JP7285286B2 - Production of polyolefin products - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a United States provisional patent application having the following number: Ching-Tai Lue et al.
RV), No. 61/93 by Ching-Tai Lue et al., filed Feb. 11, 2014.
8,472 (2014U003.PRV), filed April 18, 2014 by Franci
sC. Rix et al., 61/981,291 (2014U010.PRV), 20
Francis C., filed Apr. 28, 14; Rix et al., 61/985,151 (2014U012.PRV), Sun-Chueh Kao filed Aug. 1, 2014;
62/032,383 (2014U018.PRV), Dec. 5, 2014 to
Francis C., filed on Sept. Rix et al., 62/087,905 (2014 U0
35. PRV), Daniel P., filed Dec. 5, 2014; Zilker, Jr.
62/088,196 (2014U036.PRV), Dec. 5, 2014 to
No. 62/087,911 by Ching-Tai Lue et al.
37. PRV), and Francis C. claims the benefit of Rix et al. 62/087,914 (2014U038.PRV);
These disclosures are incorporated herein by reference in their entirety.

Ethylene α-olefin (polyethylene) copolymers are typically produced in low pressure reactors using, for example, solution, slurry, or gas phase polymerization processes. Polymerization occurs in the presence of a catalyst system such as, for example, a catalyst system using Ziegler-Natta catalysts, chromium-based catalysts, metallocene catalysts, or combinations thereof.

Several catalyst compositions containing single-site (eg, metallocene) catalysts have been used to prepare polyethylene copolymers to produce relatively uniform polymers with good polymerization rates. Single-site catalyst compositions, such as metallocene catalysts, in contrast to traditional Ziegler-Natta catalyst compositions, are catalyst compounds in which each catalyst molecule contains one or only a few polymerization sites. Single-site catalysts often produce polyethylene copolymers with narrow molecular weight distributions. Although there are single-site catalysts that can lead to broader molecular weight distributions, these catalysts often exhibit a narrowing of the molecular weight distribution as the reaction temperature is increased, for example to increase the rate of production. In addition, single-site catalysts often incorporate comonomer at a relatively uniform rate between the polyethylene copolymer molecules.
The molecular weight distribution and the amount of comonomer incorporation can be used to determine the compositional distribution.

The compositional distribution of ethylene α-olefin copolymers refers to the distribution of comonomers that form short chain branches among the molecules that make up the polyethylene polymer. When the amount of short chain branching differs among the polyethylene molecules, the resin is said to have a "broad" composition distribution. 100
When the amount of comonomer per zero carbon is similar among polyethylene molecules of different chain lengths, the composition distribution is said to be "narrow."

Compositional distribution is known to affect copolymer properties such as stiffness, toughness, extractable content, environmental stress crack resistance, and heat weld, among other properties. The compositional distribution of polyolefins can be determined by methods known in the art, such as temperature-rising elution fractionation (Tempe
Nature Raising Elution Fractionation) (TR
EF) or by crystallization analysis fractionation (CRYSTAF).

It is generally known in the art that the compositional distribution of polyolefins is largely dictated by the type of catalyst used and is typically invariant for a given catalyst system. Ziegler-Natta catalysts and chromium-based catalysts produce resins with a broad composition distribution (BCD), while talocene catalysts typically produce resins with a narrow composition distribution (NCD).

Broad orthogonal compositional distribution, in which comonomers are predominantly incorporated into high molecular weight chains
orthogonal composition distribution) (BO
CD) have improved physical properties such as toughness properties and environmental stress crack resistance (E
SCR). Since this improved physical properties of resins with orthogonal composition distributions are required for commercially desirable products, there is a need for controlled techniques for forming polyethylene copolymers with broad orthogonal composition distributions. gender exists.

Exemplary embodiments described herein provide methods for alkylating organometallic compounds while substantially standardizing stereochemical configuration. The method comprises slurrying an organometallic compound in dimethoxyethane (DME) and adding a solution of RMgBr in DME, where R is a methyl or benzyl group and RMgBr is , greater than about 2.3 equivalents relative to the organometallic compound. After the addition of RMgBr, the slurry is at least about 4
time mixed. The alkylated organometallic is isolated and the methylated species is about 0.9
It has a meso/rac ratio that is to about 1.2.

Another exemplary embodiment described herein provides a method of alkylating an organometallic compound while substantially standardizing the stereochemical configuration. The method comprises slurrying an organometallic compound in ether and adding a solution of RLi in ether, where R is a methyl or benzyl group and RMgBr is an organometallic compound about 2 for
. more than 3 equivalents. After adding the RMgBr, the slurry is mixed for at least about 4 hours.
Alkylated organometallic isolated and methylated species have a meso/rac ratio that is from about 0.9 to about 1.2.

