the at least one activator is an activator-support selected from chlorided alumina, fluorided alumina, fluorided aluminophosphate, sulfated alumina, fluorided silica-alumina, a pillared clay, or any combination thereof.
[12] 12. The catalyst composition of Claim 1, wherein the organoaluminoxane compound comprises a cyclic aluminoxane having the formula: R ; wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 3 to about 10; a linear aluminoxane having the formula: WO 2007/092753 PCT/US2007/061519 102 R R AI-O A( R R; wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from I to about 50; a cage aluminoxane having the formula R 5 +Rbm,-A1 4 ,,O 3 n, wherein m is 3 or 4 and a is = nA(3) - no(2) + nO(4); wherein nAI(3) is the number of three coordinate aluminum atoms, nO( 2 ) is the number of two coordinate oxygen atoms, no(4) is the number of 4 coordinate oxygen atoms, Rt represents a terminal alkyl group, and R represents a bridging alkyl group; wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms; or any combination thereof.
[13] 13. The catalyst composition of Claim 1, wherein the organoboron compound or the organoborate compound is selected from tris(pentafluorophenyl)boron, tris[3,5 bis(trifluoromethyl)phenyl]boron, NN-dimethylanilinium tetrakis (pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, NN-dimethylanilinium tetrakis[3,5 bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5 bis(trifluoromethyl)phenyl]borate, or any combination thereof.
[14] 14. The catalyst composition of Claim 1, further comprising an ionizing ionic compound selected from tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4 dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n butyl)ammonium tetrakis(pentafluorophenyl)borate, NN-dimethylanilinium tetrakis(p-tolyl)borate, NN-dimethylanilinium tetrakis(m-tolyl)borate, N,N dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, NN-dimethylanilinium tetrakis[3,5-bis(trifluoro methyl)phenyl]borate, NN-dimethylanilinium tetrakis(pentafluorophenyl)borate, WO 2007/092753 PCT/US2007/061519 103 triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoro methyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate, lithium tetrakis(p tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4 dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl) borate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m tolyl)boratc, potassium tetrakis(2,4-dimethylphonyl)borate, potassium tetrakis(3,5 dimethylphenyl)borate, potassium tetrafluoroborate, triphenylcarbenium tetrakis(p tolyl)aluminate, triphenylcarbenium tetrakis(m-tolyl)aluminate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbenium tetrakis(3,5 dimethylphenyl)aluminate, triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, tropylium tetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate, tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropylium tetrakis(3,5 dimethylphenyl)aluminate, tropylium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4 dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5 dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetrakis(phenyl)aluminate, potassium WO 2007/092753 PCT/US2007/061519 104 tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis (3,5 dimethylphenyl)aluminate, potassium tetrafluoroaluminate, triphenylcarbenium tris(2,2',2"-nonafluorobiphenyl)fluoroaluminate, silver tetrakis( 1,1,1,3,3,3 hexafluoroisopropanolato)aluminate, or silver tetraki s(perfluoro-t-butoxy)aluminate, or any combination thereof.
[15] 15. The catalyst composition of Claim 1, wherein: a) the at least one ansa-metallocene comprises t-Bu t-Bu t-Bu t-Bu t-B t-Bu Ph Ph Phi , Ph;, Ph--' Ph--'C Zr*' -'CI Ph- C t-B t-u tBu -Bu t.-Bu t-Bu - ~- tt-KBu tB /u t-Bu tB -uP,,, PhPn Ph Zz .,C1 PhC Ph_ Ph-* Ph- C t-Bu t-Bu t-Bu t-Bu Ph,,,,,. CI Ph nCI Ph" 5 'CI Ph-C' or any combination thereof; b) the at least one organoaluminum compound comprises tricthylatuminum, tri-n-butylahuminum, triisobutylaluminum, or any combination thereof; and c) the at least one activator comprises a sulfated solid oxide. WO 2007/092753 PCT/US2007/061519 105
[16] 16. The catalyst composition of Claim 1, wherein: a) the at least one ansa-metallocene comprises t-Bu / t t-Bu / Bu t-Bu 9 / t-Bu t-Bu t-Bu / t-Bu P h- " r CPh Z r Ch-*" PhPh Ph Zr, or any combination thereof; b) the at least one organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; and c) the at least one activator comprises sulfated alumina.
[17] 17. A catalyst composition comprising the contact product of: 1) at least one ansa-metallocene; and 2) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: (XI)(X 2 )(X 3 )(X 4 )M1, wherein M' is titanium, zirconium, or hafnium; (X') and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indcnyl, or a substituted fluorenyl; one substituent on (X') and (X 2 ) is a bridging group having the formula ER'R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R2 is an aryl group; WO 2007/092753 PCT/US2007/061519 106 at least one substituent on (X') or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; wherein at least one (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; and b) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-cxchangeable activator support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron compound or an organoborate compound; or iv) any combination thereof.
[18] 18. The catalyst composition according to Claim 17, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: R4A R 4 B R 2"'EM R 3 R 3 B (IV), wherein M 1 is zirconium or hafnium; WO 2007/092753 PCT/US2007/061519 107 X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph; E is C or Si; R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R7 is an aryl group; RA and R are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and R 4 A and R 4 " are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; and b) the at least one activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof.
[19] 19. A process for producing a polymerization catalyst composition comprising contacting: 1) at least one ansa-metallocene; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: (X1)(X 2 )(X 3 )(X 4 )MI, wherein M' is titanium, zirconium, or hafnium; WO 2007/092753 PCT/US2007/061519 108 (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X') and (X 2 ) is a bridging group having the formula ER 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; b) the at least one organoaluminum compound comprises a compound having the formula: Al(X5).(X6)3-., wherein (X-) is a hydrocarbyl having from 1 to 20 carbon atoms; (X6) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive; and c) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron compound or an organoborate compound; or WO 2007/092753 PCT/US2007/061519 109 iv) any combination thereof; wherein the at least one organoaluminum compound is optional when: 1) at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 2) the at least one activator comprises an organoaluminoxane compound; or 3) both conditions 1 and 2 are present.
