HK1131997B - Polymerization catalysts for producing polymers with low levels of long chain branching - Google Patents

Description

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

Technical Field

The present invention relates to the field of organometallic compositions, olefin polymerization catalyst compositions, methods of olefin polymerization and copolymerization using the catalyst compositions, and polyolefins.

Background

It is known that mono-1-olefins (alpha-olefins), including ethylene, can be polymerized with catalyst compositions using titanium, zirconium, vanadium, chromium or other metals, often in combination with solid oxides, and in the presence of a cocatalyst. These catalyst compositions can be used for the homopolymerization of ethylene as well as the copolymerization of ethylene with comonomers such as propylene, 1-butene, 1-hexene or other higher alpha-olefins. Accordingly, there is an ongoing search for the development of new olefin polymerization catalysts, catalyst activation methods, and methods of making and using catalysts that will provide enhanced catalytic activity and polymeric materials suitable for particular end uses.

Polyethylene (PE) produced by many processes typically contains small to moderate amounts of long chain branched molecules. In some cases, long-chain branching (LCB) is desirable to improve bubble stability during film blowing or to enhance processability of resins prepared with metallocene catalysts. For many applications, however, the presence of LCB is considered undesirable due to the increased elasticity that it typically imparts to the resin. Therefore, the ability to control LCB levels in polyethylene using metallocene-based catalysts is a desirable goal.

An example of this need is seen in the application of bridged or ansa-metallocene catalysts, which are desirable catalysts for some purposes, but which may tend to produce polymers with LCB levels that are detrimental to film performance. Therefore, new catalyst compositions and methods that enable better control of LCB levels within desired specification ranges are desirable goals.

Summary of The Invention

The invention includes catalyst compositions, methods of making catalyst compositions, olefin polymerization processes, and ethylene polymers and copolymers. In the course of studying olefin polymerization catalysts based on metallocene catalysts, it was found that: the long-chain branching (LCB) content of PE resins prepared with such catalysts is related to the type of metallocene catalyst used, among others, and also to the specific activator, which includes a specific solid oxide activator or "activator-support" capable of constituting one component of the catalyst composition.

In one aspect of the invention, for example, it is found that: even under relatively high temperature conditions, certain metallocene-based catalyst systems can produce high molecular weight polyethylene with low levels of LCB. Metallocenes useful in preparing the catalyst compositions of the present invention include, but are not limited to, tightly bridged (tiglyl-bridged) ansa-metallocenes (ansa-metallocenes) comprising a pendant alkenyl (olefin-containing) group attached to at least one of the cyclopentadienyl-type moieties of the tightly-bridged ligand, and also comprising one or two aryl groups, particularly one or two phenyl groups, bound to the bridging atom of the tightly-bridged ligand.

Accordingly, in one aspect, the invention includes a catalyst composition comprising: at least one tightly bridged ansa-metallocene compound comprising a pendant olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bound 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 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, the invention includes a contact product of: at least one tightly bridged ansa-metallocene compound comprising a side chain olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bound to the bridging atom of the bridging ligand; optionally, at least one organoaluminum compound; and at least one activator, as provided herein. In this aspect, the invention includes compositions of matter, catalyst compositions for polymerizing olefins, methods of preparing catalyst compositions, methods of polymerizing olefins, novel ethylene polymers and copolymers, and the like, comprising in each case: at least one tightly bridged ansa-metallocene compound comprising a side chain olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bound 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, i.e., it can be an activator-support comprising a solid oxide treated with an electron-withdrawing anion.

In one aspect, the catalyst composition of the present invention may 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 formula:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to (X)¹) And (X)²) Wherein R is¹And R²Independently is an alkyl group or an aryl group, any of which having up to 12 carbon atoms, or hydrogen, wherein R is¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) f, Cl, Br, or I; 2) hydrocarbon radicals having up to 20 carbon atoms, H, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl or 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; halogen root; or hydrogen;

b) the at least one organoaluminum compound comprises a compound having the formula:

Al(X⁵)_n(X⁶)_3-n，

wherein (X)⁵) Is a hydrocarbyl group having 1 to 20 carbon atoms; (X)⁶) Is alkoxy (alkoxy) or aryloxy (aryloxide) -any of which having 1 to 20 carbon atoms, a halide or a hydride; and n is a number from 1 to 3, 1 and 3 being included; and

c) the at least one activator is independently selected 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 or organoborate compound; or

iv) any combination thereof.

In one aspect of the invention, when: 1) (X)³) And (X)⁴) At least one of (A) is a hydrocarbon group having up to 20 carbon atoms, H or BH₄(ii) a 2) The at least one activator comprises at least one organoaluminoxane compound; or 3) when both conditions 1 and 2 are present, the at least one organoaluminum compound can be optional. Thus, while not intending to be bound by theory, one of ordinary skill will recognize that metallocene-based compositions exhibiting catalytic polymerization activity generally comprise the contact product of: 1) a metallocene component; 2) providing such ligands, e.g., alkyl or hydride ligands, to the components of the metallocene when the metallocene compound does not comprise an activatable ligand; and 3) an activator component. In some cases, one component may function as both a component providing an activatable ligand and an activator component, e.g., an organoaluminoxane. In other cases, both functions may be provided by two separate components, such as an organoaluminum compound capable of providing an activatable alkyl ligand to the metallocene, and a solid oxide treated with an electron-withdrawing anion capable of providing an activator function. Further, in some cases, metallocene compoundsAn activatable ligand such as an alkyl ligand is already included, and thus the component providing the activatable ligand is not necessary, but may be an optional component of the contact product. Thus, as understood by one of ordinary skill, by designating at least one organoaluminum compound as "optional" in a contact product, it is intended to reflect that the organoaluminum compound may be optional, when it is not necessary to impart catalytic activity to a composition comprising the contact product.

In another aspect of the present invention, the present 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:

(I) wherein

M¹Is zirconium or hafnium;

x is independently F, Cl, Br or I;

e is C or Si;

R¹and R²Independently is an alkyl or aryl group, either of which having up to 10 carbon atoms, or is hydrogen, wherein R is¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently any of which has up to 20 carbon atoms, or a trihydrocarbylsilyl group; or hydrogen;

n is an integer from 0 to 10, including 0 and 10; and is

R^4AAnd R^4BIndependently 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-support comprises a solid oxide treated with an electron-withdrawing anion, wherein

The solid oxide is silica, alumina, silica-alumina, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstates (hetetoolytungstates), 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.

In yet 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:

a) the at least one ansa-metallocene comprises a compound having the formula:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²The bridging group of (a) is,wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to (X)¹) And (X)²) Wherein R is¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) fluorine (F), chlorine (Cl), bromine (Br) or iodine (I); 2) hydrocarbon radicals having up to 20 carbon atoms, hydrogen, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl group or an aryl group, any of which having up to 12 carbon atoms; at least one of them (X)³) And (X)⁴) Is a hydrocarbon radical having up to 20 carbon atoms, hydrogen or BH₄(ii) a 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; halogen root; or hydrogen; and

b) the at least one activator is independently selected 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 organoborate compound; or

iv) any combination thereof.

Yet another aspect of the 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:

wherein

M¹Is zirconium or hafnium;

x is independently hydrogen, BH4, methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH₂CMe₂Ph；CH₂SiMe₂Ph；CH₂CMe₂CH₂Ph; or CH₂SiMe₂CH₂Ph；

E is carbon or silicon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently a hydrocarbyl group or a trihydrocarbylsilyl group-any of which has up to 20 carbon atoms, or hydrogen;

n is an integer from 0 to 10, inclusive; and

R^4Aand R^4BIndependently 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, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, 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.

In a further aspect of the invention, the activator-support can comprise a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide comprises silica, alumina, silica-alumina, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, 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, 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. In addition, the activator-support can further comprise 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 is fluoride, chloride, bromide, iodide, phosphate, triflate, hydrogensulfate, 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.

In yet another aspect of the present invention, the activator-support may comprise a layered mineral, an ion-exchangeable activator-support, or any combination thereof. In this aspect, the activator-support can include a clay mineral, a pillared 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.

In another aspect, the present 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 a composition wherein at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator are defined herein. In yet another aspect, the present invention provides a process for polymerizing olefins comprising contacting ethylene and optionally an alpha-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition is provided as disclosed herein. In still a further aspect, the present invention provides ethylene polymers and copolymers, and articles made therefrom, produced by contacting an ethylene polymer and optionally an alpha-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition is provided as disclosed herein.

In one aspect of the invention, the activity of the catalyst composition of the invention can be enhanced by pre-contacting some of the polymerization components for a first period of time to form a first mixture, and then contacting the mixture with the remaining polymerization components for a second period of time to form a second mixture. For example, the ansa-metallocene compound can be precontacted with some other polymerization reaction component including, but not limited to, for example, an alpha-olefin monomer and an organoaluminum cocatalyst for a period of time, before the mixture is contacted with the remaining polymerization reaction component including, but not limited to, a solid oxide activator-support. The first mixture is generally referred to as a "precontacted mixture" and includes precontacted components, and the second mixture is generally referred to as a "postcontacted mixture" and includes postcontacted components. For example, a mixture of at least one metallocene, at least one olefin monomer, and at least one organoaluminum co-catalyst compound is one type of "pre-contact" mixture prior to contacting the mixture with the activator-support. The pre-contact mixture is contacted with the acidic activator-support to form a mixture of metallocene, monomer, organoaluminum cocatalyst, and acidic activator-support, and is therefore referred to as a "post-contact" mixture. The term is used regardless of the type of reaction that occurs between the components of the mixture, if any. For example, according to the present description, once a precontacted organoaluminum compound is mixed with a metallocene or multiple metallocenes and olefin monomers, the precontacted organoaluminum compound may have a different chemical formula and structure than the different organoaluminum compounds used to prepare the precontacted mixture.

The present invention also includes a process for preparing a catalyst composition utilizing at least one ansa-metallocene catalyst, optionally at least one organoaluminum compound, and at least one activator. The process of the present invention comprises precontacting any selected catalyst, e.g., metallocene and organoaluminum cocatalyst, with the olefin, typically but not necessarily the monomer to be polymerized or copolymerized, and then contacting the precontacted mixture with any remaining catalyst component, in this example, the solid oxide activator-support.

In still another aspect, the invention further includes novel catalyst compositions, methods of making catalyst compositions, and olefin polymerization processes that can result in improved productivity. In one aspect, these processes can be carried out without the need to use large excess concentrations of expensive organoaluminoxane co-catalysts such as Methylaluminoxane (MAO), or the catalyst compositions can be substantially free of aluminoxanes such as MAO. That is, the catalyst composition of the present invention can have polymerization activity in the substantial absence of aluminoxane. However, the present invention also provides a catalyst composition comprising an ansa-metallocene and an aluminoxane. Thus, in this aspect, the catalyst composition need not include any acidic activator-support, wherein the activator-support comprises a chemically-treated solid oxide, and the catalyst composition need not include an organoaluminum compound.

Additionally, the invention includes a method comprising contacting at least one monomer with a catalyst composition under polymerization conditions to produce a polymer. Accordingly, the present invention includes a process for polymerizing olefins using a catalyst composition prepared as described herein.

The present invention also includes novel polyolefins.

The invention also includes articles comprising polymers produced with the catalyst compositions of the invention.

These and other features, aspects, embodiments, and advantages of the present invention will become apparent upon reading the following detailed description of the disclosed features.

Brief Description of Drawings

FIG. 1 illustrates the structure of a specific metallocene used in an example of the present invention.

FIG. 2 illustrates the structure of a specific metallocene used in the comparative examples.

FIG. 3 illustrates data (R) obtained by SEC-MALS analysis of ethylene homopolymers produced in examples 1-4 of the present invention_gTo M_wDrawing).

FIG. 4 illustrates the ethylene produced in examples 5-7 of this inventionData obtained by SEC-MALS analysis of homopolymers (R)_gTo M_wDrawing).

FIG. 5 illustrates data (R) obtained by SEC-MALS analysis of ethylene homopolymers produced in examples 10 and 11 of the present invention_gTo M_wDrawing).

FIG. 6 provides a plot of zero shear viscosity (zero shear viscosity) versus molecular weight, specifically log (. eta. eta.) for polymers prepared in accordance with inventive examples 1-11₀) Log (M)_w) And (6) drawing.

FIG. 7 provides a plot of zero shear viscosity versus molecular weight, specifically log (. eta.) for polymers prepared according to inventive examples 14-16₀) Log (M)_w) And (6) drawing.

FIG. 8 provides comparative Gel Permeation Chromatograms (GPCs)) of ethylene homopolymers of examples 1-11(E1-E11) of the present invention and comparative examples 14-16 (E14-16).

Detailed Description

The present invention provides novel catalyst compositions, methods of making catalyst compositions, methods of polymerizing olefins using the catalyst compositions, olefin polymers, and articles made therefrom. In one aspect, the invention includes 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 bound to a bridging atom of the bridged ligand, at least one activator, and optionally at least one organoaluminum compound. In another aspect, the invention includes a method of making the catalyst composition disclosed herein, and in yet a further aspect, the invention includes a method of polymerizing olefins using the catalyst composition disclosed herein. As noted above, designating at least one organoaluminum compound as an optional component in the contact product is intended to reflect that the organoaluminum compound may be optional when it is not necessary to impart catalytic activity to the composition comprising the contact product, as will be appreciated by the skilled artisan. The components of the contact product are detailed below.

Catalyst composition and components

Metallocene compound

In one aspect, the present invention provides a catalyst composition comprising at least one tightly bridged ansa-metallocene compound comprising an olefin-containing moiety bound to a cyclopentadienyl-type ligand and at least one aryl group bound to a 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-metallocenes simply refers to compounds in which two η in the molecule are present⁵-metallocene compounds in which cyclic dienyl ligands are linked by a bridging moiety. Useful ansa-metallocenes are generally "tightly bridged", meaning that two η⁵The cyclic dienyl ligands being linked by a bridging group, where⁵The shortest connection of the bridging moieties between the cycloalkadienyl-type ligands is a single atom. Thus, at two η⁵The length of the bridge or chain between the cycloalkadienyl-type ligands is one atom, although the bridging atom is substituted. The metallocenes of the invention are therefore bridged bis (. eta.)⁵-cycloalkadienyl) type compound, wherein eta⁵Cycloalkadienyl moieties include substituted cyclopentadienyl ligands, substituted indenyl ligands, substituted fluorenyl ligands and the like, wherein one substituent on the cyclopentadienyl ligands is of the formula ER¹R²Wherein E is a carbon atom, a silicon atom, a germanium atom or a tin atom, and wherein E is bonded to two cyclopentadienyl ligands. In this aspect, R¹And R²Can be independently selected from any of alkyl or aryl groups having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group.

In this aspect, one substituent on the cyclopentadienyl ligand of the metallocene may be ofFormula (II)>CR¹R²、>SiR¹R²、>GeR¹R²Or>SnR¹R²Wherein R is¹And R²Can be independently selected from alkyl groups or aryl groups, either of which having up to 12 carbon atoms, or hydrogen, wherein R is¹And R²At least one of (a) is an aryl group. Bridging ER¹R²Examples of groups include, but are not limited to>CPh₂、>SiPh₂、>GePh₂、>SnPh₂、>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 η⁵-at least one substituent on at least one of the cyclodienyl-type ligands is a substituted or unsubstituted alkene-containing hydrocarbyl group having up to 12 carbon atoms, which is referred to herein as an "alkenyl group", regardless of the site chemistry (regiochemistry) of the alkene functionality. In this aspect, the olefin-containing hydrocarbyl group is joined to an η of a bridging ligand⁵-binding of ligands of the cyclodiene type, wherein the olefinic bond is remote from η⁵-a cycloalkadienyl-type ligand, and may thus be described as a pendant alkenyl group. Thus, one substituent on a substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl group of a metallocene comprises an alkenyl group, in which case the ansa-metallocene may be described as comprising a hydrocarbon chain comprising an olefinic moiety linked to one cyclopentadienyl-type ligand.

In another aspect, the at least one ansa-metallocene of the present invention comprises a compound having the formula:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is substituted with (X)¹) And (X)²) In combination, wherein R¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) fluorine, chlorine, bromine or iodine; 2) hydrocarbon radicals having up to 20 carbon atoms, hydrogen, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs 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; halogen root; or hydrogen.

In another aspect of the invention, η of the olefin-containing hydrocarbyl group with a bridging ligand⁵-one of the cyclodienyl-type ligands is bound, i.e. the alkenyl group may have up to about 20 carbon atoms. In another aspectThe 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 alkenyl groups include, but are 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 groups can contain from about 3 to about 7 carbon atoms from the cyclopentadienyl-type ligand itself, and in another aspect, from 3 to about 4 carbon atoms from the cyclopentadienyl-type ligand itself.

In yet another aspect, the olefin-containing hydrocarbyl group, i.e., alkenyl group, can be substituted or unsubstituted. For example, any substituent on the alkenyl group, when present, 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 substituted analogs thereof, any of which having from 1 to about 20 carbon atoms; halogen root; or hydrogen. In the case where hydrogen may be added to the unsaturated moiety in the alkenyl group, the hydrogen is listed as a possible substituent on the alkenyl group as long as it does not destroy the alkenyl group. Thus, hydrogen is a possible substituent on any unsaturated moiety within an alkenyl group, as long as hydrogen is not added through the alkene portion just thought to be essential to that group of the alkenyl group. Further, this description of other substituents on the alkenyl group atom may include substituted, unsubstituted, branched, straight chain or heteroatom substituted analogs of these moieties.

Examples of alkylene hydrocarbyl groups, particularly alkenyl groups, which may be bonded to at least one cyclopentadienyl-type moiety include, but are not limited to, 3-butenyl (CH)₂CH₂CH＝CH₂) 4-pentenyl (CH)₂CH₂CH₂CH＝CH₂) 5-hexenyl (CH)₂CH₂CH₂CH₂CH＝CH₂) 6-heptenyl (CH)₂CH₂CH₂CH₂CH₂CH＝CH₂) 7-octenyl (CH)₂CH₂CH₂CH₂CH₂CH₂CH＝CH₂) 3-methyl-3-butenyl (CH)₂CH₂C(CH₃)＝CH₂) 4-methyl-3-pentenyl (CH)₂CH₂CH＝C(CH₃)₂) 1, 1-dimethyl-3-butenyl (C (CH)₃)₂CH₂CH＝CH₂) 1, 1-dimethyl-4-pentenyl (C (CH)₃)₂CH₂CH₂CH＝CH₂) Etc., or any substituted analog thereof. In one aspect, the unsaturated group bonded to the bridging group can be 3-butenyl (CH)₂CH₂CH＝CH₂) 4-pentenyl (CH)₂CH₂CH₂CH＝CH₂) Or substituted analogs thereof.

In addition to containing compounds having the formula ER¹R²And at least one alkenyl group as disclosed herein, the cyclopentadienyl-type ligand may also have other substituents. For example, these substituents may be selected from (X) capable of acting as ansa-metallocenes³) And (X)⁴) The same chemical group or moiety of a ligand. Thus, any additional substituents on the cyclopentadienyl-type ligand; and any substituents on the substituted alkenyl group; and (X)³) And (X)⁴) Can be independently selected from aliphatic groups, aromatic groups, cyclic groups, combinations of aliphatic and cyclic groups, oxygen groups, sulfur groups, nitrogen groups, phosphorus groups, arsenic groups, carbon groups, silicon groups, boron groups, or substituted derivatives thereof, any of which having from 1 to about 20 carbon atoms; halogen root; or hydrogen; as long as these groups do not terminate the activity of the catalyst composition. In addition, this list includes substituents which may be characterized by more than one of these classes, such as benzyl. This list also includes hydrogen, and thus, the concept of substituted indenyl and substituted fluorenyl includes partially saturated indenyl and fluorenyl groups including, but not limited to, tetrahydroindenyl, tetrahydrofluorenyl, and octahydrofluorenyl groups.

Examples of each of these substituents include, but are not limited to, the following groups. In each of the examples presented below, unless otherwise specified, 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-, alkoxy-, or amide-substituted analog or derivative thereof; any of them having from 1 to about 20 carbon atoms; or hydrogen. Also included in these groups are any unsubstituted, branched or straight chain analogs thereof.

Examples of aliphatic groups include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, alkadienyl, cyclic groups, and the like, and include all substituted, unsubstituted, branched, and straight chain analogs or derivatives thereof, having from 1 to about 20 carbon atoms in each case. Thus, aliphatic groups include, but are not limited to, hydrocarbyl groups such as paraffins and alkenyl groups. For example, as used herein, aliphatic groups include methyl, ethyl, propyl, n-butyl, t-butyl, sec-butyl, isobutyl, pentyl, isopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, and the like.

Examples of aromatic groups include, but are not limited to, phenyl, naphthyl, anthracenyl, and the like, including substituted derivatives thereof, in each case having from 6 to about 25 carbon atoms. Substituted derivatives of aromatic compounds include, but are not limited to, tolyl, xylyl, mesityl (mesityl), and the like, including any heteroatom-substituted derivatives thereof.