Another exemplary embodiment provides a catalyst composition comprising a first catalyst compound and a second catalyst compound co-supported to form a co-supported catalyst system, the first catalyst compound comprising: the formula for
_{( C5HaR1b )} ^{( C5HcR2d} _{) HfX2 _ _}

and each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. Each ^R2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group,
or a heteroatom group. The values of a and c are ≧3 and a+b=c+d=5.
At least one R ¹ and at least one R ² are hydrocarbyl or substituted hydrocarbyl groups. Adjacent radicals R ¹ and R ² groups may be joined to form a ring. Each X is independently a leaving group selected from labile hydrocarbyls, substituted hydrocarbyls, or heteroatom groups. The second catalyst compound comprises a mixture of the following enantiomers,

The ratio of meso to rac enantiomers is about 1.0 to
substantially normalized to about 1.2. Each ^R3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. ^R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group. Each ^R5 is independently H,
It is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. R ³ , R ⁴ and R ⁵ may be the same or different. Each X is a methyl group.

Another exemplary embodiment provides a method of polymerizing an olefin to produce a polyolefin polymer having a multimodal composition distribution, comprising contacting ethylene and a comonomer with a catalyst system, the The catalyst system comprises a first catalyst compound and a second catalyst compound co-supported to form a co-supported catalyst system, the first catalyst compound having the formula:
_{( C5HaR1b )} ^{( C5HcR2d} _{) HfX2 _ _}

and each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. Each ^R2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group,
or a heteroatom group. The values of a and c are ≧3 and a+b=c+d=5.
At least one R ¹ and at least one R ² are hydrocarbyl or substituted hydrocarbyl groups. Adjacent radicals R ¹ and R ² groups may be joined to form a ring. Each X is independently a leaving group selected from labile hydrocarbyls, substituted hydrocarbyls, or heteroatom groups. The second catalyst compound contains a mixture of the following enantiomers.

The meso enantiomer is at least about 15 parts in the mixture and the rac enantiomer is
Less than about 5 parts in the mixture. Each ^R3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. ^R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group. Each ^R5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. R ³ , R ⁴ and R ⁵
may be the same or different. Each X is independently a leaving group selected from labile hydrocarbyls, substituted hydrocarbyls, heteroatom groups, or divalent radicals linked to ^R3 , ^R4 , or ^R5 groups.

Another exemplary embodiment provides a polyolefin polymer comprising ethylene and an α-olefin having from 4 to 20 carbon atoms , the polyolefin polymer being co-supported to form a co-supported catalyst system. and a second catalyst compound, wherein the first catalyst compound has the formula:
_{( C5HaR1b )} ^{( C5HcR2d} _{) HfX2 _ _}

wherein each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R ² is independently H, a hydrocarbyl group, a substituted hydrocarbyl group,
or a heteroatom group, a and c are ≧3, a+b=c+d=5, at least one R ¹ and at least one R ² is a hydrocarbyl or substituted hydrocarbyl group, and in adjacent groups Certain R ¹ and R ² groups may be joined to form a ring, each X is independently a leaving group selected from labile hydrocarbyl, substituted hydrocarbyl, or heteroatom groups; contains a mixture of the following enantiomers:

The ratio of one enantiomer to the other enantiomer is at least about three. Each R ³
is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. ^R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoa
tom) groups and each R ⁵ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group,
or a heteroatom group, and R ³ , R ⁴ , and R ⁵ may be the same or different,
Each X is independently a leaving group selected from labile hydrocarbyls, substituted hydrocarbyls, heteroatom groups, or divalent radicals linked to ^R3 , ^R4 , or ^R5 groups.

Another exemplary embodiment provides a method of forming a catalyst composition. The method comprises dissolving 1-ethylindenyllithium in dimethoxyethane to form a precursor solution, cooling the precursor solution to about −20° C., and solid ZrCl ₄ for about 5 minutes. to initiate the reaction, continuing the reaction overnight, removing volatiles to form a raw product, and extracting the raw product with CH ₂ Cl ₂ . and the CH
removing ₂ Cl ₂ under vacuum to form a mixture comprising about 19 parts meso-(1-EtInd) ₂ ZrCl ₂ and about 1 part rac-(1-EtInd) ₂ ZrCl ₂ . .

1 is a schematic diagram of a gas phase reactor system showing the addition of at least two catalysts, at least one of which is added as a trim catalyst; FIG. 1 is a plot of a series of polymers prepared to test the relative ability of a series of metallocene catalysts to prepare resins having a melt index (MI) of about 1 and a density (D) of about 0.92. . FIG. 3 is a plot of the series of polymers of FIG. 2 showing the melt index ratio (MIR) of a series of polymers made with different metallocene (MCN) catalysts; 1 is a flow chart of a method for making a co-supported polymerization catalyst.