[20] 20. The process for producing a polymerization catalyst composition according to Claim 19, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: R4A R 4 E R2 E R 3 A R 3 B (I), wherein M 1 is zirconium or hafnium; X is, independently, F, Cl, Br, or I; E is C or Si; R 1 and R2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group; RA and R 3 B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and RA and R4 are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and WO 2007/092753 PCT/US2007/061519 110 c) the at least one activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof.
[21] 21. A process for producing a polymerization catalyst composition comprising contacting: 1) at least one ansa-metallocene; and 2) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: (X')(X 2 )(X 3 )(X 4 )M', wherein M 1 is titanium, zirconium, or hafnium; (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula ERR 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X') and (X 2 ), and wherein R1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R' and R 2 is an aryl group; at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any WO 2007/092753 PCT/US2007/061519 111 of which having up to 12 carbon atoms; wherein at least one (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; and b) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron compound or an organoborate compound; or iv) any combination thereof.
[22] 22. The process for producing a polymerization catalyst composition according to Claim 21, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: R4A R 4 B RwE M--.%,~ R 3 A R3B (IV), wherein M1 is zirconium or hafnium; X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph; E is C or Si; WO 2007/092753 PCT/US2007/061519 112 R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group; R 3 A and R 3 3 are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and R 4 A and R 4 B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; and b) the at least one activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, alurninophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkancsulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof.
[23] 23. A method ofpolymerizing olefins, comprising: contacting ethylene and an optional ca-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition comprises the contact product of: 1) at least one ansa-metallocene; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: (X')(X 2 )(X 3 )(X 4 )MI, wherein M' is titanium, zirconium, or hafnium; (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; WO 2007/092753 PCT/US2007/061519 113 one substituent on (X') and (X 2 ) is a bridging group having the formula ER 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X') and (X 2 ), and wherein R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X') or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BT 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from I to 20 carbon atoms; a halide; or hydrogen; b) the at least one organoaluminum compound comprises a compound having the formula: Al(.(X6g)3-n, wherein (X 5 ) is a hydrocarbyl having from 1 to 20 carbon atoms; (X 6 ) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive; and c) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron compound or an organoborate compound; or iv) any combination thereof; WO 2007/092753 PCT/US2007/061519 114 wherein the at least one organoaluminum compound is optional when: 1) at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 2) the at least one activator comprises an organoaluminoxane compound; or 3) both conditions 1 and 2 are present.
[24] 24. The method of polymerizing olefins according to Claim 23, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: R 4 A 4B R 2 'X R2I EM R 3 A R 38 (I), wherein M 1 is zirconium or hafnium; X is, independently, F, Cl, Br, or I; E is C or Si; R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R1 or R 2 is an aryl group; R3A and RE are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and R 4 A and R 4 B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and c) the at least one activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein WO 2007/092753 PCT/US2007/061519 115 the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof.
[25] 25. A polymer produced by the method of Claim 21.
[26] 26. An article comprising a polymer produced by the method of Claim 21.
[27] 27. A method of polymerizing olefins, comprising: contacting ethylene and an optional a-olofin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition comprises the contact product of: 1) at least one ansa-metallocene; and 2) at least one activator, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: (X')(X 2 )(X 3 )(X 4 )MI, wherein M' is titanium, zirconium, or hafnium; (X') and (X 2 ) arc independently a substituted cyclopcntadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula ER'R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R 2 is an aryl group; at least one substituent on (X') or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; WO 2007/092753 PCT/US2007/061519 116 (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBRA 2 or SO 3 RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; wherein at least one (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; and b) the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron compound or an organoborate compound; or iv) any combination thereof.
[28] 28. The method ofpolymerizing olefins according to Claim 27, wherein: a) the at least one ansa-metallocene comprises a compound having the formula: R 4 A R 4 B R2~ R2VPIE MI*W R3A R 3 B (IV), wherein M 1 is zirconium or hafnium; WO 2007/092753 PCT/US2007/061519 117 X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph; E is C or Si; R' and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R1 or R 2 is an aryl group; R 3 A and R 3 are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and R 4 A and R 4 " are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; and b) the at least one activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof.
[29] 29. A polymer produced by the method of Claim 27.
[30] 30. An article comprising a polymer produced by the method of Claim 27. WO 2007/092753 PCT/US2007/061519 118
[31] 31. A compound having the formula: t-Bu t-Bu Phe"'".M2.OanCI PhO C ,wherein M 2 is Zr or Hf.

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法律状态:
2013-04-04| FGA| Letters patent sealed or granted (standard patent)|

优先权:

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申请号 | 申请日 | 专利标题

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US11/345,966|US7517939B2|2006-02-02|2006-02-02|Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching|

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US11/345,966||2006-02-02||

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PCT/US2007/061519|WO2007092753A2|2006-02-02|2007-02-02|Polymerization catalysts for producing polymers with low levels of long chain branching|

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