Examples of cyclic groups include, but are not limited to, cycloalkanes, cycloalkenes, cycloalkynes, arenes, such as phenyl, bicyclic groups, and the like, including substituted derivatives thereof, in each case having from about 3 to about 20 carbon atoms. Thus, heteroatom-substituted cyclic groups such as furyl are also included herein.

In each case aliphaticAnd cyclic groups are groups comprising an aliphatic moiety and a cyclic moiety, examples of which include, but are not limited to, groups such as: - (CH)₂)_mC₆H_qR_5-qWherein m is an integer from 1 to about 10, and q is an integer from 1 to 5, inclusive of 1 and 10 and 1 and 5; - (CH)₂)_mC₆H_qR_11-qWherein m is an integer from 1 to about 10, and q is an integer from 1 to 11, inclusive of 1 and 10 and 1 and 11; or- (CH)₂)_mC₅H_qR_9-qWherein m is an integer from 1 to about 10, and q is an integer from 1 to 9, inclusive of 1 and 10 and 1 and 9. In each case 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 halide-, alkoxy-, or amide-substituted derivatives or analogs thereof; any of them having from 1 to about 20 carbon atoms; or hydrogen. In one aspect, aliphatic and cyclic groups include, but are not limited to: -CH₂C₆H₅；-CH₂C₆H₄F；-CH₂C₆H₄Cl；-CH₂C₆H₄Br；-CH₂C₆H₄I；-CH₂C₆H₄OMe；-CH₂C₆H₄OEt；-CH₂C₆H₄NH₂；-CH₂C₆H₄NMe₂；-CH₂C₆H₄NEt₂；-CH₂CH₂C₆H₅；-CH₂CH₂C₆H₄F；-CH₂CH₂C₆H₄Cl；-CH₂CH₂C₆H₄Br；-CH₂CH₂C₆H₄I；-CH₂CH₂C₆H₄OMe；-CH₂CH₂C₆H₄OEt；-CH₂CH₂C₆H₄NH₂；CH₂CH₂C₆H₄NMe₂；-CH₂CH₂C₆H₄NEt₂(ii) a Any positional isomer thereof (regiooisomer), and any substituted derivative thereof.

In each case, examples of halides include, but are not limited to, fluoride, chloride, bromide, and iodide.

In each case, the oxygen group is an oxygen-containing group, examples of which include, but are not limited to, alkoxy OR aryloxy groups (-OR) and the like, including substituted derivatives thereof, wherein R is an alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, OR substituted aralkyl group having from 1 to about 20 carbon atoms. Examples of alkoxy OR aryloxy (-OR) groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like.

In each case, the sulfur group is a sulfur-containing group, examples of which include, but are not limited to, -SR and the like, including substituted derivatives thereof, wherein R in each case is an alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl group having from 1 to about 20 carbon atoms.

In each case, a nitrogen group is a nitrogen-containing group, including but not limited to-NR₂Or pyridyl groups and the like, including substituted derivatives thereof, wherein R is in each case alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl having from 1 to about 20 carbon atoms.

In each case, the phosphorus group is a phosphorus-containing group including, but not limited to, -PR₂And the like, including substituted derivatives thereof, wherein R is in each case alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.

In each case, the arsenic group is an arsenic-containing group including, but not limited to, -AsR₂And the like, including substituted derivatives thereof, wherein R is in each case alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.

In each case, the carbon group is a carbon-containing group including, but not limited to, alkyl halide groups including halide-substituted alkyl groups having 1 to about 20 carbon atoms, alkenyl or haloalkenyl groups having 1 to about 20 carbon atoms, aralkyl or haloaralkyl groups having 1 to about 20 carbon atoms, and the like, including substituted derivatives thereof.

In each case, the silicon group is a silicon-containing group including, but not limited to, silyl groups, such as alkylsilyl groups, arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like, in each case having from 1 to about 20 carbon atoms. For example, silicon groups include trimethylsilyl and phenyloctylsilyl groups.

In each case, the boron group is a boron-containing group, including but not limited to-BR₂、-BX₂-BRX, wherein X is a monoanionic group, such as a halide, hydride, alkoxy, alkylthiolate (alkyl thiolate), and the like, and wherein R is in each case an alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl group having from 1 to about 20 carbon atoms.

In another aspect of the present invention, (X)³) And (X)⁴) Independently selected from the group consisting of an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, an amide group, a phosphorus group (phosphido group), an alkyl ether group (alkyloxide group), an aryl ether group (aryloxide group), an alkane sulfonate (alkanesulfonate), an arene sulfonate, or a trialkylsilyl group or substituted derivative thereof, any of which having from 1 to about 20 carbon atoms; or a halide. In yet another aspect, (X)³) And (X)⁴) Independently are:1) fluorine (F), chlorine (Cl), bromine (Br) or iodine (I); 2) hydrocarbon radicals having up to 20 carbon atoms, hydrogen, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl group or an aryl group, any of which having up to 12 carbon atoms. In yet another aspect, (X)³) And (X)⁴) Independently selected from hydrocarbyl radicals having from 1 to about 10 carbon atoms, or halides. In another aspect, (X)³) And (X)⁴) Independently selected from fluoride, chloride, bromide or iodide. In yet another aspect, (X)³) And (X)⁴) Is chloride. In yet another aspect, (X)³) And (X)⁴) Independently a hydrocarbon radical having up to 20 carbon atoms, hydrogen or BH₄。

A further aspect of the invention provides at least one ansa-metallocene of the invention comprising a compound having the formula:

wherein

Wherein M is¹Is zirconium or hafnium;

x is independently fluorine, chlorine, bromine or iodine;

e is carbon (C) or silicon (Si);

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently 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 is

R^4AAnd R^4BIndependently a hydrocarbyl group having up to 12 carbon atoms; or hydrogen;

in yet another aspect, at least one ansa-metallocene of the present invention comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is fluorine, chlorine, bromine, or iodine;

e is carbon or silicon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently hydrogen (H), methyl, allyl, benzyl, butyl, pentyl, hexyl or trimethylsilyl;

n is an integer from 1 to 6, inclusive; and is

R^4AAnd R^4BIndependently a hydrocarbyl group having up to 6 carbon atoms; or hydrogen.

In yet another aspect, at least one ansa-metallocene of the present invention comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is chlorine (Cl), bromine (Br), or iodine (I);

e is (C) carbon or silicon (Si);

R¹and R²Independently is methyl or phenyl, wherein R¹Or R²At least one of (a) is phenyl;

R^3Aand R^3BIndependently hydrogen (H) or methyl;

n is 1 or 2; and is

R^4AAnd R^4BIndependently hydrogen (H) or tert-butyl.

In yet another aspect, the at least one ansa-metallocene of the present invention may comprise a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently hydrogen, BH₄Methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH₂CMe₂Ph；CH₂SiMe₂Ph；CH₂CMe₂CH₂Ph; or CH₂SiMe₂CH₂Ph；

E is carbon or silicon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently 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 is

R^4AAnd R^4BIndependently a hydrocarbyl group having up to 12 carbon atoms; or hydrogen;

in a further aspect, the at least one ansa-metallocene of the present invention may comprise a compound having the formula:

or any combination thereof.

In yet another aspect, the at least one ansa-metallocene of the present invention may comprise, or may be selected from:

or any combination thereof. Yet another aspect of the present invention provides a metallocene compound having the formula:

wherein M is²Is Zr or Hf.

Many methods for preparing metallocene compounds that can be used in the present invention have been reported. Such processes are described, for example, in U.S. Pat. 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, 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. Other methods of preparing metallocene compounds that can be used in the present invention have been reported in the following references, such as:，A.Alt，H.G.J.Mol.CatalA.2001，165, 23; 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-; alt, h.g.; jung, m.j.organomet.chem.1998, 568, 87-112; jung, m., docoral discovery, University of Bayreuth, Germany, 1997; piefer, b., docoral discovery, University of bayer, Germany, 1995; and Zenk, r., docoral discovery, university of bayreth, Germany, 1994. The following papers 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.; chemistry of organic-Zirconium and-Hafnium Compounds; halstead Press; new York, 1986.

Organic aluminum compound

In one aspect, the present invention provides a catalyst composition comprising at least one tightly bridged ansa-metallocene compound containing an olefin-containing moiety bound to a cyclopentadienyl-type ligand and at least one aryl group bound to a bridging atom of the bridging ligand; at least one solid oxide activator-support; and optionally at least one organoaluminum compound. Thus, as disclosed herein, the designation of at least one organoaluminum compound is intended to be optional, as understood by one of ordinary skill, and the organoaluminum compound may be optional where it is not necessary to impart catalytic activity to the composition containing the contact product.

Organoaluminum compounds that may be used in the present invention include, but are not limited to, compounds having the formula:

Al(X⁵)_n(X⁶)_3-n，

wherein (X)⁵) Is a hydrocarbyl group having from 1 to about 20 carbon atoms; (X)⁶) Is alkoxy or aryloxy-any of which has 1 toAbout 20 carbon atoms, halide or hydride; and n is a number from 1 to 3, 1 and 3 being included. In one aspect, (X)⁵) Is an alkyl group having from 1 to about 10 carbon atoms. (X)⁵) Examples of moieties include, but are not limited to, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, and the like. In another aspect, (X)⁵) Examples of moieties include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, 1-hexyl, 2-hexyl, 3-hexyl, isohexyl, heptyl, octyl, and the like. In another aspect, (X)⁶) May be independently selected from fluoride, chloride, bromide, methoxy, ethoxy or hydride. In yet another aspect, (X)⁶) May be chloride.

In the formula Al (X)⁵)_n(X⁶)_3-nIn (b), n is a number of 1 to 3 including 1 and 3, and generally, n is 3. The value of n is not limited to integers and thus the formula includes sesquihalide (sesquihalide) compounds, other organoaluminum clusters, and the like.

In general, examples of organoaluminum compounds that can be used in the present invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. Examples of organoaluminum compounds useful in the present invention include, but are not limited to: trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tri-n-butylaluminum (TNBA), Triisobutylaluminum (TIBA), trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof. If a particular alkyl isomer is not specified, the compound is intended to include all isomers that can result from the specifically specified alkyl group. Thus, in another aspect, examples of organoaluminum compounds that can be used in the present 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 invention comprises precontacting an ansa-metallocene with at least one organoaluminum compound and an olefin monomer to form a precontacted mixture, and then contacting the precontacted mixture with a solid oxide activator-support to form an active catalyst. When the catalyst composition is prepared in this manner, typically, although not necessarily, a portion of the organoaluminum compound is added to the precontacted mixture, while another portion of the organoaluminum compound is added to the postcontacted mixture prepared when the precontacted mixture is contacted with the solid oxide activator. However, all organoaluminum compounds can be used to prepare the catalyst in either a pre-contact or post-contact step. Alternatively, all catalyst components may be contacted in one step.

In addition, one or more organoaluminum compounds can be used in the precontacting or postcontacting step, or in any step in which the catalyst components are contacted. When the organoaluminum compound is added in multiple steps, the amount of organoaluminum compound disclosed herein includes the total amount of organoaluminum compound used in the precontacted and postcontacted mixtures as well as any additional organoaluminum compound added to the polymerization reactor. Thus, the total amount of organoaluminum compounds is disclosed regardless of whether a single organoaluminum compound is used or whether more than one organoaluminum compound is used. In another aspect, typical organoaluminum compounds used in the present invention include, but are not limited to, triethylaluminum (tea), tri-n-butylaluminum, triisobutylaluminum, or any combination thereof.

Activating agent

In one aspect, the invention includes a catalyst composition comprising at least one 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 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.

Chemically treated solid oxide activator-support

In one aspect, the invention includes a catalyst composition comprising an acidic activator-support, which may comprise a chemically-treated solid oxide, and which is typically used in conjunction with an organoaluminum compound. In another aspect, the activator-support comprises at least one solid oxide treated with at least one electron-withdrawing anion; wherein the solid oxide can be silica, alumina, silica-alumina, aluminum phosphate, aluminophosphates, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed 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, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof.

The activator-support comprises the contact product of at least one solid oxide compound and at least one source of electron-withdrawing anions. In one aspect, the solid oxide compound comprises an inorganic oxide. The solid oxide may optionally be calcined prior to contacting the electron-withdrawing anion source. The contact product may also be calcined during or after contacting the solid oxide compound with the source of electron-withdrawing anions. In this aspect, the solid oxide compound may or may not be calcined. In another aspect, the activator-support can comprise the contact product of at least one calcined solid oxide compound and at least one source of electron-withdrawing anions.

The activator-support exhibits enhanced activity compared to the corresponding untreated solid oxide compound. The activator-support also functions as a catalyst activator compared to the corresponding untreated solid oxide. While not wishing to be bound by theory, it is believed that the activator-support functions as a solid oxide support compound, while having an additional ionization, polarization, or bond weakening function, collectively referred to as an "activation" function, by weakening the metal-ligand bond between the anionic ligand and the metal in the metallocene. Thus, the activator-support is believed to perform an "activating" function, whether or not it ionizes the metallocene, abstracts anionic ligands to form ion pairs, weakens the metal-ligand bond in the metallocene, simply coordinates with an anionic ligand when it is contacted with the activator-support, or any other mechanism by which ionization, polarization, or bond weakening can occur. In preparing the metallocene-based catalyst compositions of the present invention, when the metallocene compound does not contain an activatable ligand, the activator-support is typically used with a component that provides the metallocene with an activatable ligand such as an alkyl or hydride ligand, including but not limited to at least one organoaluminum compound.

In yet another aspect, the activator-support of the present invention comprises a solid inorganic oxide material, a mixed oxide material, or a combination of inorganic oxide materials, which is chemically treated with an electron-withdrawing component, and optionally treated with at least one other metal ion. Thus, the solid oxides of the present invention include oxide materials such as alumina, their "mixed oxide" compounds such as silica-alumina or silica-zirconia or silica-titania, as well as combinations and mixtures thereof. Mixed metal oxide compounds, such as silica-alumina, having more than one metal combined with oxygen to form a solid oxide compound can be prepared by cogelling, impregnation or chemical deposition and are encompassed by the present invention.

In yet another aspect of the 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 also include a metal or metal ion include, but are not limited to, zinc-impregnated chlorided alumina (zinc-impregnated chlorided alumina), zinc-impregnated fluorided alumina (zinc-impregnated fluorided alumina), zinc-impregnated chlorided silica-alumina (zinc-impregnated chlorided silica-alumina), zinc-impregnated fluorided silica-alumina (zinc-impregnated fluorided silica-alumina), zinc-impregnated sulfated alumina (zinc-impregnated sulfated alumina), or any combination thereof.

In another aspect, the activator-support of the present invention comprises a relatively high porosity solid oxide that exhibits lewis acidic or bronsted acidic properties. The solid oxide is chemically treated with an electron-withdrawing component, typically an electron-withdrawing anion, to form an activator-support. While not wishing to be bound by the following statement, it is believed that treating the inorganic oxide with an electron-withdrawing component increases or increases the acidity of the oxide. Thus, the activator-support exhibits a lewis or bronsted acidity that is generally greater than the lewis or bronsted acidity of the untreated solid oxide. One method of quantifying the acidity of chemically treated and untreated solid oxide materials is by comparing the polymerization activities of the treated and untreated oxides in an acid-catalyzed reaction.

In one aspect, the chemically-treated solid oxide comprises a solid inorganic oxide containing oxygen and at least one element selected from groups 2, 3,4, 5,6, 7,8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or oxygen and at least one element selected from the lanthanides or actinides. (see: Hawley's condensed Chemical Dictionary, 11)^thEd.，John Wiley &Sons; 1995; cotton, f.a.; wilkinson, g.; murillo; C.A.; and Bochmann; advanced Inorganic Chemistry, 6^thEd, Wiley-Interscience, 1999. ) Typically, the inorganic oxide contains oxygen and at leastAn element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn or Zr.

Suitable examples of solid oxide materials or compounds that can be used in the chemical treatment of solid oxides of the present invention include, but are not limited to, Al₂O₃、B₂O₃、BeO、Bi₂O₃、CdO、Co₃O₄、Cr₂O₃、CuO、Fe₂O₃、Ga₂O₃、La₂O₃、Mn₂O₃、MoO₃、NiO、P₂O₅、Sb₂O₅、SiO₂、SnO₂、SrO、ThO₂、TiO₂、V₂O₅、WO₃、Y₂O₃、ZnO、ZrO₂And the like, including mixed oxides thereof and combinations thereof. Examples of mixed oxides that may Be used in the activator-support of the present invention include, but are not limited to, 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 may be used in the activator-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, aluminophosphates, and the like.

In a further aspect of the invention, the solid oxide material is chemically treated by contacting it with at least one electron-withdrawing component, typically a source of electron-withdrawing anions. In addition, the solid oxide material is optionally chemically treated with at least one other metal ion, which may be the same as or different from any of the metallic elements making up the solid oxide material, and then calcined to form a metal-containing or metal-impregnated chemically treated solid oxide. Alternatively, the solid oxide material and the source of electron-withdrawing anions are contacted and calcined simultaneously. Methods of contacting the oxide with an electron-withdrawing component, typically a salt or acid of an electron-withdrawing anion include, but are not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like. Generally, after any contacting process, the contacted mixture of oxide compound, electron-withdrawing anion, and optionally metal ion is calcined.

The electron withdrawing component used to treat the oxide may be any component that increases the lewis or bronsted acidity of the solid oxide upon treatment. In one aspect, the electron-withdrawing component is generally an electron-withdrawing anion derived from a salt, acid, or other compound, such as a volatile organic compound that can serve as a source or precursor for the anion. Examples of electron-withdrawing anions include, but are not limited to, 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, and the like, including any mixtures and combinations thereof. In addition, other ionic or nonionic compounds that are sources of these electron-withdrawing anions may also be used 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 a sulfated alumina.

The terms alkanesulfonate and alkylsulfate refer to compounds having the general formula [ R ] respectively^BSO₂O]^-And [ (R)^BO)SO₂O]^-Wherein R is^BIs a straight or branched alkyl group having up to 20 carbon atoms, optionally with at least one group independently selected from F, Cl, Br, I, OH, OMc, OEt, OCF₃Ph, xylyl group,Radical, or OPh. Thus, alkanesulfonates and alkylsulfates may be referred to as substituted or unsubstituted. In one aspect of the present invention,the alkyl group of the alkanesulfonate or alkylsulfate can have up to 12 carbon atoms. In another aspect, the alkyl group of the alkanesulfonate or alkylsulfate 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, methylsulfonate, ethylsulfonate, 1-propylsulfonate, 2-propylsulfonate, 3-methylbutylsulfonate, trifluoromethylsulfonate, trichloromethylsulfonate, fluoromethylsulfonate, 1-hydroxyethylsulfonate, 2-hydroxy-2-propylsulfonate, 1-methoxy-2-propylsulfonate, and the like. In yet another aspect, examples of alkyl sulfates include, but are not limited to, methyl sulfate, ethyl sulfate, 1-propyl sulfate, 2-propyl sulfate, 3-methylbutyl sulfate, trifluoromethane sulfate, trichloromethyl sulfate, chloromethyl sulfate, 1-hydroxyethyl sulfate, 2-hydroxy-2-propyl sulfate, 1-methoxy-2-propyl sulfate, and the like.

The term arenesulfonate refers to a compound having the general formula [ Ar ]^ASO₂O]^-Anion of (2), wherein Ar^AIs an aryl radical having up to 14 carbon atoms, optionally with at least one radical independently selected from F, Cl, Br, I, Me, Et, Pr, Bu, OH, OMe, OEt, OPr, OBu, OCF₃Ph, OPh or R^CWherein R is^CIs a straight or branched alkyl group having up to 20 carbon atoms. Accordingly, arenesulfonate can be referred to as substituted or unsubstituted arenesulfonate. Since it is possible to use alkyl side chains R comprising long alkyl side chains^CSubstituted aryl group Ar^AThe term arenesulfonate is therefore intended to include 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 limited to, benzenesulfonate, naphthalenesulfonate, p-toluenesulfonate, m-toluenesulfonate, 3, 5-xylenesulfonate, trifluoromethoxybenzenesulfonate, trichloromethoxybenzenesulfonate, trifluoromethylbenzenesulfonate, fluorobenzenesulfonate, chlorobenzenesulfonateSulfonate, 1-hydroxyethylidenephenzenesulfonate, 3-fluoro-4-methoxybenzenesulfonate, and the like.

When the electron-withdrawing component comprises a salt of an electron-withdrawing anion, the counterion or cation of the salt can be any cation that will revert or decompose the salt back to the acid during calcination. Factors indicating suitability of a particular salt as an electron-withdrawing anion source include, but are not limited to: solubility of the salt in the desired solvent, 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 salts of electron-withdrawing anions include, but are not limited to, ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H⁺、[H(OEt₂)₂]⁺And the like.

Furthermore, combinations of one or more different electron-withdrawing anions in different proportions can be used to tailor the specific acidity of the activator-support to a desired level. The combination of electron withdrawing components may be contacted with the oxide material simultaneously or separately, and in any order that provides the desired acidity of the activator-support. For example, one aspect of the present invention is the use of two or more electron-withdrawing anion source compounds in two or more separate contacting steps. Thus, one example of such a process according to which the activator-support is prepared is as follows. Contacting a selected solid oxide compound or combination of oxide compounds with a first electron-withdrawing anion source compound to form a first mixture, then calcining the first mixture, then contacting the calcined first mixture with a second electron-withdrawing anion source compound to form a second mixture, and then calcining the second mixture to form a treated solid oxide compound. In such a process, the first and second electron-withdrawing anion source compounds are generally different compounds, although they may be the same compound.