When a support is impregnated with multiple catalysts, it is possible to obtain new polymeric materials with improved stiffness, toughness, and processability, for example, by controlling the amount and type of catalyst present on the support. Do you get it. With the selection of appropriate catalysts and ratios, as described in embodiments herein, for example, to provide a polymer with a broad orthogonal composition distribution (BOCD) of the polymer, the molecular weight distribution (MWD), Short chain branching distribution (SCBD) and long chain branching distribution (LCBD) can be adjusted. MWD, SCBD, and LCBD are
Appropriate weight average molecular weight (Mw), comonomer incorporation, and long chain branching (L
CB) will be controlled by combining catalysts with formation.

Production of products in one reactor instead of multiple reactors by employing multiple pre-catalysts co-supported on a single support mixed with an activator such as silica methylaluminoxane (SMAO) can bring about cost advantages. Furthermore, the use of a single support ensures intimate mixing of the polymers and improved operability for the preparation of polymer mixtures of different Mw and densities independent of multiple catalysts in a single reactor. also provide. A pre-catalyst, as used herein, is a catalyst compound prior to exposure to an activator.

As an example, for linear low density polyethylene film (LLDPE) film applications, a molecular weight of about 90 Kg/mol to 110 Kg/mol, or about 100 Kg/mol,
and an average density of about 0.9 to 0.925, or about 0.918. A typical MWD for linear metallocene resins is 2
. 5 to 3.5. Blending studies indicate that it may be desirable to broaden this distribution by employing two catalysts each yielding a different average molecular weight. The Mw ratio of the low molecular weight component to the high molecular weight component is from 1:1 to 1:10, or from about 1:2 to 1:5
Will.

The density of polyethylene copolymers is an indicator of comonomer incorporation into the polymer, with lower densities indicating higher incorporation. the difference between the density of the low molecular weight (LMW) component and the density of the high molecular weight (HMW) component is preferably greater than about 0.02, or greater than about 0.04;
HMW components have a lower density than LMW components. 25 Kg/mol and 125
For two resins with Mw of Kg/mol, the density difference in comonomer incorporation capacity is about 1.5:1, or preferably about 2:1, or more preferably about 3:1, or more preferably Requires a difference of 4:1 or even more than 4:1. It is also desirable to minimize the level of long chain branching (LCB) in the polymer, which imbalances MD/TD tear strength and reduces toughness, as it provides strong orientation in film production.

These factors can be adjusted by controlling MWD and SCBD, M
WD and SCBD can in turn be adjusted by changing the relative amounts of the two pre-catalysts on the support. This can be adjusted during the formation of the pre-catalyst, for example by supporting two catalysts on a single support. In some embodiments, the relative amount of pre-catalyst can be adjusted by adding one of the components to the catalyst mixture on its way to the reactor in a process called "trim." Metallocene (MCN
) are known to trim well with other catalysts.

Furthermore, various resins with different MWD, SCBD, and LCBD can be prepared from a limited number of catalysts. To perform this function, the pre-catalyst should be well trimmed onto the activator support. Two parameters that are beneficial to this are the solubility of the alkane solvent and the rapid loading onto the catalyst slurry on its way to the reactor. For this, it is advantageous to obtain controlled MWD, SCBD and LCBD using MCN. Techniques for selecting catalysts that can be used to produce target molecular weight compositions, including BOCD polymer systems, are disclosed herein.

A variety of catalyst systems and components can be used to produce the disclosed polymers and molecular weight compositions. These are discussed in the next section. Section 1 discusses catalyst compounds that may be used in embodiments. Section 2 discusses the production of catalyst slurries that can be used to practice the described techniques. Section 3 discusses catalyst supports that may be used. Section 4 discusses catalyst activators that may be used. Section 5 discusses catalyst component solutions that can be used to add additional catalyst to the trim system. Gas phase polymerization uses static control agents or continuity agents, which are discussed in Section 6. Gas phase polymerization reactors with trim feed systems are discussed in Section 7. The use of catalyst compositions to control product properties is discussed in Section 8, and exemplary polymerization processes are discussed in Section 9. An example of the procedure discussed is incorporated in Section 10.

Catalyst Compounds Metallocene Catalyst Compounds Metallocene catalyst compounds comprise at least one Group 3-12 metal atom and one or more leaving group(s) attached to at least one metal atom 1 more than one C
It may include "half-sandwich" and/or "full-sandwich" compounds with p-ligands (ligands isolobal to cyclopentadienyl and cyclopentadienyl). As used herein, all references to the Periodic Table of the Elements and Groups thereof, unless reference is made to a previous IUPAC form noted in Roman numerals (indicated therein),
or HAWLEY'S CONDENSED CHEMICA unless otherwise stated
L DICTIONARY, Thirteenth Edition, John Wil
ey & Sons, Inc. (1997) (reproduced therein with permission of IUPAC).

The Cp ligands are one or more rings or ring system(s), at least some of which contain π-bonded systems such as cycloalkadienyl ligands and heterocyclic analogues. The ring(s) or ring system(s) typically comprise atoms selected from the group consisting of atoms of Groups 13-16, and in certain exemplary embodiments the Cp ligand are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, wherein carbon comprises at least 50% of the ring members .
In a more particular exemplary embodiment, the Cp ligand(s) is selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl; Non-limiting examples thereof include cyclopentadienyl, indenyl, fluorenyl, and other structures. Further non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentaocyclod Decene, phenanthlinedenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9] Anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or " _H4 indo"), substituted versions of these (described in more detail below discussed and described), and heterocyclic versions of these.

The metal atom "M" of the metallocene catalyst compound is, in one exemplary embodiment, selected from the group consisting of Groups 3-12 atoms and Lanthanum Group atoms, and in a more particular exemplary embodiment,
selected from the group consisting of atoms of Groups 3-10, and in even more particular exemplary embodiments,
c, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh,
selected from the group consisting of Ir and Ni, and in an even more particular exemplary embodiment fourth,
5, and Group 6 atoms, and in even more particular exemplary embodiments,
selected from the group consisting of Ti, Zr, Hf atoms, and in an even more particular exemplary embodiment,
Hf. The oxidation state of the metal atom “M” may range from 0 to +7 in one exemplary embodiment, and may be +1, +2, +3, +4, or +5 in more specific exemplary embodiments. , and in even more specific exemplary embodiments may be +2, +3 or +4. The groups attached to the metal atom "M" are those groups such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated. The Cp ligand forms at least one chemical bond with the metal atom M to form a "metallocene catalyst compound". Cp ligands are distinct from leaving groups attached to catalyst compounds in that they are not highly susceptible to substitution/abstraction reactions.

The one or more metallocene catalyst compounds have formula (I),
Cp ^A Cp ^B MX _n (I)

wherein M is as defined above, each X is chemically bonded to M, and each Cp
The group is chemically bonded to M and n is 0 or an integer from 1 to 4, and in certain exemplary embodiments is either 1 or 2.

The ligands represented by Cp ^A and Cp ^B in formula (I) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, may contain heteroatoms and either or both of them may be substituted with the group R. In at least one particular embodiment, Cp ^A and Cp ^B are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

Independently, each Cp ^A and Cp ^B of formula (I) can be unsubstituted or substituted with any one or combination of substituents R. Non-limiting examples of substituents R used in structure (I), as well as ring substituents of structures Va-d discussed and described below, include hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, from the group consisting of aryl, acyl, aroyl, alkoxy, aryloxy, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino, and combinations thereof Selected groups are included. formula(
More specific non-limiting examples of alkyl substituents R in relation to I)-(Va-d) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups, including isomers thereof such as tertiary butyl, isopropyl, and the like.

As used in the specification and claims, hydrocarbyl substituents or hydrocarbyl groups are composed of 1 to 100 or more carbon atoms, the remainder being hydrogen. Non-limiting examples of hydrocarbyl substituents include linear or branched or cyclic alkyl radicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals , or combinations thereof. Non-limiting examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl; olefinically unsaturated substituents containing vinyl-terminated ligands (e.g., but-3-enyl, prop- 2-enyl, hex-5-enyl, etc.), benzyl or phenyl groups and the like, including all isomers thereof such as tertiary butyl, isopropyl and the like.

As used in the specification and claims, substituted hydrocarbyl substituents, or hydrocarbyl groups, are comprised of from 1 to 100 or more carbon atoms, the remainder being hydrogen, fluorine,
Chlorine, bromine, iodine, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, germanium, or tin atoms, or other atomic systems that are resistant to olefin polymerization systems. Substituted hydrocarbyl substituents are carbon-based radicals. Non-limiting examples of substituted hydrocarbyl substituents are the trifluoromethyl radical, the trimethylsilanemethyl (Me ₃ SiCH ^2- ) radical.

As used herein and in the claims, heteroatom substituents, or heteroatom groups, include fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, germanium, or tin based radicals. is. These may themselves be heteroatom atoms. Additionally, heteroatom substituents include organometalloid radicals. Non-limiting examples of heteroatom substituents include chloro radicals, fluoro radicals, methoxy radicals, diphenylamino radicals, thioalkyls, thioalkenyls,
trimethylsilyl radical, dimethylaluminum radical, alkoxydihydrocarbylsilyl radical, siloxydiydrocab
ylsilyl) radical, tris(perfluorophenyl) boron, and the like.

Other possible radicals are substituted alkyl and aryl, such as fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl, hydrocarbyl-substituted organometalloid radicals (trimethylsilyl, trimethylgermyl, methyl diethylsilyl, etc.), and halocarbyl-substituted organometallic radicals (including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl, etc.), and disubstituted boron radicals (e.g., dimethylboron). ), and disubstituted Group 15 radicals (including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine), and Group 16 radicals (including methoxy, ethoxy, propoxy, phenoxy, methylsulfide, and ethylsulfide). include. Other substituents R include, but are not limited to, olefins such as olefinically unsaturated substituents (including vinyl-terminated ligands such as 3-butenyl, 2-propenyl, 5-hexenyl, etc.). . In one exemplary embodiment,
at least two R groups (in one particular exemplary embodiment, two adjacent R groups) are joined and consist of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, and combinations thereof forming a ring structure having 3 to 30 atoms selected from the group; Also, a substituent R such as 1-butanyl can form a bond association to the element M.