In one aspect of the invention, the solid oxide activator-support is produced by a process comprising:

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 a solid oxide activator-support.

In another aspect of the invention, the solid oxide activator-support is produced by a process comprising:

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

4) calcining the second mixture to form a solid oxide activator-support. Thus, the solid oxide activator-support is sometimes referred to simply as a treated solid oxide compound.

Another aspect of the present invention is to produce or form a solid oxide activator-support by contacting at least one solid oxide with at least one electron-withdrawing anion source compound, wherein the at least one solid oxide compound is calcined before, during, or after contacting with the electron-withdrawing anion source, and wherein alumoxane and organo borates are substantially absent.

In one aspect of the invention, once the solid oxide has been treated and dried, it may be subsequently calcined. Calcination of the treated solid oxide is generally carried out at a temperature of about 200 ° to about 900 ℃ under ambient or inert atmosphere, typically a dry ambient atmosphere, and for a time of about 1 minute to about 100 hours. In another aspect, the calcination is carried out at a temperature of from about 300 ℃ to about 800 ℃, and in another aspect, the calcination is carried out at a temperature of from about 400 ℃ to about 700 ℃. In yet another aspect, the calcining is carried out for about 1 hour to about 50 hours, and in another aspect, the calcining is carried out for about 3 hours to about 20 hours. In yet another aspect, the calcining is carried out at a temperature of from about 350 ℃ to about 550 ℃ for from about 1 hour to about 10 hours.

Furthermore, any type of suitable ambient atmosphere may be used during calcination. Generally, the calcination is carried out in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, may be used.

In another aspect of the invention, the solid oxide component used to prepare the chemically-treated solid oxide has a pore volume of about 0.1cc/g or greater. In another aspect, the solid oxide component has a pore volume of about 0.5cc/g or greater, and in yet another aspect, about 1.0cc/g or greater. In yet another aspect, the solid oxide component has from about 100 to about 1000m²Surface area in g. In another aspect, the solid oxide component has from about 200 to about 800m²Surface area per gram, and in another aspect, from about 250 to about 600m²/g。

The solid oxide material can be treated with a source of halide ions or sulfate ions, or a combination of anions, and optionally at least one metal ion, and 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, referred to as a sulfating agent (sulfating agent), a source of chloride ions, referred to as a chlorinating agent (chlorinating agent), a source of fluoride ions, referred to as a fluorinating agent (fluorinating agent), or a combination thereof, and calcined to provide a solid oxide activator. In another aspect, useful acidic activator-supports include, but are not limited to: aluminum oxide bromide; chloridized alumina; fluorided alumina; sulfated alumina; brominated silica-alumina; chlorinated silica-alumina; fluorided silica-alumina; sulfated silica-alumina; brominated silica-zirconia; chlorinated silica-zirconia; fluorided silica-zirconia; sulfated silica-zirconia; zinc chloride-alumina, triflate-treated silica-alumina, pillared clays such as pillared montmorillonite, optionally treated with fluoride, chloride or sulfate; phosphated alumina or other aluminophosphates, optionally treated with sulfate, fluoride or chloride; or any combination thereof. In addition, any activator-support can optionally be treated with at least one other metal ion, typically derived from a metal salt or compound, wherein the metal ion can be the same as or different from any metal making up the solid oxide material.

In one aspect of the invention, the treated oxide activator-support comprises a fluorinated solid oxide in the form of a particulate solid, whereby a fluoride ion source is added to the oxide by treatment with a fluorinating agent. In yet another aspect, fluoride ions can be added to the oxide by forming a slurry of the oxide in a suitable solvent, such as an alcohol or water, including but not limited to alcohols of 1 to 3 carbon atoms, because of their volatility and low surface tension. Examples of fluorinating agents that can be used in the present invention include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH)₄F) Ammonium hydrogen fluoride (NH)₄HF₂) Ammonium boron fluoride (NH)₄BF₄) Ammonium silicofluoride (hexafluorosilicate) (NH)₄)₂SiF₆) Ammonium hexafluorophosphate (NH)₄PF₆) Tetrafluoroboric acid (HBF)₄) Ammonium hexafluorotitanate (NH) ((NH)₄)₂TiF₆) Ammonium hexafluorozirconate (NH)₄)₂ZrF₆) Their analogs and combinations thereof. For example, ammonium bifluoride NH₄HF₂Can be used as a fluorinating agent because of its ease of use and ready availability.

In another aspect of the invention, the solid oxide can be treated with a fluorinating agent during the calcination step. Any fluorinating agent that is capable of sufficiently contacting the solid oxide during the calcination step can be used. For example, volatile organic fluorinating agents can be used in addition to those described previously. Examples of volatile organic fluorinating agents useful in the present aspect of the invention include, but are not limited to, freon, perfluorohexane (perfluorohexane), perfluorobenzene (perfluorobenzene), fluoromethane, trifluoroethanol, and combinations thereof. Gaseous hydrogen fluoride or fluorine itself may also be used together with the fluorination of the solid oxide during calcination. One convenient method of contacting the solid oxide with the fluorinating agent is to evaporate the fluorinating agent into the gas stream used to fluidize the solid oxide during calcination.

Also, in another aspect of the invention, the chemically-treated solid oxide comprises a chlorinated solid oxide in the form of solid particles, whereby a source of chloride ions is added to the oxide by treatment with a chlorinating agent. Chloride ions may be added to the oxide by forming a slurry of the oxide in a suitable solvent. In another aspect of the invention, the solid oxide may be treated with a chlorinating agent during the calcination step. Any chlorinating agent that can serve as a source of chloride and can adequately contact the oxide during the calcination step can be used. For example, volatile organic chlorinating agents may be used. Examples of volatile organic chlorinating agents useful in the present aspect of the invention include, but are not limited to, certain freons (freons), perchloro benzene, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, trichloroethanol, or any combination thereof. Gaseous hydrogen chloride or chlorine itself may also be used with the solid oxide during calcination. One convenient method of contacting the oxide with the chlorinating agent is to evaporate the chlorinating agent into the 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 generally be added to the solid oxide in an amount of about 1% or more by weight of the solid oxide. In another aspect, the electron-withdrawing anion can be added to the solid oxide in an amount of 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.

In one aspect, the amount of electron-withdrawing anion, e.g., fluoride or chloride, present prior to calcining the solid oxide is generally from about 2 to about 50% by weight, wherein weight percent is based on the weight of the solid oxide, e.g., silica-alumina, prior to calcining. In another aspect, the electron-withdrawing anion, e.g., fluoride or chloride, is present in an amount of from about 3 to about 25% by weight, and in another aspect, from about 4 to about 20% by weight, prior to calcining the solid oxide. When halide ions are used as the electron-withdrawing anion, they are used in an amount sufficient to deposit about 0.1% to about 50% by weight halide ions after calcination, relative to the weight of the solid oxide. In another aspect, the halide is used in an amount sufficient to deposit about 0.5% to about 40% by weight halide ion after calcination, relative to the weight of the solid oxide, or about 1% to about 30% by weight halide ion, relative to the weight of the solid oxide. If fluoride or chloride ions are added during calcination, e.g. as in CCl₄When calcined in the presence, there is generally no or only trace levels of fluoride or chloride ions in the solid oxide prior to calcination. Once impregnated with halide, the halogenated oxide may be dried by any method known in the art, including but not limited to evaporation after suction filtration (suspension filtration), drying under vacuum, spray drying, and the like, although it is also possible to start the calcination step immediately without drying the impregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina may have a pore volume above about 0.5 cc/g. In one aspect, the pore volume can be above about 0.8cc/g, while in another aspect, the pore volume can be above about 1.0cc/gThe above. Further, the silica-alumina may have about 100m²A surface area of greater than g. In one aspect, the surface area is about 250m²Above,/g, and in another aspect, the surface area may be about 350m²More than g. Generally, the silica-alumina of the present invention has an alumina content of from about 5 to about 95%. In one aspect, the alumina content of the silica-alumina can be from about 5 to about 50%, while in another aspect, the alumina content of the silica-alumina can be from about 8% to about 30% by weight.

Sulfated solid oxides include sulfates and solid oxide components such as alumina or silica-alumina, in the form of particulate solids. Optionally, the sulfated oxide is further treated with metal ions such that the calcined sulfated oxide contains metal. In one aspect, the sulfated solid oxide comprises sulfate and alumina. In one aspect of the invention, the sulfated alumina is formed by a process in which 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, the process may be carried out by forming a slurry of alumina in a suitable solvent, such as alcohol or water, in which a sulfating agent (sulfating agent) has been added at a desired concentration. Suitable organic solvents include, but are not limited to, alcohols of 1 to 3 carbons due to their volatility and low surface tension.

In this regard, the amount of sulfate ions present prior to calcination is generally from about 1% to about 50% by weight, from about 2% to about 30% by weight, from about 5% to about 25% by weight, wherein the weight percentages are based on the weight of the solid oxide prior to calcination. Once impregnated with sulfate, the sulfated oxide may be dried by any method known in the art, including but not limited to evaporation after suction filtration (suction filtration), drying under vacuum, spray drying, and the like, although it is also possible to begin the calcination step immediately.

In addition to treatment with electron-withdrawing components such as halide or sulfate ions, the solid inorganic oxides of the present invention can optionally be treated with a metal source, including metal salts or metal-containing compounds. In one aspect of the invention, these compounds may be added or impregnated onto the solid oxide in solution form and subsequently converted to a support metal upon calcination. Thus, the solid inorganic oxide may further comprise a metal 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 a metal salt or a metal-containing compound before, after, or simultaneously with the treatment of the solid oxide with the electron-withdrawing anion.

Further, any method of impregnating a solid oxide substance with a metal may be used. The oxide is contacted with a metal source, typically a salt or metal-containing compound, by this method, which includes, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like. After any contacting process, the contacted mixture of oxide compound, electron-withdrawing anion, and metal ion is typically calcined. Optionally, the solid oxide material, the 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 the olefin monomer and the organoaluminum cocatalyst for a first period of time, and then the mixture is contacted with the acidic activator-support. Once the precontacted mixture of metallocene, monomer, and component providing the metallocene activatable ligand, including but not limited to the organoaluminum cocatalyst, is contacted with the acidic activator-support, the composition further comprising the acidic activator-support is referred to as a "postcontacted" mixture. The post-contacted mixture may be maintained in further contact for a second period of time prior to being fed to the reactor in which the polymerization process is to be conducted.

Various methods of preparing solid oxide activator-supports that can be used in the present invention have been reported. Such methods are described, for example, in U.S. Pat. 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, each of which is incorporated herein by reference in its entirety.

Ion-exchangeable activator-support and layered mineral activator-support

In one aspect of the invention, the activator-support used to prepare the catalyst composition of the invention may comprise an ion-exchangeable activator-support, including but not limited to silicates and aluminosilicate compounds or minerals, having a layered or non-layered structure, and any combination thereof. In another aspect of the invention, an ion-exchangeable layered aluminosilicate such as a pillared clay can be used as the activator-support. When the acidic activator-support comprises an ion-exchangeable activator-support, it can optionally be treated with at least one electron-withdrawing anion such as those disclosed herein, although typically, the ion-exchangeable activator-support is not treated with an electron-withdrawing anion.

In one aspect, the activator-support of the invention can include a clay mineral having exchangeable cations and expandable layers. Typical clay 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 should be considered an active part of the catalyst composition because of its close association with the ansa-metallocene and a component capable of providing an activatable ligand to the metallocene, such as an organoaluminum. While not wishing to be bound by theory, it is believed that the ion-exchangeable activator-support acts as an insoluble reactant that reacts with the ansa-metallocene and the organoaluminum component to form a catalyst composition for producing a polymer.

In one aspect, the clay material of the present invention includes materials in their natural state, or materials that have been treated with various ions by wetting, ion exchange, or pillaring (pillaring). Typically, the clay material activator-support of the present invention comprises a clay that has been ion exchanged with large cations, including polynuclear, highly charged metal complex cations. However, the clay material activator-supports of the present invention also include 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 halides, acetates, sulfates, nitrates, or nitrites.

In one aspect, the clay activator-support of the present invention comprises a pillared clay. The term pillared clay 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 may have, for example, a 7+ charge, various polyoxometallates, and other large ions. Thus, the term pillaring refers to a simple exchange reaction in which exchangeable cations of the clay species are replaced by large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the interlayer of the clay and, when calcined, are converted into metal oxide "pillars" that effectively support the clay layers as columnar structures. Thus, after the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded lattice structure is maintained and the porosity is increased. The shape and size of the pores formed may vary as a function of the pillaring material and the parent clay material used. Examples of pillared and pillared clays are found in the following documents: T.J. Pinneavaia, Science220(4595), 365-; thomas, interaction Chemistry, (s.whittington and a.jacobson editors) 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 method utilizes clay minerals with exchangeable cations and layers capable of expansion. Any pillared clay that can enhance olefin polymerization in the catalyst composition of the present invention can be used. Thus, suitable clay minerals for use in the pillaring include, but are not limited to: quartz of water aluminium; smectites, dioctahedral (a1) and trioctahedral (Mg) and their derivatives such as montmorillonite (bentonite), nontronite, hectorite or lithium magnesium silicate (laponites); halloysite; vermiculite; mica; fluorinated micas (fluoromics); chlorite; mixing layer clay; fibrous clays including, but not limited to, sepiolite, attapulgite, and palygorskite (palygorskites); serpentine clay (serpentine clay); illite; lithium magnesium silicate; talc powder; or any combination thereof. In one aspect, the pillared clay activator-support comprises bentonite or montmorillonite, noting that the major component of bentonite is montmorillonite.

The pillared clay may be pretreated in the present invention. For example, in one embodiment, the pillared bentonite is pretreated by drying at about 300 ℃ for about 3 hours under an inert atmosphere, typically dry nitrogen, prior to being fed into the polymerization reactor. This example of pretreatment is not limiting as such a preheating step can be conducted at many other temperatures and times, including combinations of temperature and time steps, all of which are included in the present invention.

The ion-exchangeable activator-support, such as the pillared clay used to prepare the catalyst composition of the present invention, may be combined with other inorganic support materials including, but not limited to, zeolites, inorganic oxides, phosphated inorganic oxides, and the like. In one aspect, typical support materials that may be used in this aspect include, but are not limited to, silica-alumina, titania, zirconia, magnesia, boria, fluorided alumina, silicated alumina, thoria, aluminophosphates, zinc aluminate, phosphated silica, phosphated alumina, silica-titania, co-precipitated silica/titania, fluorided/silicated alumina, and any combinations or mixtures thereof.

The amount of ansa-metallocene compound relative to the ion-exchangeable activator-support used to prepare the catalyst composition of the present invention is based on the weight of the activator-support component (rather than on the final metallocene-clay mixture), and generally is from about 0.1 wt% to about 15 wt% of the ansa-metallocene complex. It has also been found that about 1 wt% to about 10 wt% ansa-metallocene works well to provide a catalyst that operates at the desired activity.

The mixture of ansa-metallocene and clay activator-support may be contacted and mixed for any length of time to provide sufficient contact between the ansa-metallocene and the activator-support. Sufficient deposition of the metallocene component on the clay can be achieved without heating the mixture of clay and metallocene complex. For example, the ansa-metallocene and the clay material are simply mixed from about room temperature to about 200 ° f to effect deposition of the ansa-metallocene on the clay activator-support. In another aspect, the ansa-metallocene and the clay material are mixed from about 100 ° f to about 180 ° f to effect deposition of the ansa-metallocene on the clay activator-support.

In another aspect, the invention includes a catalyst composition comprising an acidic activator-support, which may include a layered mineral. The term "layered mineral" is used herein to describe materials such as clay minerals, pillared clays, ion exchanged clays, delaminated 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 anion such as those disclosed herein, although typically, the layered mineral is not treated with an electron-withdrawing anion. For example, at least one clay mineral may be used as an activator-support.

Clay minerals generally comprise a large group of fine crystalline, plate-like layered minerals which are found in nature in fine-grained precipitates, sedimentary rocks, etc., and which constitute a class of hydrated silicate and aluminosilicate minerals having a plate-like structure and very high surface area. The term is also used to describe hydrous magnesium silicate having a phyllosilicate (phyllosilicate) structure. Examples of clay minerals that may be used in the present invention include, but are not limited to: quartz of water aluminium; smectites, dioctahedral (a1) and trioctahedral (Mg) and their derivatives such as montmorillonite (bentonite), nontronite, hectorite or lithium magnesium silicate; halloysite; vermiculite; mica; fluorinated mica; chlorite; mixing layer clay; fibrous clays including, but not limited to, sepiolite, attapulgite, and palygorskite; serpentine clay; illite; lithium magnesium silicate; talc powder; or any combination thereof. Many common clay minerals belong to the kaolinite, montmorillonite or illite group of clays. Pillared clays can also be used as the activator-support of the present invention, as disclosed herein. Pillared clays include clay minerals typically belonging to the smectite group and other layered silicates besides sepiolite and palygorskite that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations.

In one aspect of the invention, when layered minerals are used as activator-supports or metallocene activators, the layered minerals are typically calcined before they are used as activators. Typical calcination temperatures may range from about 100 ℃ to about 700 ℃, from about 150 ℃ to about 500 ℃, or from about 200 ℃ to about 400 ℃.

Non-limiting examples of catalyst compositions

Examples of the catalyst composition of the present 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:

a) the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently fluorine (F), chlorine (Cl), bromine (Br), or iodine (I);

e is carbon (C) or silicon (Si);

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently 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; and is

R^4AAnd R^4BIndependently 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 (diethyl aluminum ethoxide), diisobutylaluminum hydride (diisobutylaluminum hydride), diethylaluminum chloride (diethyl aluminum chloride), or any combination thereof; and

c) at least one activator support comprises a solid oxide treated with an electron-withdrawing anion, wherein:

the solid oxide is silica, alumina, silica-alumina, aluminophosphates, 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, or the like, substituted or unsubstituted alkylsulfate, or any combination thereof.

Also in this aspect, the at least one ansa-metallocene may also comprise or may be selected from compounds having the formula:

wherein

M¹Is zirconium or hafnium;

x is fluorine, chlorine, bromine, or iodine;

e is carbon or silicon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently hydrogen, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl;

n is an integer from 1 to 6, including 1 and 6; and is

R^4AAnd R^4BIndependently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen.

Also in this aspect, the at least one ansa-metallocene may also comprise a compound having the formula, or may be selected from compounds having the formula:

wherein

M¹Is zirconium or hafnium;

x is chlorine, bromine, or iodine;

e is carbon or silicon;

R¹and R²Independently is methyl or phenyl, wherein R¹Or R²At least one of (a) is phenyl;

R^3Aand R^3BIndependently is hydrogen or methyl;

n is 1 or 2; and is

R^4AAnd R^4BIndependently hydrogen or tert-butyl.

Also in this aspect, the at least one ansa-metallocene may also include or may be selected from:

or any combination thereof.

In another aspect or non-limiting example, the catalyst composition can comprise at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-support, or the catalyst combination can comprise 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:

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.

In yet another aspect or non-limiting example, the catalyst composition can comprise at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-support, or the catalyst combination can comprise 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:

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 sulfated alumina.

In yet another aspect or non-limiting example, the catalyst composition can comprise at least one pre-contacted ansa-metallocene, at least one pre-contacted organoaluminum compound, at least one pre-contacted olefin, and at least one post-contacted activator-support, or the catalyst combination can comprise the contact product of at least one pre-contacted ansa-metallocene, at least one pre-contacted organoaluminum compound, at least one pre-contacted olefin, and at least one post-contacted activator-support, wherein each of the ansa-metallocene, organoaluminum compound, olefin, and activator-support is as disclosed herein.

Another aspect of the invention provides a catalyst composition comprising the contact product of: at least one tightly bridged ansa-metallocene compound comprising a side chain olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bound to the bridging atom of the bridging ligand; and at least one agent capable of acting to convert the metallocene to an active catalyst that is different from the combination of the solid oxide activator-support and the organoaluminum compound disclosed herein. Thus, in one aspect, an active catalyst composition may be formed, typically upon activation of the metallocene, which may include converting the metallocene compound to its cationic form, and by providing a hydrocarbyl ligand thereto before, after or during its conversion to a cation capable of initiating olefin polymerization. The at least one agent capable of converting the metallocene into an active catalyst generally comprises: where the metallocene compound does not already include an activatable ligand, such as an alkyl group, the metallocene is provided with a component of such a ligand, as well as an activator component, as provided herein. In some cases, both functions may be accomplished with one component, such as an organoaluminoxane. In other cases, both functions may be provided by two separate components, e.g., 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 alkylating agent of the ansa-metallocene compound can be at least one organoaluminoxane, such as methylaluminoxane or isobutylaluminoxane. In another aspect, for example, the activator may be a lewis acidic organoboron compound capable of abstracting an anionic ligand from the metallocene, such as tris (pentafluorophenyl) boron (tris (pentafluorophenyl) boron) or triphenylcarbenium tetrakis (pentafluorophenyl) borate, which is typically used in combination with an alkylating agent, such as an organoaluminum compound. In yet another aspect, dialkylated tightly-bridged ansa-metallocene compounds 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 metallocene cation. Yet another aspect provides dialkylated tightly-bridged ansa-metallocene compounds capable of reacting 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 cation, and that a number of reaction steps may be used to produce such a catalyst.