Each X of formula (I) above and formulas/structures (II)-(Va-d) below is independently, in one exemplary embodiment, any leaving group; in the form of halogen ions,
hydride, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₂ aryl, C
₇ - _C20 alkylaryl, _C1 - _C12 alkoxy, _C6 - _C16 aryloxy,
C ₇ -C ₈ alkylaryloxy, C ₁ -C ₁₂ fluoroalkyl, C ₆ -C ₁₂ fluoroaryl, and C ₁ -C ₁₂ heteroatom-containing hydrocarbons, and substituted derivatives thereof; hydrides, halogen ions, C ₁ - _C6 alkyl, _C2 - _C6 alkenyl, _C7 - _C18 alkylaryl, _C1 - _C6 alkoxy, _C6 - _C14 aryloxy, _C7 - _C16 alkylaryloxy, leading to new polymerization catalysts C ₁ -C ₆ alkyl carboxyl (a
lkylcarboxyla), C ₁ -C ₆ fluorinated alkyl carboxylates, C ₆ -
C ₁₂ aryl carboxylates, C ₇ -C ₁₈ alkyl aryl carboxylates, C
₁ -C ₆ fluoroalkyl, C ₂ -C ₆ fluoroalkenyl, and C ₇ -C ₁₈ fluoroalkylaryl; in even more specific exemplary embodiments, hydride, chloride, fluoride, methyl, phenyl, phenoxy , benzooxy, tosyl, fluoromethyl, and fluorophenyl; C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₂ aryl,
C ₇ -C ₂₀ alkylaryl, substituted C ₁ -C ₁₂ alkyl, substituted C ₆ -C ₁₂ aryl, substituted C ₇ -C ₂₀ alkylaryl, and C ₁ -C ₁₂ heteroatom-containing alkyl, C ₁
to C ₁₂ heteroatom-containing aryl, and C ₁ -C ₁₂ heteroatom-containing alkylaryl;
In even more specific exemplary embodiments, chloride, fluoride, C ₁ -C ₆ alkyl, C ₂ -
C ₆ Alkenyl, C ₇ -C ₁₈ Alkylaryl, C ₁ -C ₆ Alkyl Halide, C ₂ -C ₆ Alkenyl Halide, and C ₇ -C ₁₈ Alkyl Aryl Halide; Even More Specific Exemplary Embodiments Fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyl (mono-, di-, and trifluoromethyl), and fluorophenyl (mono-, di-, tri-, tetra-, and pentafluorophenyl); and in even more particular exemplary embodiments, fluoride.

Other non-limiting examples of X groups include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having _from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., _-C6F5 (pentafluorophenyl)), fluorinated alkyl carboxylates (eg CF ₃ C(O)O ⁻ ), hydrides, halogen ions, and combinations thereof. Other examples of X ligands are cyclobutyl, cyclohexyl, methyl,
heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),
Examples include alkyl groups such as dimethylamide and dimethylphosphide radicals. In one exemplary embodiment, two or more X form part of a fused ring or ring system. In at least one particular embodiment, X is chloride ion, bromide ion, C ₁ -C ₁₀ alkyl, and C ₂
It may be a leaving group selected from the group consisting of _-C12 alkenyls, carboxylates, acetylacetonates, and alkoxides.

Metallocene catalyst compounds include those of formula (I), wherein Cp ^A and Cp ^B are bridged together by at least one bridging group (A), such that the structure is represented by formula (II) be.
Cp ^A (A) Cp ^B MX _n (II)

These bridged compounds represented by formula (II) are known as "bridged metallocenes". Elements Cp ^A , Cp ^B , M, X, and n of structure (II) are as defined above for formula (I), wherein each Cp ligand is chemically bonded to M, (A) is chemically bonded to each Cp. Bridging group (A) contains at least one group 13-16 atom, such as at least one of carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, tin atoms, and combinations thereof It can include divalent hydrocarbon groups, where heteroatoms can also be C ₁ -C ₁₂ alkyl or aryl substituted to satisfy neutral valences. In at least one particular embodiment, bridging group (A) may also include substituent groups R as defined above (with respect to formula (I)), including halogen radicals and iron. In at least one particular embodiment, bridging group (A) is C ₁ -C ₆ alkylene, substituted C ₁ -C ₆
alkylene, oxygen, sulfur, _R'2C =, _R'2Si =, =Si(R') _2Si ( _R'2 )
=, R' ₂ Ge=, and R'P=, where "=" represents two chemical bonds and "R'" independently represents hydride, hydrocarbyl, substituted hydrocarbyl , halocarbyls, substituted halocarbyls, hydrocarbyl-substituted organic semimetals, halocarbyl-substituted organic semimetals, disubstituted boron, disubstituted group 15 atoms, substituted group 16 atoms, and halogen radicals, and two or more R ' can be joined to form a ring or ring system. In at least one particular embodiment, the bridged metallocene catalyst compound of formula (II) comprises two or more bridging groups (A). In one or more embodiments, (A) is a divalent _Cl -C
₂₀ hydrocarbyl and hydroxyl-containing C ₁ -C ₂₀ heteroatoms attached to both Cp ^A and Cp ^B , wherein the hydrocarbyl-containing heteroatom Atoms include 1-3 heteroatoms.