Yet a further aspect of the invention provides a catalyst composition comprising the contact product of at least one tightly bridged ansa-metallocene comprising at least one hydrocarbyl ligand capable of initiating 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 side chain olefin-containing moiety linked to at least one cyclopentadienyl-type ligand, one or two aryl groups bound to a bridging atom of a bridging ligand, and at least one hydrocarbyl ligand capable of initiating olefin polymerization. No organoaluminum compound would be required to alkylate this type of "prealkylated" ansa-metallocene, since it already contains a hydrocarbyl ligand capable of initiating olefin polymerization.

Organic aluminoxane activators

In one aspect, the present invention provides a catalyst composition comprising: at least one ansa-metallocene; optionally, at least one organoaluminum compound; and at least one activator, or the invention provides a catalyst composition comprising the contact product of: at least one ansa-metallocene; optionally, at least one organoaluminum compound; and at least one activator, wherein the activator can be independently selected from the group consisting of:

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) at least one organoaluminoxane compound;

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 treated with an electron-withdrawing anion; and optionally, an aluminoxane cocatalyst. In another aspect, the invention provides a catalyst composition comprising an ansa-metallocene-containing moiety having pendant unsaturation, an aluminoxane cocatalyst, optionally an activator-support, and optionally an organoaluminum compound. However, in one aspect, the catalyst composition of the present invention is substantially free of aluminoxane and, in another aspect, the catalyst composition of the present invention has polymerization activity in the substantial absence of aluminoxane.

In another aspect, the present invention provides a catalyst composition comprising at least one ansa-metallocene and an aluminoxane. In this aspect, the catalyst composition need not comprise any activator-support, wherein the activator-support comprises a chemically-treated solid oxide, and the catalyst composition need not comprise an organoaluminum compound. Thus, any of the ansa-metallocene compounds disclosed herein can be combined with any of the aluminoxanes (poly (hydrocarbylaluminum oxides)) disclosed herein or any combination of aluminoxanes disclosed herein to form the catalyst composition of the present invention. Further, any of the ansa-metallocene compounds 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 the catalyst composition of the present invention.

Aluminoxanes are also known as poly (hydrocarbylaluminum oxides) or organoaluminoxanes. Generally, the other catalyst components are contacted with the aluminoxane in a saturated hydrocarbon solvent, although 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 methods known to those of ordinary skill in the art including, but not limited to, filtration, or the catalyst composition can be introduced into the polymerization reactor without separation.

In one aspect, the aluminoxane compounds of the present invention are oligomeric aluminum compounds, wherein the aluminoxane compounds can comprise linear, cyclic, or cage structures, or, in general, mixtures of all three structures. Cyclic aluminoxane compounds having the formula are encompassed by the present invention:

wherein

R is a straight or branched chain alkyl group having 1 to 10 carbon atoms and n is an integer of 3 to about 10. Shown here (AlRO)_nMoieties also constitute repeating units in linear aluminoxanes. Thus, linear aluminoxanes having the formula:

wherein

R is a straight or branched chain alkyl group having 1 to 10 carbon atoms and n is an integer of 1 to about 50.

Furthermore, the aluminoxane may also have the formula R^t _5m+αR^b _m-αAl_4mO_3mWherein m is 3 or 4, and α ═ n_Al(3)-n_o(2)+n_o(4)(ii) a Wherein n is_Al(3)Is the number of three-coordinate aluminum atoms, n_o(2)Is the number of bidentate oxygen atoms, n_o(4)Is the number of 4 coordinating oxygen atoms, R^tRepresents a terminal alkyl group, R^bRepresents a bridging alkyl group; wherein R is a linear or branched alkyl group having 1 to 10 carbon atoms.

Thus, aluminoxanes may generally be represented by the formula such as (R-Al-O)_n、R(R-Al-O)_nAlR₂Etc., wherein the R group is generally straight or branched C₁-C₆Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl or hexyl, wherein n generally represents an integer from 1 to about 50. In one embodiment, the aluminoxane compounds of the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or combinations thereof.

Although organoaluminoxanes having different types of R groups are encompassed by the present invention, Methylaluminoxane (MAO), ethylaluminoxane or isobutylaluminoxane are typical optional co-catalysts for use in the catalyst compositions of the present invention. It is also within the scope of this invention to use aluminoxanes together with trialkylaluminums, such as disclosed in U.S. Pat. No. 4,794,096, which is incorporated herein by reference in its entirety.

The present invention contemplates aluminoxanes having the formula (R-Al-O)_nAnd R (R-Al-O)_nAlR₂And preferably n is at least about 3. However, depending on how the organoaluminoxane is prepared, stored, and used, the value of n can be variable in a single sample of aluminoxane, and such combinations of organoaluminoxanes are included in the methods and compositions of the present invention.

In preparing the catalyst compositions of the present invention, including the optional aluminoxane, the molar ratio of the aluminum in the aluminoxane to the metallocene in the composition is typically from about 1:10 to about 100,000: 1. In another aspect, the molar ratio of aluminum in the aluminoxane to metallocene in the composition is typically from about 5:1 to about 15,000: 1. The amount of optional aluminoxane added to the polymerization reaction zone is an amount in the range of from about 0.01mg/L to about 1000mg/L, from about 0.1mg/L to about 100mg/L, or from about 1mg/L to about 50 mg/L.

The organoaluminoxane can be prepared by various methods well known in the art. Examples of organoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099 and 4,808,561, each of which is incorporated herein by reference in its entirety. An example of how alumoxanes can be prepared is as follows. Water dissolved in an inert organic solvent may be reacted with an alkyl aluminum compound such as AlR₃To form the desired organoaluminoxane compound. While not wishing to be bound by this statement, it is believed that this synthetic method can provide both linear and cyclic (R-Al-O)_nMixtures of aluminoxane species, both of which are encompassed by the present invention. Alternatively, by reacting an alkylaluminum compound such as AlR₃Organoaluminoxanes can be prepared by reaction 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 composition comprising: at least one ansa-metallocene; optionally, at least one organoaluminum compound; and at least one activator, or the invention provides 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 may be independently selected from: at least one activator-support as provided herein; at least one organoaluminoxane compound; at least one organoboron or organoborate compound; or any combination thereof. Thus, in one aspect of the invention, the at least one activator may be selected from at least one organoboron compound, at least one organoborate compound, or combinations 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 organoborate promoter. In another aspect, the present invention provides a catalyst composition comprising the contact product of: at least one ansa-metallocene compound containing pendant unsaturation; an organoboron or organoborate cocatalyst; an organoaluminum compound; and optionally an activator-support. In this aspect, the catalyst composition need not comprise an activator-support. Any of the ansa-metallocene compounds disclosed herein can be combined with any of the organoboron or organoborate cocatalysts disclosed herein, or any combination of the organoboron or organoborate cocatalysts disclosed herein, along with a component that provides a metallocene activatable ligand, such as an alkyl or hydride ligand, for example an organoaluminum compound, when the metallocene compound does not contain such a ligand, to form a catalyst composition. Further, any of the ansa-metallocene compounds disclosed herein can be combined with: any organoboron or organoborate cocatalyst; an organoaluminum compound; optionally, at least one aluminoxane; and optionally, an activator-support to form the catalyst composition of the invention. However, in one aspect the catalyst composition of the invention is substantially free of organoboron or organoborate compounds, and in another aspect the catalyst composition of the invention is polymerizable 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, borates, or combinations thereof. For example, the organoboron compound of the present invention can include a fluoroorganoboron compound, a fluoroorganoborate compound, or a combination thereof. Any fluoroorganoboron or fluoroorganoborate compound known in the art may be used. The term fluoroorganoboron compound has its usual meaning and refers to a neutral compound of the form BY 3. The term fluoroorganoborate compound also has its ordinary meaning and refers to a compound of the form [ cationic ]]⁺[BY₄]^-Wherein Y represents a fluorinated organic group. For convenience, the fluoroorganoboron and fluoroorganoborate compounds are generally referred to collectively as organoboron compounds or by either name as the context requires.

Examples of fluoroorgano borate compounds that may be used as cocatalysts in the present invention include, but are not limited to, fluorinated aryl borates such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, and the like, including mixtures thereof. Examples of fluoroorganoboron compounds that may be used as cocatalysts in the present invention include, but are not limited to, tris (pentafluorophenyl) boron (tris (trifluoromethyl) boron), tris [3, 5-bis (trifluoromethyl) phenyl ] boron (tris [3, 5-bis (trifluoromethyl) phenyl ] boron), and the like, including mixtures thereof.

While not wishing to be bound by the following theory, these examples of fluoroorganoborate and fluoroorganoboron compounds and related compounds are believed to form "weakly-coordinating" anions when combined with organometallic compounds, as disclosed in U.S. Pat. No. 5,919,983.

In general, any number of organoboron compounds can be used in the present invention. In one aspect, the molar ratio of organoboron compound to metallocene compound in the composition is about 0.1:1 to about 10: 1. Generally, the amount of fluoroorganoboron or fluoroorganoborate compound used as the cocatalyst for the metallocene is in the range of about 0.5 mole to about 10 moles of boron compound per mole of metallocene compound. In one aspect, the amount of fluoroorganoboron or fluoroorganoborate compound used as the cocatalyst for the metallocene is in the range of about 0.8 mole to about 5 moles of boron compound per mole of metallocene compound.

Optionally an ionizing ionic compound promoter

In one aspect, the present invention provides a catalyst composition comprising: 1) at least one tightly bridged ansa-metallocene compound comprising an olefin-containing moiety bound to a cyclopentadienyl-type ligand and at least one aryl group bound to a bridging atom of the bridging ligand; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, as disclosed herein, or the present invention provides a catalyst composition comprising the contact product of: 1) at least one tightly bridged ansa-metallocene compound comprising an olefin-containing moiety bound to a cyclopentadienyl-type ligand and at least one aryl group bound to a 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 invention provides a catalyst composition as disclosed herein, comprising, in addition to these other components, an optional ionizing ionic compound promoter. However, in one aspect, the catalyst composition of the present invention is substantially free of ionizing ionic compounds, while in another aspect, the catalyst composition of the present invention has polymerization activity in the substantial absence of ionizing ionic compounds. In yet another aspect, the present invention provides a catalyst composition comprising at least one ansa-metallocene compound as disclosed 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 compounds are disclosed in U.S. patent nos. 5,576,259 and 5,807,938.

Ionizing ionic compounds are ionic compounds that may function to enhance the activity of the catalyst composition. While not being bound by theory, it is believed that the ionizing ionic compound is capable of reacting with the metallocene compound and converting the metallocene to a cationic metallocene compound. Also, while not wishing to be bound by theory, it is believed that the ionizing ionic compound may function as an ionizing compound by extracting, in whole or in part, anionic ligands, which may be non- η, from the metallocene⁵Alkadienyl ligands, e.g. X³) Or (X)⁴). However, ionizing ionic compounds are activators, whether or not they: ionizing the metallocene; by abstraction in such a way that ion pairs are formed (X)³) Or (X)⁴) A ligand; weakening of the Metal- (X) in metallocenes³) Or metal- (X)⁴) A key; simply with (X)³) Or (X)⁴) Coordinating a ligand; or any other mechanism or combination of mechanisms by which activation occurs. Furthermore, the ionizing ionic compound need not only activate the metallocene. The activating function of the ionizing ionic compound is generally evident in enhancing the activity of the catalyst composition as compared to a catalyst composition containing a catalyst composition that does not include any ionizing ionic compound.

Examples of ionizing ionic compounds include, but are not limited to, the following: tri (n-butyl) ammonium tetra (p-tolyl) borate, tri (n-butyl) ammonium tetra (m-tolyl) borate, tri (n-butyl) ammonium tetra (2, 4-dimethylphenyl) borate, tri (n-butyl) ammonium tetra (3, 5-dimethylphenyl) borate, tri (n-butyl) ammonium tetra [3, 5-bis (trifluoromethyl) phenyl ] borate]Borate, tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (p-tolyl)) Borate, N-dimethylanilinium tetrakis (m-tolyl) borate, N-dimethylanilinium tetrakis (2, 4-dimethylphenyl) borate, N-dimethylanilinium tetrakis (3, 5-dimethylphenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate]Borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (p-tolyl) borate, triphenylcarbonium tetrakis (m-tolyl) borate, triphenylcarbonium tetrakis (2, 4-dimethylphenyl) borate, triphenylcarbonium tetrakis (3, 5-dimethylphenyl) borate, triphenylcarbonium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, and mixtures thereof]Borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, a process for producing a polycarbonate,Onium tetrakis (p-tolyl) borate,Onium tetrakis (m-tolyl) borate,Onium tetrakis (2, 4-dimethylphenyl) borate,Onium tetrakis (3, 5-dimethylphenyl) borate,Onium tetrakis [3, 5-bis (trifluoromethyl) phenyl]A borate salt,Onium 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) boratePotassium, potassium tetrakis (2, 4-dimethylphenyl) borate, potassium tetrakis (3, 5-dimethylphenyl) borate, potassium tetrafluoroborate, triphenylcarbonium tetrakis (p-tolyl) aluminate, triphenylcarbonium tetrakis (m-tolyl) aluminate, triphenylcarbonium tetrakis (2, 4-dimethylphenyl) aluminate, triphenylcarbonium tetrakis (3, 5-dimethylphenyl) aluminate, triphenylcarbonium tetrakis (pentafluorophenyl) aluminate, potassium tetrakis (3, 4-dimethylphenyl) borate, potassium tetrafluoroborate, potassium triphenylcarbonium tetrakis (p-tolyl) aluminate, potassium triphenylcarbonium tetrakis (m-tolyl) aluminate, potassium triphenylcarbonium tetrakis (2, 4-,Onium tetrakis (p-tolyl) aluminate,Onium tetrakis (m-tolyl) aluminate,Onium tetrakis (2, 4-dimethylphenyl) aluminate,Onium tetrakis (3, 5-dimethylphenyl) aluminate,Onium 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 tetrakis (p-tolyl) aluminate, potassium tetrakis (m-tolyl) aluminate, potassium tetrakis (2, 4-dimethylphenyl) aluminate, potassium tetrakis (3, 5-dimethylphenyl) aluminate, potassium tetrakis (p-tolyl) aluminate, lithium tetrakis (2, 4-dimethylphenyl) aluminate, lithium tetrakis (, Potassium tetrafluoroaluminate, triphenylcarbenium tris (2, 2', 2 "-nonafluorobiphenyl) fluoroaluminate, silver tetrakis (1, 1,1, 3, 3, 3-hexafluoroisopropanolate) aluminate (silver tetrakis (1, 1,1, 3, 3, 3-hexafluoroisopropanol) or silver tetrakis (perfluoro-t-butoxy) aluminate (silver tetrakis (per fluoro-t-butoxy) aluminate), or any combination thereof. However,these ionizing ionic compounds are exemplary, and the ionizing ionic compounds are not limited to these in the present invention.

Olefin monomer

In one aspect, unsaturated reactants useful in polymerization processes utilizing the catalyst composition and in the processes of the present invention include olefinic compounds having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond. The present invention includes homopolymerization processes using a single olefin, such as ethylene or propylene, as well as copolymerization processes with at least one different olefin compound. In one aspect of the copolymerization of ethylene, the copolymer of ethylene comprises a major amount of ethylene (>50 mole percent) and a minor amount of comonomer (<50 mole percent), although this is not a requirement. Comonomers that can copolymerize with ethylene should have 3 to about 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), intermediate, linear, branched, substituted, unsubstituted, functionalized, and unfunctionalized olefins may be used in the present invention. For example, typical unsaturated compounds that can be polymerized with the catalyst of the present invention include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, four n-octenes, four n-nonenes, five n-decenes, and mixtures of any two or more thereof. Cyclic and bicyclic olefins include, but are not limited to, cyclopentene, cyclohexene, norbornene, norbornadiene, and the like, which can also be polymerized, as described above.

In one aspect, when a copolymer is desired, the monomer ethylene can be copolymerized with the comonomer. In another aspect, examples of comonomers include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, four n-octenes, four n-nonenes, or five n-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 the reactor zone to produce the copolymer is generally from about 0.001 to about 99 weight percent comonomer based on the total weight of monomer and comonomer. In one aspect, the amount of comonomer introduced into the reactor zone to produce the copolymer is generally from about 0.01 to about 50 weight percent comonomer based on the total weight of monomer and comonomer. In another aspect, the amount of comonomer introduced into the reactor zone is from about 0.01 to about 10 weight percent comonomer, and in yet another aspect, from about 0.1 to about 5 weight percent comonomer, based on the total weight of monomer and comonomer. Alternatively, an amount sufficient to produce the above-mentioned weight concentrations in the resulting copolymer may be used.

While not wishing to be bound by this theory, in the case where branched, substituted, or functionalized olefins are used as reactants, it is believed that steric hindrance may prevent and/or slow the polymerization process. Thus, it is expected that the branched and/or cyclic portion(s) of the olefin some distance from the carbon-carbon double bond will not hinder the reaction in such a way that the same olefinic substituent located closer to the carbon-carbon double bond may hinder the reaction. In one aspect, at least one reactant of the catalyst composition of the present invention is ethylene, and thus the polymerization is a homopolymerization or a copolymerization with a different acyclic, cyclic, terminal, intermediate, linear, branched, substituted, or unsubstituted olefin. In addition, the catalyst composition of the present invention may be used in the polymerization of diolefins including, but not limited to, 1, 3-butadiene, isoprene, 1, 4-pentadiene and 1, 5-hexadiene.

Preparation of the catalyst composition

In one aspect, the invention includes catalyst compositions and methods comprising contacting at least one close-bridged ansa-metallocene compound, at least one activator, and optionally at least one organoaluminum compound, as disclosed herein. The methods disclosed herein include any series of contacting steps to contact each of the components provided, any order of contacting the components or mixture of components. Although not intended to be limiting, examples of contacting steps are generally exemplified herein using a treated solid oxide activator support and an organoaluminum cocatalyst. These exemplary steps may include any number of pre-contacting and post-contacting steps, and further include using an olefin monomer as a contacting component in any of these steps. An example of a preparation method for preparing the catalyst composition of the present invention is as follows.

In one aspect of the invention, the ansa-metallocene can be precontacted with an olefin monomer, not necessarily the olefin monomer to be polymerized, and an organoaluminum cocatalyst for a first period of time, prior to contacting the precontacted mixture with the solid oxide activator-support. For example, the first period of contact, the precontact time, between the ansa-metallocene, the olefin monomer, and the organoaluminum cocatalyst typically ranges from about 1 minute to about 24 hours, with from about 0.1 to about 1 hour being typical. Precontacting times of from about 10 minutes to about 30 minutes are also typical.

Once the precontacted mixture of the ansa-metallocene, the olefin monomer, and the organoaluminum cocatalyst is contacted with the solid oxide activator, the composition (which also includes the solid oxide activator) is referred to as a postcontacted mixture. Generally, the post-contacted mixture may be maintained in contact for a second period of time, post-contact time, prior to beginning the polymerization process. In one aspect, the post-contact time between the solid oxide activator-support and the precontacted mixture is generally in the range of about 1 minute to about 24 hours, and from about 0.1 hour to about 1 hour is typical. Post-contact times of from about 10 minutes to about 30 minutes are also typical.

In another aspect of the invention, the various catalyst components (e.g., the ansa-metallocene, the activator-support, the organoaluminum cocatalyst, and optionally the unsaturated hydrocarbon) can be contacted simultaneously in the polymerization reactor while the polymerization reaction is in progress. Alternatively, any two or more of these catalyst components may be "pre-contacted" in a vessel or tube prior to their entry into the reaction zone. The precontacting step may be a continuous process, wherein the precontacted product is continuously fed into the reactor, or it may be a step-wise or batch process, wherein one batch of precontacted product may be added to prepare the catalyst composition. The precontacting step may be performed over a time period ranging from a few seconds up to several days or more. In this aspect, the continuous precontacting step may generally last from about 1 second to about 1 hour. Also in this aspect, the continuous precontacting step may generally last from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Alternatively, the precontacting process may be carried out in multiple steps, rather than a single step, wherein multiple mixtures are prepared, each comprising a different set of catalyst components. For example, at least two catalyst components may be contacted to form a first mixture, followed by contacting the first mixture with at least one other catalyst component to form a second mixture, and so forth.

The precontacting step may be carried out a plurality of times in a single vessel or in a plurality of vessels. Furthermore, the precontacting step may be carried out several times in succession (sequentially), simultaneously or in a combination thereof. For example, a first mixture of two catalyst components may be formed in a first vessel, and a second mixture comprising the first mixture plus one additional catalyst component may be formed in the first vessel or a second vessel, which is generally placed downstream of the first vessel.