The bridging group (A) is methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,
1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n
-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t-butyl) phenyl)silyl, di(p-
tolyl)silyl and corresponding moieties where Si atoms are replaced with Ge or C atoms, as well as dimethylsilyl, diethylsilyl, dimethylgermyl, and diethylgermyl. The bridging groups (A) are -SiMe ₂ -O-SiMe ₂ - and -SiPh ₂ -O-SiPh ₂
It can also include -Si(hydrocarbyl) ₂ -O-(hydrocarbyl) ₂ Si--Si(substituted hydrocarbyl) ₂ -O-(substituted hydrocarbyl) ₂ Si- groups such as - and the like.

Bridging group (A) may also be cyclic, for example having 4 to 10 ring members, and in more particular exemplary embodiments, bridging group (A) may have 5 to 7 ring members. . Ring members may be selected from the elements described above, and in certain embodiments may be selected from one or more of B, C, Si, Ge, N, and O. Non-limiting examples of ring structures that can be present as or part of a bridging moiety include cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, and one or two A corresponding ring in which a carbon atom is substituted with at least one of Si, Ge, N and O. In one or more embodiments, 1
One or two carbon atoms may be replaced with at least one of Si and Ge. The bonding configuration between the ring and the Cp group can be cis-, trans-, or a combination thereof.

The cyclic bridging group (A) may be saturated or unsaturated and/or may bear one or more substituents and/or may be fused to one or more other ring structures. When present, the one or more substituents may, in at least one particular embodiment, be selected from the group consisting of hydrocarbyl (eg, alkyl such as methyl), and halogen (eg, F, Cl). The one or more Cp groups to which the above cyclic bridging moieties may optionally be fused may be saturated or unsaturated and have 4 to 10, more particularly 5, 6, or 7 ring members (certain exemplary In an embodiment,
C, N, O, and S), for example selected from the group consisting of cyclopentyl, cyclohexyl, phenyl, and the like. Additionally, these ring structures may themselves be fused, for example, in the case of naphthyl groups. Additionally, these (optionally fused) ring structures may carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbyl (especially alkyl) groups and halogen atoms. The ligands Cp ^A and Cp ^B of formulas (I) and (II) may be different from each other. The ligands Cp ^A and Cp ^B of formulas (I) and (II) may be identical. Metallocene catalyst compounds can include bridged mono-ligand metallocene compounds (eg, monocyclopentadienyl catalyst components).

The metallocene catalyst components discussed and described above include their structural or optical or enantiomeric isomers (racemic mixtures), and in one exemplary embodiment can be pure enantiomers. is assumed. As used herein, a single bridged asymmetrically substituted metallocene catalyst compound having racemic and/or meso isomers does not itself constitute at least two different bridged metallocene catalyst components.

As noted above, the amount of transition metal component of the one or more metallocene catalyst compounds in the catalyst system is about 0.01 weight percent, about 0.2 weight percent, based on the total weight of the catalyst system. %, from a lower limit of about 3%, about 0.5%, or about 0.7% to about 1%, about 2%, about 2%.
It can range up to an upper limit of 5 wt%, about 3 wt%, about 3.5 wt%, or about 4 wt%.

A "metallocene catalyst compound" can include any combination of any of the "embodiments" discussed and described herein. For example, metallocene catalyst compounds include bis(n-propylcyclopentadienyl)hafnium (CH ₃ ) ₂ , bis(n-propylcyclopentadienyl)hafnium F ₂ , bis(n-propylcyclopentadienyl)hafnium C
l ₂ , bis(n-butyl,methylcyclopentadienyl)zirconium Cl ₂ , or [
(2,3,4,5,6Me5C6N) _CH2CH2 ] _2NHZrBn2 , where Bn is _{a benzyl} group, or any combination thereof _{, but} is limited to not.