In another aspect, one or more catalyst components may be separated and used in different precontacting treatments. For example, a portion of the catalyst component may be fed into a first precontacting vessel for precontacting with at least one other catalyst component, while the remaining portion of the same catalyst component may be fed into a second precontacting vessel for precontacting with at least one other catalyst component, or may be fed directly into the reactor, or a combination thereof. The precontacting can be performed in any suitable equipment, such as tanks, stirred mixing tanks, various static mixing devices, tubes, flasks, any type of vessel, or any combination thereof.

In one aspect, for example, the catalyst composition of the invention is prepared by: the active catalyst is formed by contacting 1-hexene, triisobutylaluminum, or tri-n-butylaluminum with an ansa-metallocene for at least about 30 minutes, followed by contacting the precontacted mixture with a sulfated alumina activator-support for at least about 10 minutes up to 1 hour.

The precontacting step generally increases the productivity of the polymer as compared to the same catalyst composition prepared without the precontacting step. The enhanced activity catalyst composition of the present invention can be used for homopolymerization of alpha-olefin monomers such as ethylene or copolymerization of alpha-olefin and comonomer. However, neither the pre-contacting step nor the post-contacting step is essential to the present invention.

The post-contact mixture may be heated at a temperature and for a duration sufficient to allow the pre-contact mixture and the solid oxide activator-support to adsorb, impregnate, or interact such that a portion of the components of the pre-contact mixture are immobilized, adsorbed, or deposited thereon. For example, the mixture may be contacted after heating between about 0F and about 150F. Temperatures of about 40F to about 95F are typical if the mixture is fully heated.

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 to the organoaluminum 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 molar ratio of the total amount of the ansa-metallocene compound to the organoaluminum compound in the precontacted mixture and the combined postcontacted mixture.

When a precontacting step is employed, in general, the molar ratio of olefin monomer to ansa-metallocene 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 the invention, the weight ratio of solid oxide activator to organoaluminum compound can be between about 1:5 and about 1,000: 1. In another aspect, the weight ratio of solid oxide activator to organoaluminum compound can be from about 1:3 to about 100:1, and in another aspect, from about 1:1 to about 50: 1.

in yet another aspect of the invention, the weight ratio of the ansa-metallocene compound to the solid oxide activator-support can be from about 1:1 to about 1:1,000,000. In yet another aspect of the invention, the weight ratio of the ansa-metallocene to the solid oxide activator-support can be from about 1:10 to 1: about 100,000, and in another aspect from about 1:20 to about 1: 1000.

It is an aspect of the present invention that aluminoxanes are not necessary to form the catalyst compositions disclosed herein and that the feature allows for lower polymer production costs. Thus, in one aspect, the present invention can utilize AlR in the absence of alumoxane₃-organoaluminum compound of type and activator-support. While not wishing to be bound by theory, it is believed that the organoaluminum compound may not activate the metallocene catalyst in the same manner as the organoaluminoxane.

In addition, expensive borate compounds or MgCl₂It is not necessary to form the catalyst composition of the present invention, although alumoxanes, borate compounds, MgCl₂Or any combination thereof, may optionally be used in the catalyst composition of the present invention. Further, in one aspect, cocatalysts such as aluminoxanes, organoboron compounds, ionizing ionic compounds, or any combination thereof may be used asCocatalyst for ansa-metallocenes, either in the presence or absence of an activator-support. In addition, a cocatalyst such as an aluminoxane, an organoboron compound, an ionizing ionic compound, or any combination thereof, can be used as a cocatalyst for the ansa-metallocene, whether in the presence or absence of an organoaluminum compound, as described herein. Thus at least one ligand on the metallocene is a hydrocarbyl group, H, or BH₄When the current is over; when the at least one activator comprises an organoaluminoxane compound; or both of these conditions, at least one organoaluminum compound is optional. However, the catalyst composition of the present invention is active in the substantial absence of a cocatalyst such as an aluminoxane, an organoboron compound, an ionizing ionic compound, or any combination thereof.

Accordingly, in one aspect, the present invention provides a method of producing a catalyst 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

contacting the precontacted mixture with at least one activator-support and optionally an additional organoaluminum compound for a second period of time to form a postcontacted mixture comprising at least 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 ansa-metallocene can comprise a compound having the formula:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl;

(X¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is a carbon atom, a silicon atom, a germanium atom or a tin atom, and E is bonded to (X)¹) And (X)²) And wherein R is¹And R²Independently an alkyl group or an aryl group, any of which having up to 12 carbon atoms, or R¹And R²Independently is hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

(X¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) f, Cl, Br or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs 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; halogen root; or hydrogen.

In one aspect, the catalyst of the invention generally has a catalyst activity greater than or equal to about 100 grams of polyethylene per gram of chemically-treated solid oxide per hour (abbreviated gP/(gCTSO hr)). In another aspect, the catalyst of the invention can be characterized by an activity greater than or equal to about 250gP/(gCTSO hr), and in another aspect by an activity greater than or equal to about 500gP/(gCTSO hr). In yet another aspect, the catalyst of the invention can be characterized by an activity greater than or equal to about 1000gP/(gCTSO hr), and in another aspect by an activity greater than or equal to about 2000gP/(gCTSO hr). In one aspect, the activity is generally measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90 ℃, and at an ethylene pressure of about 550 pounds per square inch gauge (psig). In another aspect, the activity is measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of from about 80 ℃ to about 105 ℃ and at an ethylene pressure of from about 450 psig to about 550 psig. In making these measurements, the reactor should be substantially free of any signs of wall scale, coating, or other forms of fouling.

Use of catalyst compositions in polymerization processes

The catalysts of the present invention are intended for use in any olefin polymerization process known in the art, using various types of polymerization 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. Various types of reactors include those that may be referred to as batch, slurry, gas phase, solution, high pressure, tubular, or autoclave reactors. The gas phase reactor may comprise a fluidized bed reactor or a staged horizontal reactor (stageddorizontal reactors). Slurry reactors may comprise vertical loops (vertical loops) or horizontal loops (horizontal loops). The high pressure reactor may comprise an autoclave reactor or a tubular reactor. Reactor types may include batch or continuous processes. Continuous processes may use batch or continuous product unloading. The process may also include partial or complete direct recycle of unreacted monomer, unreacted comonomer and/or diluent.

The polymerization reactor system of the present invention may comprise one system of one type of reactor or a plurality of reactors of the same or different types. The production of polymer in a plurality of reactors may comprise several stages in at least two separate polymerization reactors connected to each other by transfer means, which makes it possible to transfer the polymer produced by a first polymerization reactor to a second reactor. The desired polymerization conditions in one reactor may be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include manual transfer of polymer from one reactor to a subsequent reactor for continuous polymerization. The multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, combinations of loop and gas phase reactors, multiple high pressure reactors, or combinations of high pressure reactors with loop and/or gas phase reactors. Multiple reactors may be operated in parallel or in series.

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. The monomer, diluent, catalyst and optionally any comonomer are continuously fed to a loop reactor where polymerization occurs. In general, a continuous process may include continuously introducing monomer, catalyst, and diluent into a polymerization reactor, and continuously removing a suspension containing polymer particles and diluent from the reactor. The reactor effluent may be flashed to remove solid polymer from the liquid comprising diluent, monomer and/or comonomer. Various techniques may be used for this separation step including, but not limited to, flashing which may include any combination of heating and pressure reduction; separation by cyclone action in a cyclone or hydrocyclone; or by centrifugation.

Typical slurry polymerization processes, also known as particle form processes, are well known in the art and are disclosed, for example, in U.S. Pat. nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415, each of which is incorporated herein by reference in its entirety.

Suitable diluents for use in slurry polymerization are well known in the art and include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerizations can occur under bulk conditions (bulk conditions) without the use of a diluent. One example is the polymerization of propylene monomers as disclosed in U.S. Pat. No. 5,455,314, which is incorporated herein by reference in its entirety.

According to yet another aspect of the 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 continuously circulated through the fluidized bed in the presence of the catalyst under polymerization conditions, the recycle stream containing one or more monomers. The recycle stream may be withdrawn from the fluidized bed and recycled back to the reactor. At the same time, polymer product may be withdrawn from the reactor and new or fresh monomer may be added to replace the monomer being polymerized. Such gas phase reactors may comprise a process for the multi-step gas phase polymerization of olefins, wherein olefins are polymerized in the gas phase in at least two separate gas phase polymerization zones, while a catalyst-containing polymer formed in a first polymerization zone is fed to a second polymerization zone. One type of gas phase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4588, 790 and 5,436,304, each of which is incorporated herein by reference in its entirety.

According to yet another aspect of the present invention, the high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor, both of which are known in the art. The tubular reactor may have several zones to which fresh monomer, initiator or catalyst is added. The monomer is carried in an inert gas stream and introduced in one zone of the reactor. The initiator, catalyst and/or catalyst components may be carried in a gas stream and introduced in another zone of the reactor. The gas streams are mixed to effect polymerization. Heat and pressure may be suitably utilized to obtain optimal polymerization conditions.

According to yet another aspect of the invention, the polymerization reactor may comprise a solution polymerization reactor wherein the monomer is contacted with the catalyst composition by suitable agitation or other means. A carrier comprising an inert organic diluent or excess monomer may be used. If desired, the monomer may be contacted with the catalytic reaction product in the vapor phase, in the presence or absence of liquid material. The polymerization zone is maintained at a temperature and pressure that will result in the formation of a solution of the polymer in the reaction medium. Agitation may be used to obtain better temperature control and to maintain a uniform polymerization mixture throughout the polymerization zone. Suitable methods are used to dissipate the exothermic heat of polymerization. Such reactors are known in the art.

Polymerization reactors suitable for the present invention may further comprise any combination of at least one feedstock feed system, at least one catalyst or catalyst component feed system, and/or at least one polymer recovery system. Suitable reactor systems for use in the present invention may further include systems for feedstock purification, catalyst storage and preparation, extrusion (extrusion), reactor cooling, polymer recovery, fractionation, recycle, storage, output (load out), laboratory analysis, and process control.

The conditions controlled for polymerization effectiveness and to provide resin properties include temperature, pressure, and concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. A suitable polymerization temperature may be any temperature below the depolymerization temperature according to the gibbs free energy equation. Typically, this includes from about 60 ℃ to about 280 ℃, for example from about 70 ℃ to about 110 ℃, depending on the type of polymerization reactor.

Suitable pressures will also vary depending on the reactor and type of polymerization. The pressure of the liquid phase polymerization in the loop reactor is typically below 1000 psig. The pressure of the gas phase polymerization is generally about 200 to 500 psig. High pressure polymerizations in tubular or autoclave reactors are typically run at about 20,000 to 75,000 psig. The polymerization reactor may also be operated in the supercritical region, which typically occurs at higher temperatures and pressures. Operation above the critical point of the pressure/temperature diagram (supercritical phase) may provide advantages.

The concentration of the various reactants can be controlled to produce a resin having specific physical and mechanical properties. The proposed end use product formed by the resin and the method of forming the product determines the desired resin properties. Mechanical properties include tensile, bending, impact, creep (creep), stress relaxation and hardness tests. Physical properties include density, molecular weight distribution, melting temperature, glass transition temperature, crystalline melting temperature, density, stereoregularity, crack propagation, long chain branching, and rheological measurements.

The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifier and electron donor are important in producing these resin properties. Comonomer is used to control product density. Hydrogen is used to control product molecular weight. The co-catalyst can be used to alkylate, scavenge poisons and control molecular weight. Modifiers can be used to control product properties, and electron donors affect stereoregularity. In addition, the concentration of poisons must be minimized because they affect the reaction 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 (geomembranes), and liners. Various methods may be used to form these articles including, but not limited to, blow molding, extrusion molding, roto-molding, thermoforming, cast molding, and the like. After polymerization, additives and modifiers may be added to the polymer during manufacture to provide better handling and achieve desired properties of the final product. Additives include surface modifiers such as slip agents, anti-blocking agents (antiblocks), binders; antioxidants such as primary and secondary antioxidants; a pigment; processing aids (processing aids) such as waxes/oils and fluoroelastomers; and special additives such as flame retardants, antistatic agents, scavengers, absorbents, odor enhancers (odor enhancers), and degradants.

Ethylene polymers prepared according to the invention

In one aspect, ethylene polymers produced using the catalyst compositions of the present invention are generally characterized by lower levels of Long Chain Branching (LCB) even when the comparative metallocene comprises at least one aryl group attached to a bridging atom of a bridged ligand, as compared to that typically observed when using tightly bridged ansa-metallocene compounds having no olefin-containing moiety attached to a cyclopentadienyl-type ligand. In a further aspect, ethylene polymers produced using the catalyst compositions of the present invention are characterized by having a higher molecular weight than is generally observed when using tightly bridged ansa-metallocene compounds that do not have at least one aryl group attached to the bridging atom of the bridging ligand, even when the comparative metallocene comprises an olefin-containing moiety attached to a cyclopentadienyl-type ligand. Fig. 3 through 8 illustrate various aspects of olefin homopolymers produced according to the present invention.

Size Exclusion Chromatography (SEC) coupled with multi-angle light scattering (MALS) detection was used to detect and characterize polymer branching. From the SEC-MALS analysis, the radius of gyration (R) of the ethylene homopolymers produced in examples 1-7 and examples 10-11 was determined as shown in FIGS. 3-5_g) Pair M, a measure of the size of the molecule_wThe plots obtained demonstrate one aspect of the utility of the present invention in reducing LCB. Radius of gyration (R)_g) The deviation from the known linear control (in this case, HiD9640) indicates branching. Thus, the data of FIGS. 3-5 show that: in the Rg versus Mw plot, the polymers prepared using the catalyst compositions according to the invention deviate only slightly from the linear standard HiD9640 at the high molecular weight end.

FIGS. 6 and 7 illustrate the log (. eta.) of the polymers prepared according to examples 1-11 and comparative examples 14-16, respectively₀) Log (M)_w) Figure and further illustrates how reduced LCB levels are confirmed (see table 1). The linear polyethylene polymer was observed to have a zero shear viscosity η₀And its weight average molecular weight M_wIn the middle of the recipeFollowing the power law relationship, the powers are very close to 3.4. At drawing η₀Logarithm of (M)_wThe relationship is shown by a straight line with a slope of 3.4. The deviation of the linear polymer strands is generally believed to be caused by the presence of Long Chain Branching (LCB). Janzen and Colby propose a model that predicts the log (. eta.) of a given LCB frequency as a function of the weight average molecular weight of the polymer₀) Log (M)_w) Expected deviation of the linear plot. See: [ "Diagnosting-chain breaking in polyethylenes," J.Mol.struct.485-486, 569-]Which is hereby incorporated by reference in its entirety.

Thus, FIGS. 6 and 7 plot the η of polymers prepared according to the present invention₀Logarithm of (M)_wIllustrates the zero shear melt viscosity and weight average molecular weight (M)_w) And shows that these polymers have very little deviation from the well-known 3.4 power law "Arnett line" used as a marker for linear polymers (j. phys. chem.1980, 84, 649). In agreement with this observation, both the SEC-MALS and the rheological data show that the metallocenes of the present invention produce extremely low LCB in ethylene polymerization, as illustrated in FIG. 6 for examples 1-11. In contrast, the polymers prepared according to comparative examples 14-16 have much lower M relative to the polymers prepared according to examples 1-11 of the present invention_w. Typically, these polymers also have similar or higher LCB levels, as shown in fig. 7.

FIG. 8 shows a comparison of Gel Permeation Chromatography (GPC) tests of polymers produced according to the invention from examples 1-11 and examples 14-16. These GPC results (table 1 and fig. 8) show that Polyethylene (PE) prepared according to the present invention typically has a high molecular weight. While the polymers prepared according to comparative examples 14-16 were characterized as having low levels of LCB (FIG. 8), these comparative polymers had relatively lower M's than the polymers prepared according to the present invention_w. Comparative examples 12 and 13 also show that the catalysts prepared using comparative metallocene C-1 exhibit poor activity (Table 1). Further, in the preparation of GPC and SEC-MALS samples of these substances, the samples prepared according to comparative examples 12 and 13In the polymer sample, a significant amount of insoluble polymer (about 50 wt%) was observed. Thus, using the polymer samples prepared according to comparative examples 12 and 13, 25 to 28 mg of polymer were mixed in 25 ml of 1,2, 4-trichlorobenzene and stirred for 5 hours while the mixture was maintained at 150 ℃. Visual inspection of samples containing samples prepared as described showed that a precipitate formed on the side of the sample tube. This observation shows that: the polymers prepared according to examples 12 and 13 using metallocene C-1 are non-linear polymers. In the polymer prepared according to any of the other examples, no insoluble polymer was observed.

Definition of

In order to more clearly define the terms used herein, the following definitions are provided. To the extent that any definition or use provided by any document incorporated by reference conflicts with the definition or use provided herein, the definition or use provided herein follows.

The term "polymer" is used herein to refer to a homopolymer comprising ethylene and/or a copolymer of ethylene and another olefinic comonomer. "Polymer" is also used herein to refer to homopolymers and copolymers of any of the other polymerizable monomers disclosed herein.

The term "cocatalyst" (cocatalysts) "is used herein generally to refer to organoaluminum compounds that can constitute one component of the catalyst composition, but also to optional components of the catalyst composition, including, but not limited to, aluminoxanes, organoboron compounds, organoborate compounds, or ionizing ionic compounds, as disclosed herein. In one aspect, the cocatalyst can be of the formula Al (X)⁵)_n(X⁶)_3-nThe organoaluminum compound of (2), wherein (X)⁵) Is a hydrocarbyl group having from 1 to about 20 carbon atoms; (X)⁶) Is an alkoxy or aryloxy group, any of which having from 1 to about 20 carbon atoms, a halide, or a hydride; n is a number from 1 to 3, 1 and 3 being included. The term cocatalyst may be used regardless of the actual function of the compound or of what the compound may be acting onAny chemical mechanism.

The term "precontacted" mixture is used herein to describe a first mixture of catalyst components that is contacted for a first time period before the first mixture is used to form a "postcontacted" mixture or a second mixture of catalyst components, which is precontacted for a second time period. Generally, the precontacted mixture describes a mixture of metallocene, olefin monomer, and organoaluminum compound, which is then contacted with an acidic activator-support and optionally additional organoaluminum compound. Thus, "pre-contacting" describes components that are used to contact one another, but prior to contacting with the components in the second, post-contact mixture. Thus, the present invention can sometimes distinguish between the component used to prepare the precontacted mixture and that component after the mixture has been prepared. For example, according to the present description, once a precontacted organoaluminum compound is contacted with a metallocene and an olefin monomer, it is possible for the precontacted organoaluminum compound to react to form at least one different compound, composition (formulation), or structure that is different from the different organoaluminum compound used to prepare the precontacted mixture. In this case, the precontacted organoaluminum compound or component is described as including the organoaluminum compound used to prepare the precontacted mixture.

Likewise, the term "post-contacted" mixture is used herein to describe a second mixture of catalyst components that is contacted for a second period of time, and one of its compositions is a "pre-contacted" mixture or first mixture of catalyst components that is contacted for a first period of time. Generally, the term "post-contacted" mixture is used herein to describe a mixture of metallocene, olefin monomer, organoaluminum compound, and acidic activator-support that is formed by contacting a portion of a precontacted mixture of these components with any additional components that are added to make up the post-contacted mixture. In general, the additional component added to make up the post-contact mixture is a solid oxide activator, and optionally can include an organoaluminum compound that is the same as or different from the organoaluminum compound used to prepare the pre-contact mixture, as described herein. Thus, the present invention may also sometimes distinguish between a component that is used to prepare a post-contact mixture and that component after the mixture has been prepared.

The term tightly bridged ansa-metallocenes describes wherein two η's in the molecule⁵The cycloalkadienyl-type ligand being a metallocene compound linked by a bridging moiety, wherein two η⁵The shortest connection between the cycloalkadienyl-type ligands comprises one atom. Thus, the bridge or chain between two cyclopentadienyl-type ligands is a single atom in length, although the bridging atom is substituted. Thus, the metallocenes of the present invention are bridged bis (. eta.)⁵-cycloalkadienyl) type compound, wherein eta⁵Cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including substituted and partially saturated analogs thereof. Possible substituents on these ligands include hydrogen, and thus the expression "substituted derivatives thereof" includes in the present invention 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, metallocenes are simply referred to as "catalysts," as the term "cocatalyst(s)" is used herein to refer to organoaluminum compounds.

The terms "catalyst composition", "catalyst mixture" and the like do not depend on the actual product of the reaction of the mixture components, the nature of the active catalytic site, or the history of the aluminum cocatalyst, the ansa-metallocene, any olefin monomer used to prepare the precontacted mixture, or the solid oxide activator after combining these components. Thus, the terms catalyst composition, catalyst mixture, and the like may include heterogeneous compositions (heterogenetic compositions) and homogeneous compositions (homogenetic compositions).

The term "hydrocarbyl" is used to define a hydrocarbon radical, which includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, etc., and includes all substituted, unsubstituted, branched, straight-chain, heteroatom-substituted derivatives thereof. Unless otherwise specified, hydrocarbyl groups of the present invention typically contain up to about 20 carbon atoms. In one aspect, the hydrocarbyl group can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.

The term "hydrocarbyloxy" group is generally used to refer collectively to alkoxy and aryloxy groups. Unless otherwise specified, the hydrocarbyloxy groups of the invention generally comprise up to about 20 carbon atoms. In one aspect, the hydrocarbyloxy group can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.

The term "hydrocarbylamino" group is generally used to refer to alkylamino (NHR), arylamino (NHAr), dialkylamino (NR)₂) And diarylamino (NAr)₂) A group. Unless otherwise specified, the hydrocarbyl amino groups of the present invention typically include up to about 20 carbon atoms. In one aspect, the hydrocarbylamino group can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.

The term "alkenyl" is used broadly to define a hydrocarbon group that includes an alkene moiety regardless of the particular site chemistry of the alkene moiety and includes all stereochemical isomers. Thus, for example, the term alkenyl is intended to include any CH ═ CH₂-substituted or CH ═ CMe₂Substituted alkyl groups, regardless of where within the alkyl group the substitution occurs. Terms such as olefin-containing hydrocarbon groups or olefin-containing side chain groups are often used interchangeably with alkenyl groups, again it is to be understood that these terms are not intended to be limited by the specific position of the C ═ C double bond within the group. Unless otherwise specified, alkenyl groups of the present invention typically include up to about 20 carbon atoms. In one aspect, the alkenyl group can have up to 12 carbon atomsUp to 8 carbon atoms, or up to 6 carbon atoms.

The terms solid oxide activator-support, acidic activator-support, treated solid oxide compound, and the like are used herein to denote a relatively high porosity treated solid inorganic oxide that exhibits lewis acidic or bronsted acidic properties and which has been treated with an electron-withdrawing component, typically an anion, and which has been 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 and at least one electron-withdrawing anion source compound. Generally, the activator-support or "treated solid oxide compound" comprises at least one ionizing acidic solid oxide compound. The term support or activator-support is not used to imply that these components are inert and that the components should not be considered as inert components of the catalyst composition.

The term "activator", as used herein, generally refers to a material capable of converting the contact product of: 1) a metallocene component; and 2) providing the metallocene with a component that activates a ligand, such as an alkyl or hydride ligand-when the metallocene compound does not contain such a ligand. The term is used regardless of whether the activator: ionizing the metallocene, abstracting anionic ligands to form ion pairs, weakening the metal-ligand bond in the metallocene, simply coordinating with anionic ligands, or any other mechanism. As disclosed herein, the contact product comprises at least one activator, which may be independently selected 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 or organoborate compound; or iv) any combination of these components.

The term "clay" is used herein to refer to this component of the catalyst composition, a substantial portion of which constitutes a clay mineral or mixture of clay minerals, which has been pretreated by cation exchange, pillaring, or simply wetting, which can be used as an activator-support in the catalyst compositions described herein. The transition metal compound and the organometallic cocatalyst react with the clay activator-support to form an active catalyst. Although not wishing to be bound by the following statements, the clay component of the catalyst composition of the present invention may function as an activator-support for the transition metal compound as well as the cocatalyst from the standpoint of its intimate physicochemical contact with the transition metal component.

As used herein, the generic term "clay mineral" is used herein to describe a large group of fine crystalline, platy minerals that are naturally found in fine grain sediments, sedimentary rocks, and the like. Clay minerals are a class of hydrated silicate and aluminosilicate minerals having a platelet structure and very high surface area. The term is also used to describe hydrous magnesium silicate having a phyllosilicate (phyllosilicate) structure. Many common clay minerals belong to the kaolinite, montmorillonite or illite group of clays. Thus, the term "clay mineral" is not used herein to refer to fine-grained soil consisting of mineral particles, not necessarily clay minerals, having a size below about 0.002 mm.

The term "pillared clay" as used herein refers to a component of the catalyst composition comprising a clay mineral, typically the smectite group and other layered silicates besides sepiolite and palygorskite, which 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 may have a charge such as 7+, various polyoxometallates, and other large ions. Thus, the term pillaring refers to a simple exchange reaction in which exchangeable cations of the clay species are replaced by large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the interlayers of the clay and, upon calcination, are converted into metal oxide "pillars" that effectively support the clay layers as a columnar structure. Examples of pillared and pillared clays are found in the following documents: T.J. Pinneavaia, Science220(4595), 365-; thomas, interaction Chemistry, (s. whitetington and a. jacobson editors) 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.

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

All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the structures 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 inventors are not entitled to antedate such disclosure by virtue of such prior invention.

For any particular compound disclosed herein, any general structure presented also includes all conformational isomers, positional isomers (regioisomers), stereoisomers, and the like, which may arise from a particular set of substituents. The general structures also include all enantiomers, diastereomers and other optical isomers, whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context requires.

The 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 may be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled 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 are carried out under an inert atmosphere such as nitrogen and/or argon. Solvents were purchased from commercial sources and were typically dried over activated alumina prior to use. Unless otherwise specified, reagents were obtained from commercial sources.

General test procedures, characteristics, and synthetic procedures are provided herein. Synthetic methods for preparing metallocenes, treated solid oxides, and other reagents of the invention are also provided herein.

General test procedure

Melt index (MI, g/10min) was determined at 190 ℃ under 2,160 gram weight according to ASTM D1238 condition F.

High load melt index (HLMI, g/10min) was determined according to ASTM D1238 condition E at 190 ℃ under 21,600 gram weight.

The polymer density was measured in grams per cubic centimeter (g/cc) on compression molded samples, cooled at about 15 deg.C/hour, conditioned at room temperature for about 40 hours, according to ASTM D1505 and ASTM D1928, method C.

Molecular weights and molecular weight distributions were obtained using a PL-GPC220(Polymer Labs, UK) system configured with a differential refractive index detector and three 7.5mm by 300mm20um MixedA-LS columns (Polymer Labs) run at 145 ℃. The flow rate of the mobile phase, 1,2, 4-Trichlorobenzene (TCB) containing 0.5g/L2, 6-di-tert-butyl-4-methylphenol (BHT), was set to 1mL/min, and the concentration of the polymer solution was generally maintained in the range of 1.0 to 1.5mg/mL depending on the molecular weight. Sample preparation was performed at 150 ℃ for 4 hours with infrequent gentle agitation, and then the solution was transferred to a sample vial for injection. To minimize the unbalanced solvent peak, a solvent having the same composition as the mobile phase was used for the solution preparation. The molecular weights and molecular weight distributions were deduced using the integral calibration method (integration method) using a wide-line polyethylene Marlex BHB5003 from Chevron Phillips chemicals company as a wide standard. The integral table (integral table) of broad standards was pre-determined in separate experiments using SEC-MALS.

Melt viscosity measurement to determine shear viscosity characteristics

The micro-strain oscillatory shear measurements were performed on an ARES oscillatory rheometer using parallel plate geometry (TA Instrument, formerly Rheometrics Inc.). Data are typically acquired at a temperature of 190 ℃ in the angular frequency range of 0.03 to 100 rad/sec.

The loose samples (fluff samples) were stabilized with 0.1 wt.% BHT dispersed in acetone and then vacuum dried prior to molding. The samples were compression molded at 184 ℃ for a total of 3 minutes. The sample was melted at relatively low pressure for 1 minute and then subjected to high molding pressure for an additional 2 minutes. The molded samples were then quenched under cold (room temperature) pressure. Discs having a diameter of 2mm × 25.4mm were punched out of the molded plate for rheological characterization.

The test chamber of the rheometer (test chamber) was blanketed with nitrogen to minimize polymer degradation. The rheometer was preheated to the initial temperature of investigation. After sample loading and oven heat equilibration, the sample was squeezed between the plates to a thickness of 1.6mm and the excess was trimmed.

During the frequency sweep, the strain is typically kept at a single value, but larger strain values are used for low viscosity samples to maintain measurable torque. Smaller strain values were used for high viscosity samples to avoid overloading the torque transducer and to stay within the linear viscoelastic limits of the sample. The instrument automatically reduces strain at high frequencies, if necessary, to avoid overloading the torque transmitter.

The viscosity data was fitted to a modified Carreau-Yasuda model [ r. byron Bird, Robert c. armstrong and Ole Hassager, Dynamics of Polymeric Liquids, Volume 1, FluidMechanics, (John Wiley & Sons, New York, 1987), p171-172], which is incorporated herein by reference, to obtain estimates of zero shear viscosity, viscous relaxation time, and width parameters, as shown below.

|η^*|＝η₀/[1+(ωτ_η)^a]^((1-n)/a)，

Wherein: eta |^*Number of complex viscosities, in Pa · s;

ω ═ angular frequency, rad/s;

η₀zero shear viscosity, Pa · s;

τ_ηviscosity relaxation time, s;

a is a width parameter;

n is the power law parameter fixed at 0.1818.

Absolute molecular weight determination by light scattering

Molecular weight data were determined using SEC-MALS, which combines Size Exclusion Chromatography (SEC) with a Multiple Angle Light Scattering (MALS) assay. The DAWN EOS 18-angle light scattering photometer (Wyatt Technology, Santa Barbara, Calif.) was connected to either a PL-210SEC system (Polymer labs, UK) or a Waters150CV Plus system (Milford, MA) via a heat transfer line (hot transfer line), thermally controlled at the same temperature (145 ℃) as the SEC column and its Differential Refractive Index (DRI) detector. The mobile phase, 1,2, 4-Trichlorobenzene (TCB), was eluted through three 7.5mm by 300mm20 μm Mixed A-LS columns (Polymer labs) at a flow rate setting of 0.7 mL/min. A Polyethylene (PE) solution at a concentration of-1.2 mg/mL depending on the sample was prepared for 4 hours at 150 ℃, after which the solution was transferred to SEC injection vials placed in a heated conveyor at 145 ℃. For higher molecular weight polymers, longer heating times are necessary in order to obtain truly homogeneous solutions. In addition to obtaining the concentration chromatogram, for each injection, Wyatt's Astra was usedSoftware, 17 light scattering chromatograms at different angles were also obtained. At each chromatographic segment (chromatographicslice), the absolute molecular weight (M) and Root Mean Square (RMS) radius, also known as the gyration, are obtained from the intercept and slope of the Debye plot, respectivelyRadius (R)_g). Methods for this process are detailed in Wyatt, p.j., anal. chim. acta, 272, 1(1993), which is incorporated herein by reference in its entirety. The Linear PE control used was a linear high density broad Molecular Weight Distribution (MWD) polyethylene sample (Chevron Phillips Chemical Co.). From these data, the weight average molecular weight (M) was calculated_w) Number average molecular weight (M)_n) Z-average molecular weight (M)_z) And molecular weight distribution (M)_w/M_n) And present it in the respective tables.

The amount of LCB in the ethylene polymer was determined by the Zimm-Stockmayer method. Since SEC-MALS measures M and R simultaneously on each fragment of the chromatogram_gSo on each segment, the branching index g as a function of M_MThe mean square R of the branched molecules can be determined directly by measuring the mean square at the same M_gAnd linear molecular mean square R_gAs shown in equation 1:

wherein the subscripts br and lin represent branched and linear polymers, respectively.

Weighted average of LCB per molecule (B) at a given gM_3w) Calculated using Zimm-Stockmayer equation shown in equation 2, where branching occursAre assumed to be trifunctional or Y-shaped.

Then, the LCB frequency (LCB) of the i-th slice is calculated directly using equation 3_Mi) I.e. the number of LCBs per 1000C:

LCB_Mi＝1000^*14^*B_3w/M_i (3)

wherein M is_iIs the MW of the ith fragment. Thus, the LCB distribution (LCBD) of the complete polymer across the Molecular Weight Distribution (MWD) range is established.

Quantachrome Autosorb-6Nitrogen Pore Size Distribution Instrument was used to determine specific surface area ("surface area") and specific Pore volume ("Pore volume"). The instrument is available from Quantachrome Corporation of Syoset, New York.

Preparation of 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 MS13-110, containing 13% alumina, having a pore volume of about 1.2cc/g and about 400m²Surface area in g. The material is fluorinated by incipient wetness by impregnation with a solution containing ammonium bifluoride in an amount sufficient to equal 10% by weight of the silica-alumina weight. The impregnated mass was then dried in a vacuum oven at 100 ℃ for 8 hours. The so-fluorinated silica-alumina sample was then calcined as follows. Approximately 10 grams of alumina was placed in a 1.75 inch quartz tube equipped 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 a 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 to a final temperature of about 500 c at a rate of about 400 c/hour. At this temperature, the silica-alumina was fluorinated in dry air for approximately three hours. Thereafter, the silica-alumina was collected and stored under dry nitrogen and used without exposure to the atmosphere.

Preparation of sulfated alumina activator-support

In general, sulfated alumina is formed by a process in which alumina is chemically treated with a sulfate or bisulfate source, typically selected from, but not limited to, sulfuric acid, ammonium sulfate or ammonium bisulfate. One embodiment is as follows.

Commercial Alumina sold as w.r.grace Alumina a was prepared by using Alumina containing 15-20% (NH)₄)₂SO₄Or H₂SO₄Is impregnated with an aqueous solution of (a) to be sulfated. The sulfated alumina was calcined at 550 ℃ in air (240 ℃/h ramp rate) at that temperatureThere was a hold period (hold period) of 3 h. Thereafter, the silica-alumina was collected and stored under dry nitrogen and used without exposure to the atmosphere.

Metallocene preparation

Unless otherwise indicated, reagents were obtained from Aldrich Chemical Company and used as received. 2, 7-Di-tert-butylfluorene was purchased from Degussa. Grignard reagent CpMgCl (1M in THF) was purchased from Boulder Scientific Company. Hafnium (IV) chloride was purchased from Strem. The solvent THF was distilled from potassium, while dehydrated ether, methylene chloride, pentane and toluene were purchased from Fisher Scientific Company and stored on activated alumina. All solvents were degassed and stored under nitrogen. By passing¹H NMR spectroscopy (300MHz, CDCl)₃Reference CHCl at 7.24ppm₃Residual proton peak of (1) or TMS at 0 ppm) or¹³C NMR(75MHz，CDCl₃Reference CHCl at 77.00ppm₃Center line of (d), the reaction product was analyzed. The reported preparation was not optimized.

The following fulvenes F1 to F5 were prepared as disclosed herein and used to prepare the ligands provided herein

2- (pent-4-enyl) -6, 6-bis 2- (but-3-enyl) -6, 6-bis 2- (1, 1-dimethylpent-4-ene

Phenyl pentafulvene) -6, 6-diphenyl pentafulvene

F-1 F-2 F-3

6, 6-Diphenylpentafulvene 2- (pent-4-enyl) -6, 6-dibutylpentafulvene

F-4 F-5

L-1 to L5.

The following ligands L-1 to L-5 were prepared as disclosed herein.

Isomer mixture

L-1 L-2 L-3

Isomer mixture

L-4 L-5

Synthesis of 2- (pent-4-enyl) -6, 6-diphenyl pentafulvene (F-1)

Cyclopentadienyl magnesium chloride (700ml of a 1M solution in THF, 0.70 mol) was added to 5-bromo-1-pentene (100g, 95 wt%, 0.637 mol) at 0 ℃ over 1 hour. After stirring at 0 ℃ for a further 30 minutes, the mixture was allowed to warm 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. The solvent was removed under vacuum at room temperature to yield a yellow-brown liquid (98 g, crude pent-4-enylcyclopentadiene). To crude pent-4-enylcyclopentadiene (89 g) dissolved in THF (500ml) was added n-BuLi (60 mL, 10M in hexanes). The mixture was allowed to warm to room temperature and stirred overnight. The anionic solution was added to benzophenone (110 g, 0.604 mol) dissolved in THF (500ml) at 0 ℃ over 25 minutes. The mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. The mixture was extracted with pentane. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum at 40 ℃ to yield a dark red viscous oil. The oil was dissolved in hexane and filtered through silica gel. The product was collected by washing the silica gel with 5-10% CH2Cl2 in hexanes. Removal of the solvent gave the desired product (145g, 84% yield based on 5-bromo-1-pentene) as a dark red viscous oil.¹H NMR(300MHz，CDCl₃)δ7.41-7.48(m，10H)，6.59-6.62(dd，J＝5.1Hz，1.4Hz，1H)，6.40-6.42(dd，J＝5.1Hz，1.4Hz，1H)，6.12-6.15(m，1H)，5.86-6.02(m，1H)，5.08-5.20(m，2H)，2.55-2.60(t，J＝7.2Hz，2H)，2.22-2.30(m，2H)，1.76-1.88(quin，J＝7.2Hz，2H)；¹³C NMR(75MHz，CDCl₃)δ148.28，148.13，143.28，140.85，140.76，138.01，133.51，131.34，131.29，127.76，127.74，127.13，127.08，124.74，118.24，114.24，33.95，30.13，28.46。

Synthesis of 1- (3- (pent-4-enyl) cyclopentadienyl) -1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (L-1)

Dissolve in Et at 0 deg.C₂2, 7-di-tert-butylfluorene (125.1g, 0.45mol) in O (700mL) was added to n-BuLi (47mL, 10M in hexanes, 0.47 mol). The mixture was allowed to warm to room temperature and stirred overnight. The anionic solution was added to dissolved Et over 10 minutes at-78 deg.C₂O (300mL) in 2- (pent-4-enyl) -6, 6-diphenyl pentafulvene (F-1) (145g, 0.487 mol). The mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. With Et₂And O, extracting the mixture. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum to yield a light brown solid. The solid was washed with heptane and dried under vacuum. Obtained as whiteThe solid was obtained as an isomeric mixture of the desired product (191.7g, 74% yield).

Synthesis of 2- (but-3-enyl) -6, 6-diphenyl pentafulvene (F-2)

To 4-bromo-1-butene (100g, 97 wt%, 0.719mol) was added cyclopentadienyl magnesium chloride (800mL, solution in 1M THF, 0.8mol) at 0 ℃ over 50 minutes. After stirring at 0 ℃ for a further 15 minutes, the mixture was allowed to warm 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. The solvent was removed in vacuo at room temperature to give a brown liquid (94.2g, crude but-3-enylcyclopentadiene). To crude but-3-enylcyclopentadiene (94.2g) dissolved in THF (500mL) was added n-BuLi (70mL, 10M in hexane, 0.7mol) at-78 ℃. The mixture was allowed to warm to room temperature and stirred overnight. The anionic solution was added to benzophenone (133.8g, 0.735mol) dissolved in THF (400mL) at 0 deg.C over 35 minutes. The mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. The mixture was extracted with pentane. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent in vacuo at 40 ℃ gave a dark red viscous oil. The oil was dissolved in heptane and filtered through silica gel. By using 5-10% CH in heptane₂Cl₂The silica gel was washed and the product was collected. The solvent was removed to give the desired product as a dark red viscous oil (152g, 74.4% yield based on 4-bromo-1-butene).¹H NMR(300MHz，CDCl₃)δ7.29-7.41(m，10H)，6.50-6.53(dd，J＝5.2Hz，1.4Hz，1H)，6.29-6.31(dd，J＝5.2Hz，1.4Hz，1H)，6.02-6.05(m，1H)，5.82-5.98(m，1H)，4.94-5.16(m，2H)，2.53-2.60(m，2H)，2.33-2.43(m，2H)；¹³C NMR(75MHz，CDCl₃)δ148.59，147.67，143.18，140.86，140.78，137.85，133.48，131.38，131.36，127.85，127.82，127.18，127.13，124.75，118.35，114.29，33.36，30.20。

Synthesis of 1- (3- (but-3-enyl) cyclopentadienyl) -1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (L-2)

Dissolve in Et at 0 deg.C₂2, 7-di-tert-butylfluorene (91.7g, 0.33mol) in O (500mL) was added to n-BuLi (35mL, 10M in hexanes, 0.35 mol). The mixture was allowed to warm to room temperature and stirred overnight. The anionic solution was added to dissolve in Et over 35 min at 0 deg.C₂2- (but-3-enyl) -6, 6-diphenylpentafulvene (compound F-2) (104g, 0.366mol) in O (200 mL). After stirring at 0 ℃ for an additional 30 minutes, the mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. By CH₂Cl₂The mixture is extracted. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent under vacuum yielded a light brown solid. The solid was washed with heptane and dried under vacuum. The isomeric mixture of the desired product was obtained as a white solid (142g, 76.5% yield).