Other metallocene catalyst compounds that can be used include supported constrained geometry catalysts (sCG
C). In some embodiments, the sCGC catalyst may contain borate ions. The borate anion is represented by the formula [BQ _4-z' (G _q (T--H) _r ) _z' ] ^d- , where B is boron with a valence state of 3 and Q is , hydrides, dihydrocarbylamides, halides, hydrocarbyloxides, hydrocarbyls, and substituted hydrocarbyl radicals, z' is an integer from 1 to 4, and G is an M' and r group (T-- H.
) is a multivalent hydrocarbon radical having a valence of r+1, q is an integer of 0 or 1, and the group (T--H) is a radical wherein T is O , S, NR, or PR, the O, S, N, or P atom of which is bonded to a hydrogen atom, H, where R is
hydrocarbyl radical, trihydrocarbylsilyl radical, trihydrocarbylgermyl radical, or hydrogen), r is an integer from 1 to 3, and d is 1. Alternatively, the borate ion has the formula [BQ _4-z' (G _q (T--M ^o R ^C _x-1 X ^a _y ) _r ) _z' ]
^d- , where B is boron with a valence state of 3, and Q is
is selected from the group consisting of hydrides, dihydrocarbylamides, halides, hydrocarbyloxides, hydrocarbyls, and substituted hydrocarbyl radicals, z' is an integer from 1 to 4, and G is a B and r group (T-- ^Mo R ^C _x−1 X ^a _y ) is a multivalent hydrocarbon radical having a valence of r+1, q is an integer of 0 or 1, and the group (T−−M
^o R ^C _x-1 X ^a _y ) is a radical, wherein T comprises O, S, NR, or PR, the O, S, N, or P atom of which is bonded to M ^{2 o} , wherein and R is a hydrocarbyl radical, trihydrocarbylsilyl radical, trihydrocarbylgermyl radical, or hydrogen), ^Mo is a metal or metalloid selected from Groups 1-14 of the Periodic Table of the Elements, and R ^C is independently at each occurrence hydrogen or a group having 1 to 80 non-hydrogen atoms (which is hydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilyl hydrocarbyl) and X ^a is 1 to 100 (halo-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy, or halide) having a non-hydrogen atom, and x is 1 to a non-zero integer that can range from an integer equal to the valence of M ^o and y is a non-zero integer that can range from 0 or from 1 to the valence of M ^o minus 1 where x+y is equal to the valence of M ^{2 o} , r is an integer from 1 to 3, and d is 1. In some embodiments, the borate ion can be of the above formula wherein z' is 1 or 2, q is 1, and r is 1.

The catalyst system may include other single-site catalysts such as Group 15-containing catalysts. The catalyst system includes single-site catalyst compounds such as chromium-based catalysts, Ziegler-Natta catalysts, one or more additional single-site catalysts (such as metallocene or Group 15-containing catalysts), bimetallic catalysts, and mixed catalysts, in addition to It may contain one or more secondary catalysts. The catalyst system is AlCl ₃ , cobalt,
It may also contain iron, palladium, or combinations thereof.

Examples of structures of MCN compounds that can be used in embodiments include hafnium compounds shown as formula (II), zirconium compounds shown as formula (IV-A-C), and formula (V
-A-B) are bridged zirconium compounds.

Although these compounds are shown with methyl- and chloro-groups attached to the central metal, it is understood that these groups may be different without altering the catalyst involved. For example, each of these substituents may independently be a methyl group (Me), a chloro group (Cl), a fluoro group (F), or any number of other groups including organic or heteroatom groups. good.
Additionally, these substituents change during the reaction as the pre-catalyst is converted to the active catalyst for the reaction. Additionally, any number of other substituents may be used on the ring structure, including any of the substituents described above with respect to formulas (I) and (II).

Group 15 Atoms and Metal-Containing Catalyst Compounds The catalyst system may comprise one or more Group 15 metal-containing catalyst compounds. Group 15 metal-containing compounds generally comprise Groups 3-14 metal atoms, Groups 3-7, or Groups 4-6 metal atoms. In many embodiments, the Group 15 metal-containing compound is bound to at least one leaving group and is also bound to at least two Group 15 atoms, of which at least one
Includes a Group 4 metal atom which is also bonded to a Group 15 or 16 atom through another group.

In one or more embodiments, at least one of the Group 15 atoms can be a C ₁ -C ₂₀ hydrocarbon group, a heteroatom-containing group, silicon, germanium, tin, lead, or another group that can be phosphorus. is also bonded to a group 15 or 16 atom via a group 15 or 16 atom that is also bonded to nothing or to hydrogen, a group 14 atom-containing group, a halogen, or a heteroatom-containing group each of the two Group 15 atoms is also bonded to a cyclic group,
It can optionally be attached to hydrogen, halogen, heteroatoms, or hydrocarbyl groups, or heteroatom-containing groups.