Synthesis of 2- (1, 1-dimethylpent-4-enyl) -6, 6-diphenylpentafulvene (F-3)

To 6-butenyl-6-methylpentafulvene (17.8g, 122mmol) (prepared by the method of K.J.Stone and R.D.Little, J.Org.Chem., 1984, 49(11), 1849-Asca 1853) in dry THF (50mL) was added a solution of methyllithium (75mL, 1.6M in ether, 120mmol) while cooling on dry ice. After stirring for 20 h and warming to room temperature, the yellow solution was added stepwise to a solution of benzophenone (21.87g, 120mmol) in THF (50mL) while cooling on ice. The immediate red color formed and analysis of the aliquot after 4 hours showed that the reaction was nearly complete. After another hour, the mixture was cooled while adding a solution of concentrated hydrochloric acid (20mL) in water (200 mL). After addition of pentane (150mL), 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 ℃ overnight. The red crystalline product was washed with cold methanol and dried under vacuum to a red solid (32.8g, 84% yield).¹H NMR(300MHz，CDCl₃)δ7.22-7.40(m，10H)，6.56-6.58(dd，J＝5.1Hz，1.8Hz，1H)，6.24-6.26(dd，J＝5.1Hz，1.8Hz，1H)，5.91-5.93(t，J＝1.8Hz，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)；¹³C NMR(75MHz，CDCl₃)δ156.16，148.39，143.20，140.96，140.92，138.98，131.61，131.43，131.39，127.81，127.77，127.24，127.14，124.88，116.30，113.45，41.96，35.86，29.90，27.90。

Synthesis of 1- (3- (1, 1-dimethylpent-4-enyl) cyclopentadienyl) -1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (L-3)

Et Cooling in Dry Ice₂A solution of 2, 7-di-tert-butylfluorene (27.8g, 100mmol) in O (200mL) and n-BuLi (68mL, 1.6M in hexanes, 0109mmol) was added dropwise. The slurry was allowed to warm to room temperature and stirred for 24 hours. The black solution was cooled in dry ice and then 2- (1, 1-dimethylpent-4-enyl) -6, 6-diphenylpentafulvene (compound F-3) (32.8g, 54.3mmol) of Et was added rapidly₂O (100mL) solution. The mixture was warmed to room temperature and stirred for 20 hours. After cooling in ice, an aqueous solution (200mL) of concentrated hydrochloric acid (20mL) was added. After addition of pentane (100mL), the organic layer was separated and washed with water. After drying over sodium sulfate and filtration, the solvent was removed in vacuo leaving a glassy solid. The solid and methanol (100mL) were heated together and the hot methanol solution was decanted. This process was repeated four times. The solid was then dissolved in hot pentane, which was then removed in vacuo while heating. The solid was broken, dried under vacuum, and then heated with ethanol (70 mL). After cooling, the solid was filtered and dried. The isomeric mixture of the desired product was obtained as a white solid (18.1g, 30% yield).

Synthesis of 6, 6-diphenyl pentafulvene (F-4)

Benzophenone (63.8 g, 350 mmol) was dissolved in anhydrous 1, 2-Dimethoxyethane (DME) (150ml) under nitrogen. In a1 l 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 (35ml, 430 mmol) was added. After 30 minutes, a solution of benzophenone was added over 15 minutes. The flask was stirred in a refrigeratorFor 90 hours, and then while cooling in ice, 3M HCl (450 ml) was added. The mixture was diluted with pentane (500ml) and the mixture was separated. The organic layer was washed with water (2 × 200ml) and dried over sodium sulfate. The solution was filtered and allowed to dry under vacuum. The solid was dissolved in boiling pentane (600 ml) and then concentrated to 400 ml. Cooling to-15 ℃ for 40 h gave a red solid (69.5 g, 86.3% yield).¹H NMR(300MHz，CDCl₃)δ7.24-7.38(m，10H)，6.53-6.59(m，2H)，6.24-6.30(m，2H)；¹³C NMR(75MHz，CDCl₃)δ151.24，143.20，140.65，131.73，131.55，128.16，127.20，123.89。

Synthesis of 1-cyclopentadienyl-1- (2, 7 di-tert-butylfluorenyl) -1, 1-diphenylmethane (L-4)

To a solution of 2, 7-di-tert-butylfluorene (29.8 g, 107 mmol) in dry THF (100mL) cooled in dry ice was added n-BuLi (43.0 mL, 2.5M in hexanes, 107.5 mmol). The dry ice bath was removed and the black solution was stirred for 2 hours. This solution was then added dropwise to a solution of 6, 6-diphenyl pentafulvene (compound F-4) (26.0 g, 113 mmol) in THF (100ml) while cooling on ice. The reaction mixture was stirred at room temperature for 86 hours, followed by cooling in ice. 1M HCl solution (100ml) was added. The mixture was diluted with chloroform (100ml) and separated. The chloroform layer was washed with water (3 × 100ml) and dried over sodium sulfate. The solution was filtered and evaporated to a pale orange solid. The solid was dissolved in boiling chloroform (150ml) and methanol (150ml) was added slowly. After cooling for 2 days to-15 ℃, the solid was filtered, triturated and dried under vacuum. The isomeric mixture of the desired product was obtained as an off-white solid (25.4 g, 46.7% yield).

Synthesis of 5- (3- (pent-4-enyl) cyclopentadienyl) -5- (2, 7-di-tert-butylfluorenyl) nonane (L-5)

2, 7-di-tert-butylfluorene (10 g, 36 mmol), Et₂O (150ml) was charged into a flask under N₂Cooling to-78 deg.C,and stirred while adding n-BuLi (4.3 ml, 10M in hexane, 43 mmol) via syringe. The reaction mixture was allowed to warm to room temperature, stirred overnight, cooled to-78 deg.C and 2- (pent-4-enyl) -6, 6-dibutylpentafulvene (compound F-5) (13 g, 50 mmol) was added rapidly (prepared according to the methods of K.J.Stone and R.D.Little, J.Org.Chem., (1984), 49(11), 1849-. The reaction mixture was warmed to room temperature and stirred overnight. With saturated NH₄The reaction was quenched with Cl solution. The organic layer was extracted with Et2O, washed with water and washed with anhydrous Na₂SO₄And drying. Removal of the solvent under vacuum gave a yellow oil. The oil was eluted through a silica gel column using heptane to give the desired product as an isomeric mixture (12.8 g, 66% yield) as an oil.

Diphenylmethylene { eta [. eta. ]⁵- [3- (pent-4-enyl) cyclopentadien-1-yl ] -ene]}[η⁵- (2, 7-di-tert-butylfluoren-9-yl)]Synthesis of hafnium dichloride (I-1)

Dissolving in Et at 0 deg.C₂1- (3- (pent-4-enyl) cyclopentadienyl) -1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (compound L-1) (45.3 g, 78.6 mmol) in O (400ml) was added slowly to n-BuLi (68.5 ml, 2.5M in hexane, 171.3 mmol). The mixture was warmed to room temperature, stirred overnight and then added via cannula to a suspension in pentane (450 ml) and Et over 30 minutes at 0 ℃₂HfCl in O (30 ml) mixture₄(26.8 g, 83.6 mmol). The mixture was warmed to room temperature and stirred for 2 days. The slurry was concentrated and centrifuged. The liquid was decanted. The remaining solid was washed twice with pentane (100ml), then extracted with dichloromethane and centrifuged. The solution was dried under vacuum to yield a yellow solid (46.4 g, 71.7%).¹HNMR(300MHz，CDCl₃)δ7.88-7.98(m，3H)，7.78-7.88(m，3H)，7.40-7.50(m，2H)，7.29-7.38(broad t，J＝7.2Hz，2H)，7.11-7.28(m，4H)，6.28(broad s，1H)，6.24(broad s，1H)，5.87-5.93(t，J＝2.7Hz，1H)，5.61-5.78(m，1H)，5.44-5.50(t，J＝2.7Hz，1H)，5.19-5.25(t，J＝2.7Hz，1H)，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)；¹³C NMR(75MHz，CDCl₃)δ149.41，149.21，144.47，144.24，137.71，132.69，129.08，128.83，128.45，128.39，128.22，126.50，126.46，126.13，125.97，123.70，123.46，123.40，123.34，119.89，119.66，119.01，118.86，118.82，118.53，114.75，114.39，111.11，100.92，100.69，76.88，57.88，35.29，35.27，33.75，31.04，31.02，29.48，29.31。

Diphenylmethylene { eta [. eta. ]⁵- [3- (but-3-enyl) cyclopentadien-1-yl ] -ene]}[η⁵- (2, 7-di-tert-butylfluoren-9-yl)]Synthesis of hafnium dichloride (I-2)

Dissolving in Et at 0 deg.C₂1- (3- (but-4-enyl) cyclopentadienyl) -1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (compound L-2) (3.2 g, 5.7 mmol) in O (30 mL) was added n-BuLi (5.2 mL, 2.5M in hexanes, 13 mmol) slowly. The mixture was warmed to room temperature, stirred overnight, and then added via cannula to suspension in pentane (30 ml) and Et over 10min at 0 ℃₂HfCl in O (5 ml) mixture₄(2.1 g, 6.5 mmol). The mixture was warmed to room temperature and stirred for 2 days. The slurry was concentrated and centrifuged. The liquid was decanted. The remaining solid was washed twice with pentane (80 ml), then extracted with dichloromethane and centrifuged. The solution was dried under vacuum to yield a yellow solid (3.1 g, 67.4% yield).¹H NMR(300MHz，CDCl₃)δ7.87-7.98(m，3H)，7.79-7.86(m，3H)，7.43-7.49(m，2H)，7.30-7.38(dt，J＝7.5Hz，1.4Hz，2H)，7.14-7.29(m，4_H)，6.24-6.27(d，J＝0.6Hz，1H)，6.20-6.24(d，J＝0.6Hz，1H)，5.87-5.92(t，J＝2.7Hz，1H)，5.62-5.77(m，1H)，5.42-5.47(t，J＝2.7Hz，1H)，5.18-5.23(t，J＝2.7Hz，1H)，4.85-4.98(m，2H)，2.35-2.55(m，2H)，2.13-2.22(m，2H)，0.96(s，18H)；¹³C NMR(75MHz，CDCl₃)δ149.52，149.33，144.51，144.30，137.33，132.16，129.13，128.89，128.51，128.45，128.30，128.26，126.58，126.53，126.24，126.06，123.77，123.54，123.42，123.36，119.97，119.75，119.08，118.90，118.58，114.94，114.83，111.14，101.01，100.68，76.93，57.94，35.36，35.35，34.11，31.08，31.05，29.42。

Diphenylmethylene { eta [. eta. ]⁵- [3- (but-3-enyl) cyclopentadien-1-yl ] -ene]}[η⁵- (2, 7-di-tert-butylfluoren-9-yl)]Synthesis of zirconium dichloride (I-3)

At 0 ℃ to suspend in Et₂1- (3- (but-3-enyl) cyclopentadienyl) -1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (compound L-2) (40.5 g, 72.1 mmol) in O (400mL) was added n-BuLi (15.2 mL, 10M in hexanes, 152 mmol) slowly. The mixture was warmed to room temperature, stirred overnight, and then added via cannula to suspension in pentane (400ml) and Et at 0 ℃ over 15 minutes₂ZrCl in O (30 ml) mixture₄(18.5 g, 74.9 mmol). The mixture was warmed to room temperature, stirred for 1 day, and evacuated to dryness. The residue was stirred in pentane (300ml) and centrifuged. The supernatant was discarded. The remaining solid was washed twice with pentane (100ml), then extracted with dichloromethane and centrifuged. The solution was dried under vacuum to yield a red solid (38.1 g, 73.3% yield).¹H NMR(300MHz，CDCl₃) δ 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 ═ 7.5Hz, 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 (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);¹³C NMR(75MHz，CDCl₃)δ149.85，149.65，144.23，144.01，137.27，133.51，129.08，128.84，128.50，128.45，128.33，128.30，126.58，126.54，126.18，126.01，124.04，123.81，123.55，123.48，121.08，120.89，120.31，120.03，119.43，119.24，115.71，114.86，108.44，103.37，103.18，76.66，58.10，35.38，35.36，33.98，31.05，31.02，29.46。

diphenylmethylene { eta [. eta. ]⁵- [3- (pent-4-enyl) cyclopentadien-1-yl ] -ene]}[η⁵- (2, 7-di-tert-butylfluoren-9-yl)]Synthesis of zirconium dichloride (I-4)

Dissolving in Et at 0 deg.C₂1- (3- (pent-4-enyl) cyclopentadienyl) -1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (compound L-1) (34.7 g, 60.2 mmol) in O (300mL) was added slowly to n-BuLi (52 mL, 2.5M in hexane, 130 mmol). The mixture was warmed to room temperature, stirred overnight, and then added via cannula to a suspension in pentane (250 ml) and Et at 0 ℃ over 30 minutes₂ZrCl in O (20ml) mixture₄(14.7 g, 63.1 mmol). The mixture was warmed to room temperature, stirred for 1 day, and evacuated to dryness. The residue was stirred in pentane (200ml) and centrifuged. The supernatant was discarded. The remaining solid was washed twice with pentane (50ml), then extracted with dichloromethane and centrifuged. The solution was dried under vacuum to yield a red solid (33.5 g, 75.6%).¹H NMR(300MHz，CDCl₃)δ7.94-7.99(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 ═ 7.2Hz, 1.2Hz, 2H), 7.15-7.29(m, 4H), 6.23 (width s, 1H), 6.19 (width s, 1H), 5.94-5.98(t, J ═ 2.7Hz, 1H), 5.62-5.76(m, 1H), 5.50-5.54(t, J ═ 2.7Hz, 1H), 5.24-5.29(t, J ═ 2.7Hz, 1H), 4.82-4.96(m, 2H), 2.23-2.43(m, 2H), 1.97-2.05(m, 2H), 1.77 (m, 1H), 1.48-1.48 (m, 18H), 0.18H);¹³C NMR(75MHz，CDCl₃)δ149.85，149.65，144.27，144.03，137.79，134.18，129.11，128.85，128.51，128.46，128.34，126.59，126.55，126.18，126.03，124.04，123.79，123.54，123.47，121.09，120.89，120.32，120.06，119.46，119.26，115.61，114.44，108.51，103.36，103.29，76.69，58.13，35.39，35.37，33.78，31.06，31.03，29.61，29.33。

diphenylmethylene { eta [. eta. ]⁵- [3- (1, 1-dimethylpent-4-enyl) cyclopentadien-1-ylene]}[η⁵- (2, 7-di-tert-butyl)Fluoren-9-yl)]Synthesis of zirconium dichloride (I-5)

Adding Et₂A 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 O (50ml) was cooled in dry ice and n-BuLi (22.2 ml, 1.6M, in hexane, 35.5 mmol) was added dropwise. After 1 hour, the dry ice bath was removed and the mixture was stirred at room temperature for 48 hours. The mixture was added to ZrCl suspended in pentane (50ml) while cooling in ice₄(4.37 g, 18.8 mmol). The slurry was stirred at room temperature for 65 hours. The slurry was concentrated until thick and pentane (70ml) was added. The slurry was stirred overnight and the liquid was decanted. The solid was washed twice with pentane, then extracted with dichloromethane and centrifuged. The solution was dried under vacuum to yield a red solid (11.65 g, 85.2% yield).¹H NMR(300MHz，CDCl₃) δ 7.93-8.02(m, 3H), 7.80-7.91(m, 3H), 7.52-7.60(dt, J ═ 8.7Hz, 1.5Hz, 2H), 7.38-7.47(m, 2H), 7.20-7.35(m, 4H), 6.27 (width s, 2H), 6.14-6.18(t, J ═ 3.0Hz, 1H), 5.67-5.83(m, 1H), 5.61-5.64(t, J ═ 3.0Hz, 1H), 5.48-5.52(t, J ═ 3.0Hz, 1H), 4.88-5.04(m, 2H), 1.76-2.10(m, 2H), 1.44-1.53(m, 2H), 1.26(s, 3H), 1.18H, 1.02 (m, 3H), 1.07(s, 18H);¹³C NMR(75MHz，CDCl₃)δ149.67，149.60，144.31，144.13，143.46，138.49，129.15，128.89，128.51，128.48，128.39，128.33，126.58，126.52，126.11，125.97，124.18，124.10，123.73，123.36，121.09，120.78，120.20，119.75，118.88，114.16，113.84，108.10，104.30，100.60，77.19，57.65，46.43，36.32，35.38，35.36，31.06，31.03，29.47，26.99，24.19。

diphenylmethylene [ eta ] s⁵- (cyclopentadien-1-yl)][η⁵- (2, 7-di-tert-butylfluoren-9-yl)]Synthesis of zirconium dichloride (C-1)

1-cyclopentadienyl-1- (2, 7-di-tert-butylfluorenyl) -1, 1-diphenylmethane (compound L-4) (15.26 g, 30.0 mmol) was suspended in nitrogenDry Et₂O (250 ml). On cooling in dry ice, n-BuLi (24.0 mL, 2.5M in hexanes, 60 mmol) was added dropwise. The dry ice 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 (50ml) and cooled in ice. The orange slurry was stirred for 90 hours and allowed to warm to room temperature. The resulting slurry was centrifuged and the solid was mixed with dry dichloromethane (120 ml). The mixture was centrifuged, the solution removed, and allowed to dry under vacuum. The desired product was obtained as an orange solid (9.63 g, 48% yield).¹H NMR(300MHz，CDCl₃)δ7.98-8.04(d，J＝9Hz，2H)，7.91-7.96(m，2H)，7.83-7.89(m，2H)，7.55-7.60(dd，J＝9Hz，1.8Hz，2H)，7.38-7.45(dt，J＝7.5Hz，1.8Hz，2H)，7.21-7.36(m，4H)，6.30-6.34(m，4H)，5.64-5.67(t，J＝2.7Hz，2H)，1.03(s，18H)；¹³C NMR(75MHz，CDCl₃)δ149.98，144.00，128.93，128.50，128.41，126.64，126.08，124.16，123.56，121.12，120.30，119.41，117.92，109.92，102.40，77.72，58.36，35.40，31.01。

Dibutylmethylene [ eta ]⁵- [3- (pent-4-enyl) cyclopentadien-1-yl)][η⁵- (2, 7-di-tert-butylfluoren-9-yl)]Synthesis of zirconium dichloride (C-2)

5- (3- (pent-4-enyl) cyclopentadienyl) -5- (2, 7-di-tert-butylfluorenyl) nonane (compound L-5) (12.8 g, 23.8 mmol), Et₂O (200mL), stir bar was charged to the flask and cooled to-78 deg.C while slowly adding n-BuLi (5.3 mL, 10M in hexanes, 53 mmol). The mixture was allowed to warm to room temperature, stirred overnight, then added via cannula to ZrCl stirred in pentane at 0 deg.C₄(5.5 g, 23.6 mmol). 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 was discarded. By CH₂Cl₂The remaining solid was extracted, filtered, and the filtrate was evacuated to dryness to afford a red solid (7.8 g, 47% yield).¹H NMR(300MHz，CDCl₃)δ7.88-7.94(m，2H)，7.63(broad s，1H)，7.55(broad s，1H)，7.47-7.53(m，2H)，5.87-5.90(t，J＝2.7Hz，1H)，5.58-5.73(m，1H)，5.46-5.49(t，J＝2.7Hz，1H)，5.23-5.27(t，J＝2.7Hz，1H)，4.80-4.92(m，2H)，2.55-2.75(m，4H)，2.20-2.40(m，2H)，1.90-2.00(m，2H)，1.40-1.80(m，10H)，1.15(s，18H)，1.00(t，J＝6.9Hz，3H)，0.97(t，J＝6.9Hz，3H)；¹³C NMR(75MHz，CDCl₃)δ150.92，150.64，137.78，134.97，123.74，123.51，123.48，123.44，123.12，122.48，120.96，120.56，118.73，118.36，116.13，114.32，112.59，102.07，101.93，76.73，48.76，35.79，35.76，34.81，34.68，33.75，31.49，31.48，29.59，29.24，26.35，26.18，24.07，24.04，14.81，14.78。

Dibutylmethylene eta⁵- [3- (pent-4-enyl) cyclopentadien-1-yl)][η⁵- (2, 7-di-tert-butylfluoren-9-yl)]Synthesis of hafnium dichloride (C-3)

Dissolving in Et at 0 deg.C₂5- (3- (pent-4-enyl) cyclopentadienyl) -5- (2, 7-di-tert-butylfluorenyl) nonane (compound L-5) (14.6 g, 27.2 mmol) in O (150mL) was added slowly to n-BuLi (26 mL, 2.5M in hexanes, 65 mmol). The mixture was allowed to warm to room temperature, stirred overnight, and then added via cannula to a suspension in pentane (150ml) and Et at-78 ℃ over 15 minutes₂HfCl in O (20mL) mixture₄(9.2 g, 28.7 mmol). The mixture was warmed to room temperature, stirred for 2 days, and evacuated to dryness. The residue was stirred in pentane (150ml) and centrifuged. The supernatant was discarded. The remaining solid was extracted with dichloromethane and centrifuged. The solution was dried under vacuum to yield a yellow solid (6.6 g, 31% yield).¹HNMR(300MHz，CDCl₃)δ7.88-7.91(m，2H)]7.64 (width s, 1H), 7.56 (width s, 1H), 7.42-7.48(m, 2)_H)，5.80-5.84(t，J＝2.7Hz，1H)，5.58-5.73(m，1H)，5.39-5.43(t，J＝2.7Hz，1H)，5.18-5.23(t，J＝2.7Hz，1H)，4.78-4.91(m，2H)，2.55-2.75(m，4H)，2.22-2.42(m，2H)，1.88-1.97(m，2H)，1.40-1.80(m，10H)，1.27(s，18H)，0.99(t，J＝6.9Hz，3H)，0.97(t，J＝6.9Hz，3H)；¹³C NMR(75MHz，CDCl₃)δ150.63，150.32，137.78，133.55，123.42，123.40，123.36，123.15，121.99，121.30，119.48，119.02，118.30，117.97，115.26，115.07，114.30，99.44，99.39，76.79，48.73，35.74，35.72，35.01，34.89，33.78，31.52，31.49，29.53，29.30，26.46，26.30，24.09，24.05，14.83，14.79。

Examples 1 to 16

Catalytic experiments with varying metallocene, activator-support and conditions

Examples 1-16 in Table 1 illustrate ethylene polymerization runs conducted at different temperatures in a1 gallon (3.785 liter) stainless steel autoclave reactor using 2 liters of isobutane diluent and an aluminum alkyl co-catalyst and a cleaning agent. No hydrogen or comonomer was added. The metallocene solution (2mg/mL) was generally prepared by dissolving 30mg of metallocene in 15mL of toluene. A typical polymerization scheme is as follows. The alkylaluminum compound, the treated solid oxide and the metallocene solution are generally fed in this order through the feed inlet while isobutane vapor is vented. The feed port was closed and 2 liters of isobutane were added. The contents of the reactor were stirred and heated to the desired test temperature (table 1). Ethylene was fed as needed to maintain a specific pressure to achieve a specific length of polymerization run. The reactor was maintained at the desired test temperature throughout the experiment by an automated heating and cooling system.

After the specified polymerization time, the ethylene flow was stopped, the reactor was slowly depressurized and opened to recover the granular polymer. In all cases, the reactor was clean without any signs of wall scale, coating or other forms of fouling. The polymer was then removed and weighed (table 1).

Claims (63)

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:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independent of each otherSubstituted cyclopentadienyl, substituted indenyl or substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is a carbon atom, a germanium atom, or a tin atom, and E is substituted with (X)¹) And (X)²) In combination, wherein R¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) f, Cl, Br, or I; 2) hydrocarbyl, H, or BH having up to 20 carbon atoms₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl or 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 a carbon-containing group having from 1 to 20 carbon atoms; halogen root; or hydrogen;

b) the at least one organoaluminum compound comprises a compound having the formula:

Al(X⁵)_n(X⁶)_3-n，

wherein (X)⁵) Is a hydrocarbyl group having 1 to 20 carbon atoms; (X)⁶) Is any one of alkoxy or aryloxy groups having 1 to 20 carbon atoms, a halide or a hydride; and n is a number from 1 to 3, 1 and 3 being included; and

c) the at least one activator is independently selected 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 organoborate compound; or

iv) any combination thereof;

wherein, when: 1) (X)³) And (X)⁴) At least one of (A) is a hydrocarbon group having up to 20 carbon atoms, H or BH₄；

2) The at least one activator comprises an organoaluminoxane compound; or 3) the at least one organoaluminum compound is optional when both conditions 1 and 2 are present.

2. The catalyst composition of claim 1, wherein the carbon-containing group is selected from an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, a silicon-containing group, or a boron-containing group.

3. The catalyst composition of claim 1, wherein any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of an aliphatic group and a cyclic group.

4. The catalyst composition of claim 1, wherein:

a) the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently F, Cl, Br or I;

e is C;

R¹and R²Independently is an alkyl or aryl group, either of which having up to 10 carbon atoms, or is hydrogen, wherein R is¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently a hydrocarbyl or trihydrocarbylsilyl group, any of which has up to 20 carbon atoms; or hydrogen;

n is an integer from 0 to 10, including 0 and 10; and is

R^4AAnd R^4BIndependently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen;

b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, 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, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, 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.

5. The catalyst composition of claim 4, wherein the mixed oxide is silica-alumina.

6. The catalyst composition of claim 4, wherein the substituted or unsubstituted alkanesulfonate is trifluoromethanesulfonate.

7. The catalyst composition of claim 4, wherein the at least one organoaluminum compound comprises triisobutylaluminum or triisohexylaluminum.

8. The catalyst composition of claim 1, wherein the at least one activator is an activator-support further comprising a metal or metal ion.

9. The catalyst composition of claim 8, wherein the metal is zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.

10. The catalyst composition of claim 1, wherein the at least one activator is an activator-support selected from clay minerals.

11. The catalyst composition of claim 10, wherein the clay mineral is selected from the group consisting of pillared clays, delaminated clays, layered silicate minerals, non-layered silicate minerals, layered aluminosilicate minerals, non-layered aluminosilicate minerals, or any combination thereof.

12. The catalyst composition of claim 11 wherein the exfoliated clay is an exfoliated clay gelled into another oxide matrix.

13. The catalyst composition of claim 10, wherein the clay mineral comprises diaspholite, smectite, montmorillonite, nontronite, hectorite, lithium magnesium silicate, halloysite, vermiculite, mica, fluoromica, chlorite, mixed layer clay, fibrous clay, sepiolite, attapulgite, palygorskite, serpentine clay, illite, saponite, or any combination thereof.

14. The catalyst composition of claim 1, wherein the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is fluorine, chlorine, bromine, or iodine;

e is carbon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently hydrogen, methyl, allyl, benzyl, butyl, pentyl, hexyl or trimethylsilyl;

n is an integer from 1 to 6, inclusive; and

R^4Aand R^4BIndependently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen.

15. The catalyst composition of claim 1, wherein the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is chlorine, bromine, or iodine;

e is carbon;

R¹and R²Independently is methyl or phenyl, wherein R¹Or R²At least one of (a) is phenyl;

R^3Aand R^3BIndependently hydrogen or methyl;

n is 1 or 2; and

R^4Aand R^4BIndependently hydrogen or tert-butyl.

16. The catalyst composition of claim 1, wherein the at least one ansa-metallocene is selected from the group consisting of:

or any combination thereof.

17. The catalyst composition of claim 1, wherein (X)⁶) Is fluoride, chloride, bromide, methoxyl, ethoxyl or hydride.

18. The catalyst composition of claim 1, wherein Al (X)⁵)_n(X⁶)_3-nIs trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-sec-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.

19. The catalyst composition of claim 1, wherein the at least one activator is an activator-support selected from the group consisting of chlorided alumina, fluorided aluminophosphate, sulfated alumina, fluorided silica-alumina, pillared clay, or any combination thereof.

20. The catalyst composition of claim 1, wherein the organoaluminoxane compound comprises:

a cyclic aluminoxane having the formula:

wherein

R is a linear or branched alkyl group having 1 to 10 carbon atoms, n is an integer of 3 to 10;

a linear aluminoxane having the formula:

wherein

R is a linear or branched alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 50;

having the formula R¹ _5m+αR^b _m-αAl_4mO_3mWherein m is 3 or 4, and α ═ n_Al(3)-n_O(2)+n_O(4)(ii) a Wherein n is_Al(3)Is the number of three-coordinate aluminum atoms, n_O(2)Is the number of bidentate oxygen atoms, n_O(4)Is the number of 4 coordinating oxygen atoms, R^tRepresents a terminal alkyl group, R^bRepresents a bridging alkyl group; wherein R is a linear or branched alkyl group having 1 to 10 carbon atoms; or

Any combination thereof.

21. The catalyst composition of claim 1, wherein the organoboron compound or organoborate compound is selected from the group consisting of tris (pentafluorophenyl) boron, tris [3, 5-bis (trifluoromethyl) phenyl]Boron, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenesTetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl]Borate, triphenyl carbonTetrakis [3, 5-bis (trifluoromethyl) phenyl]A borate or any combination thereof.

22. The catalyst composition of claim 1, further comprising an ionizing ionic compound, said ionizing ionic compoundThe chemoattractant is selected from: tri (n-butyl) ammonium tetra (p-tolyl) borate, tri (n-butyl) ammonium tetra (m-tolyl) borate, tri (n-butyl) ammonium tetra (2, 4-dimethylphenyl) borate, tri (n-butyl) ammonium tetra (3, 5-dimethylphenyl) borate, tri (n-butyl) ammonium tetra [3, 5-bis (trifluoromethyl) phenyl ] borate]Borate, tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (p-tolyl) borate, N-dimethylanilinium tetrakis (m-tolyl) borate, N-dimethylanilinium tetrakis (2, 4-dimethylphenyl) borate, N-dimethylanilinium tetrakis (3, 5-dimethylphenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate]Borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbeniumTetra (p-tolyl) borate, triphenylcarbonTetra (m-tolyl) borate, triphenylcarbonTetrakis (2, 4-dimethylphenyl) borate, triphenylcarbenesTetrakis (3, 5-dimethylphenyl) borate, triphenylcarbenesTetrakis [3, 5-bis (trifluoromethyl) phenyl]Borate, triphenyl carbonTetrakis (pentafluorophenyl) borate,Tetra (p-tolyl) borate,Tetra (m-tolyl) borate,Tetrakis (2, 4-dimethylphenyl) borate,Tetrakis (3, 5-dimethylphenyl) borate,Tetrakis [3, 5-bis (trifluoromethyl) phenyl]A borate salt,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) borate, potassium tetrakis (2, 4-dimethylphenyl) borate, potassium tetrakis (3, 5-dimethylphenyl) borate, potassium tetrafluoroborate, triphenyl carbonTetra (p-tolyl) aluminate, triphenyl carbonTetra (m-tolyl) aluminate, triphenyl carbonTetra (2, 4-dimethylphenyl) aluminate, triphenyl carbonTetra (3, 5-dimethylphenyl) aluminate, triphenyl carbonTetrakis (pentafluorophenyl) aluminate,Tetra (p-tolyl) aluminate,Tetra (m-tolyl) aluminate,Tetra (2, 4-dimethylphenyl) aluminate,Tetra (3, 5-dimethylphenyl) aluminate,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 tetrakis (p-tolyl) aluminate, potassium tetrakis (m-tolyl) aluminate, potassium tetrakis (2, 4-dimethylphenyl) aluminate, potassium tetrakis (3, 5-dimethylphenyl) aluminate, potassium tetrakis (p-tolyl) aluminate, potassium tetrakis (m-tolyl) aluminate, potassium tetrakis (2, 4-dimethylphenyl) aluminate, lithium tetrakis (, Potassium tetrafluoroaluminate and triphenyl carbonTris (2, 2' -nonafluorobiphenyl) fluoroaluminate, tetrakis (1, 1,1, 3, 3, 3-hexafluoro-benzeneIsoalcoho) silver aluminate, or silver tetrakis (perfluoro-t-butoxy) aluminate, or any combination thereof.

23. The catalyst composition of claim 1, wherein:

a) the at least one ansa-metallocene comprises:

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 a sulfated solid oxide.

24. The catalyst composition of claim 1, wherein:

a) the at least one ansa-metallocene comprises:

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.

25. 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:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is a carbon atom, a germanium atom, or a tin atom, and E is bonded to (X)¹) And (X)²) Wherein R is¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) fluorine, chlorine, bromine or iodine; 2) a hydrocarbon group having up to 20 carbon atoms, hydrogen, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl group or an aryl group, any of which having up to 12 carbon atoms; at least one of them (X)³) And (X)⁴) Is a hydrocarbon radical having up to 20 carbon atoms, hydrogen or BH₄(ii) a And

any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently a carbon-containing group having from 1 to 20 carbon atoms; halogen root; or hydrogen; and

b) the at least one activator is independently selected 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 organoborate compound; or

iv) any combination thereof.

26. The catalyst composition of claim 25, wherein the carbon-containing group is selected from an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, a silicon-containing group, or a boron-containing group.

27. The catalyst composition of claim 25, wherein any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of an aliphatic group and a cyclic group.

28. The catalyst composition of claim 25, wherein:

a) the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently hydrogen, BH₄Methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH₂CMe₂Ph；CH₂SiMe₂Ph；CH₂CMe₂CH₂Ph; or CH₂SiMe₂CH₂Ph；

E is carbon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently a hydrocarbyl or trihydrocarbylsilyl group-any of which has up to 20 carbon atoms; or hydrogen;

n is an integer from 0 to 10, inclusive; and

R^4Aand R^4BIndependently 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, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, 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. The catalyst composition of claim 28, wherein the mixed oxide is silica-alumina.

30. The catalyst composition of claim 28, wherein the substituted or unsubstituted alkanesulfonate is trifluoromethanesulfonate.

31. A process for producing a polymerization catalyst composition comprising reacting 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)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is a carbon atom, a germanium atom, or a tin atom, and E is substituted with (X)¹) And (X)²) In combination, wherein R¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) f, Cl, Br, or I; 2) hydrocarbyl, H, or BH having up to 20 carbon atoms₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl or 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 a carbon-containing group having from 1 to 20 carbon atoms; halogen root; or hydrogen;

b) the at least one organoaluminum compound comprises a compound having the formula:

Al(X⁵)_n(X⁶)_3-n，

wherein (X)⁵) Is a hydrocarbyl group having 1 to 20 carbon atoms; (X)⁶) Is any one of alkoxy or aryloxy groups having 1 to 20 carbon atoms, a halide or a hydride; and n is a number from 1 to 3, 1 and 3 being included; and

c) the at least one activator is independently selected 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 organoborate compound; or

iv) any combination thereof;

wherein, when: 1) (X)³) And (X)⁴) At least one of (A) is a hydrocarbon group having up to 20 carbon atoms, H or BH₄(ii) a 2) The at least one activator comprises an organoaluminoxane compound; or 3) the at least one organoaluminum compound is optional when both conditions 1 and 2 are present.

32. The catalyst composition of claim 31, wherein the carbon-containing group is selected from an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, a silicon-containing group, or a boron-containing group.

33. The method of producing a polymerization catalyst composition of claim 31, wherein any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of an aliphatic group and a cyclic group.

34. The method of producing a polymerization catalyst composition of claim 31, wherein:

a) the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently F, Cl, Br or I;

e is C;

R¹and R²Independently is an alkyl or aryl group, either of which having up to 10 carbon atoms, or is hydrogen, wherein R is¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently a hydrocarbyl or trihydrocarbylsilyl group, any of which has up to 20 carbon atoms; or hydrogen;

n is an integer from 0 to 10, including 0 and 10; and is

R^4AAnd R^4BIndependently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen;

b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, 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, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, 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.

35. The catalyst composition of claim 34, wherein the mixed oxide is silica-alumina.

36. The catalyst composition of claim 34, wherein the substituted or unsubstituted alkanesulfonate is trifluoromethanesulfonate.

37. The method of producing a polymerization catalyst composition of claim 34, wherein the at least one organoaluminum compound comprises triisobutylaluminum or triisohexylaluminum.

38. A process for producing a polymerization catalyst composition comprising reacting 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:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is

A carbon atom, a germanium atom, or a tin atom, and E is bonded to (X)¹) And (X)²) Wherein R is¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) fluorine, chlorine, bromine or iodine; 2) a hydrocarbon group having up to 20 carbon atoms, hydrogen, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl group or an aryl group, any of which having up to 12 carbon atoms; at least one of them (X)³) And (X)⁴) Is a hydrocarbon radical having up to 20 carbon atoms, hydrogen or BH₄(ii) a And

any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently a carbon-containing group having from 1 to 20 carbon atoms; halogen root; or hydrogen; and

b) the at least one activator is independently selected 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 organoborate compound; or

iv) any combination thereof.

39. The catalyst composition of claim 38, wherein the carbon-containing group is selected from an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, a silicon-containing group, or a boron-containing group.

40. The method of producing a polymerization catalyst composition of claim 38, wherein any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of an aliphatic group and a cyclic group.

41. The method of producing a polymerization catalyst composition of claim 38, wherein:

a) the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently hydrogen、BH₄Methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH₂CMe₂Ph；CH₂SiMe₂Ph；CH₂CMe₂CH₂Ph; or CH₂SiMe₂CH₂Ph；

E is carbon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently a hydrocarbyl or trihydrocarbylsilyl group-any of which has up to 20 carbon atoms; or hydrogen;

n is an integer from 0 to 10, inclusive; and

R^4Aand R^4BIndependently 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, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, 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.

42. The catalyst composition of claim 41, wherein the mixed oxide is silica-alumina.

43. The catalyst composition of claim 41, wherein the substituted or unsubstituted alkanesulfonate is trifluoromethanesulfonate.

44. A process for polymerizing olefins comprising:

contacting ethylene and optionally an alpha-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer;

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:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is a carbon atom, a germanium atom, or a tin atom, and E is substituted with (X)¹) And (X)²) In combination, wherein R¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) f, Cl, Br, or I; 2) hydrocarbyl, H, or BH having up to 20 carbon atoms₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl or 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 a carbon-containing group having from 1 to 20 carbon atoms; halogen root; or hydrogen;

b) the at least one organoaluminum compound comprises a compound having the formula:

Al(X⁵)_n(X⁶)_3-n，

wherein (X)⁵) Is a hydrocarbyl group having 1 to 20 carbon atoms; (X)⁶) Is any one of alkoxy or aryloxy groups having 1 to 20 carbon atoms, a halide or a hydride; and n is a number from 1 to 3, 1 and 3 being included; and

c) the at least one activator is independently selected 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 organoborate compound; or

iv) any combination thereof;

wherein, when: 1) (X)³) And (X)⁴) At least one of (A) is a hydrocarbon group having up to 20 carbon atoms, H or BH₄(ii) a 2) The at least one activator comprises an organoaluminoxane compound; or 3) the at least one organoaluminum compound is optional when both conditions 1 and 2 are present.

45. The catalyst composition of claim 44, wherein the polymer is a copolymer.

46. The catalyst composition of claim 44, wherein the carbon-containing group is selected from an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, a silicon-containing group, or a boron-containing group.

47. The process for polymerizing olefins of claim 44, wherein 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 an aliphatic group and a cyclic group.

48. The process for polymerizing olefins according to claim 44, wherein:

a) the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently F, Cl, Br or I;

e is C;

R¹and R²Independently is an alkyl or aryl group, either of which having up to 10 carbon atoms, or is hydrogen, wherein R is¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently a hydrocarbyl or trihydrocarbylsilyl group, any of which has up to 20 carbon atoms; or hydrogen;

n is an integer from 0 to 10, including 0 and 10; and is

R^4AAnd R^4BIndependently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen;

b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, 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, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, 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.

49. The catalyst composition of claim 48, wherein the mixed oxide is silica-alumina.

50. The catalyst composition of claim 48, wherein the substituted or unsubstituted alkanesulfonate is trifluoromethanesulfonate.

51. The process for polymerizing olefins according to claim 48, wherein the at least one organoaluminum compound comprises triisobutylaluminum or triisohexylaluminum.

52. A polymer produced by the method of claim 44.

53. An article comprising the polymer produced by the method of claim 44.

54. A process for polymerizing olefins comprising:

contacting ethylene and optionally an alpha-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer;

wherein the catalyst composition comprises 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:

(X¹)(X²)(X³)(X⁴)M¹wherein

M¹Is titanium, zirconium or hafnium;

(X¹) And (X)²) Independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl;

in (X)¹) And (X)²) One substituent on is of the formula ER¹R²Wherein E is

A carbon atom, a germanium atom, or a tin atom, and E is bonded to (X)¹) And (X)²) Wherein R is¹And R²Independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein R¹And R²At least one of (a) is an aryl group;

in (X)¹) Or (X)²) At least one substituent on (a) is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms;

(X³) And (X)⁴) Independently are: 1) fluorine, chlorine, bromine or iodine; 2) a hydrocarbon group having up to 20 carbon atoms, hydrogen, or BH₄(ii) a 3) A hydrocarbyloxy group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR^A ₂Or SO₃R^AWherein R is^AIs an alkyl group or an aryl group, any of which having up to 12 carbon atoms; at least one of them (X)³) And (X)⁴) Is a hydrocarbon radical having up to 20 carbon atoms, hydrogen or BH₄(ii) a And

any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently a carbon-containing group having from 1 to 20 carbon atoms; halogen root; or hydrogen; and

b) the at least one activator is independently selected 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 organoborate compound; or

iv) any combination thereof.

55. The catalyst composition of claim 54, wherein the polymer is a copolymer.

56. The catalyst composition of claim 54, wherein the carbon-containing group is selected from an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, a silicon-containing group, or a boron-containing group.

57. The process for polymerizing olefins of claim 54, wherein any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of an aliphatic group and a cyclic group.

58. The process for polymerizing olefins according to claim 54, wherein:

a) the at least one ansa-metallocene comprises a compound having the formula:

wherein

M¹Is zirconium or hafnium;

x is independently hydrogen, BH₄Methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH₂CMe₂Ph；CH₂SiMe₂Ph；CH₂CMe₂CH₂Ph; or CH₂SiMe₂CH₂Ph；

E is carbon;

R¹and R²Independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein R¹Or R²At least one of (a) is an aryl group;

R^3Aand R^3BIndependently a hydrocarbyl or trihydrocarbylsilyl group-any of which has up to 20 carbon atoms; or hydrogen;

n is an integer from 0 to 10, inclusive; and

R^4Aand R^4BIndependently 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, aluminum phosphate, aluminophosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

the electron-withdrawing anion is fluoride, chloride, bromide, iodide, 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.

59. The catalyst composition of claim 58, wherein the mixed oxide is silica-alumina.

60. The catalyst composition of claim 58, wherein the substituted or unsubstituted alkanesulfonate is trifluoromethanesulfonate.

61. A polymer produced by the method of claim 54.

62. An article comprising the polymer produced by the method of claim 54.

63. A compound having the formula:

wherein M is²Is Zr or Hf.