Group 15-containing metal compounds may be more specifically described by the following formulas (VI) or (VII):

In the formula, M is a transition metal of Groups 3 to 12, or a typical metal of Groups 13 or 14;
, 5, or 6 metals. In many embodiments, M is a Group 4 metal such as zirconium, titanium, or hafnium. Each X is independently a leaving group, such as an anionic leaving group. Leaving groups can include hydrogen, hydrocarbyl groups, heteroatoms, halogens, or alkyls, and y is 0 or 1 (when y is 0, the L' group is absent). The term "n" is M in the oxidation state. In various embodiments, n is +3, +4, or +5. In many embodiments, n is +4. The term "m" represents the formal charge of the YZL or YZL' ligand, which in various embodiments is 0, -1, -2 or -3. In many embodiments, m is -2. L is a group 15 or 16 element such as nitrogen, and L'
an element of group 5 or 16, or a group 14 such as carbon, silicon, or germanium
is a group-containing group. Y is a group 15 element such as nitrogen or phosphorus. In many embodiments Y is nitrogen. Z is a group 15 element such as nitrogen or phosphorus. In many embodiments Z is nitrogen. R ¹ and R ² are independently C ₁ -C ₂₀ hydrocarbon groups, up to 20
heteroatom-containing groups having 1 carbon atom, silicon, germanium, tin, lead, or phosphorous. In many embodiments, R ¹ and R ² are linear, branched, or cyclic C ₂ -C _2
0 alkyl group, or a C ₂ -C ₂₀ alkyl, aryl, or aralkyl group such as a C ₂ -C ₆ hydrocarbon group. R ¹ and R ² can also be interconnected with each other. ^R3 can be absent or can be a hydrocarbon group, hydrogen, halogen, heteroatom-containing group. In many embodiments, R ³ is absent, hydrogen, or a linear, cyclic, or branched alkyl group having 1-20 carbon atoms. R ⁴ and R ⁵ are independently an alkyl group,
Aryl groups, substituted aryl groups, cyclic alkyl groups, substituted cyclic alkyl groups, cyclic aralkyl groups, substituted cyclic aralkyl groups, or polycyclic ring systems often having up to 20 carbon atoms. In many embodiments, R ⁴ and R ⁵ have 3-10 carbon atoms, or C
₁ to C ₂₀ hydrocarbon group, C ₁ to C ₂₀ aryl group, or C ₁ to C ₂₀ aralkyl group, or heteroatom-containing group. ^R4 and ^R5 may be interconnected with each other. ^R6 and ^R7
is independently absent hydrogen, an alkyl group, a halogen, a heteroatom, or a hydrocarbyl group (such as a linear, cyclic, or branched alkyl group having from 1 to 20 carbon atoms). In many embodiments, ^R6 and ^R7 are absent. R ^* can be absent, hydrogen, a Group 14 atom-containing group, a halogen, or a heteroatom-containing group.

By "formal charge of the YZL or YZL'ligand" is meant that the overall charge of the ligand lacks the metal and the leaving group X. "R ¹ and R ² may also be interconnected" means that R ¹ and R
² can be directly bonded to each other or bonded to each other through another group. "R ⁴ and R ⁵ may also be interconnected" means that R ⁴ and R ⁵ are directly bonded to each other,
or can be bonded to each other through other groups. Alkyl groups include linear and branched alkyl radicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals. , aryloxycarbonyl radicals, carbamoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, linear, branched or cyclic, alkylene radicals, or combinations thereof. An aralkyl group is defined as a substituted aryl group.

In one or more embodiments, R ⁴ and R ⁵ are independently groups represented by formula (VIII) below.

When R ⁴ and R ⁵ are as in Formula VII, R ⁸ -R ¹² are each independently hydrogen, C ₁
~ _C40 alkyl groups, halides, heteroatoms, heteroatom containing groups containing up to 40 carbon atoms. In many embodiments, R ⁸ -R ¹² are C ₁ -C ₂₀ linear or branched alkyl groups such as methyl, ethyl, propyl, or butyl groups. Any two of the R groups can form a cyclic and/or heterocyclic group. Cyclic groups can be aromatic. In one embodiment, R ⁹ , R ¹⁰ and R ¹² are independently methyl, ethyl, propyl, or butyl groups (including all isomers). In another embodiment, R ⁹ , R ¹⁰ and R ¹² are methyl groups and R ⁸ and R ¹¹ are hydrogen.

In one or more embodiments, both R ⁴ and R ⁵ are groups represented by formula (IX) below.

When ^R4 and ^R5 are according to Formula IX, M is a Group 4 metal such as zirconium, titanium, or hafnium. In many embodiments, M is zirconium. L, Y, and Z
can be nitrogen. Each of R ¹ and R ² can be -CH ₂ -CH ₂ -. R.
³ can be hydrogen and R ⁶ and R ⁷ can be absent.

The Group 15 metal-containing catalyst compound can be represented by Formula (X) below.

In Formula X, Ph represents phenyl.

Catalyst Slurry The catalyst system can include a catalyst or catalyst component in a slurry that can have an initial catalyst compound and an additive solution catalyst component added to the slurry. The initial catalyst component slurry may have no catalyst. In this case, two or more solution catalysts can be added to the slurry to support each.

Any number of combinations of catalyst components may be used in embodiments. For example, a catalyst component slurry can include an activator and a support, or a supported activator. Additionally, the slurry may contain a catalyst compound in addition to the activator and support. As noted, the catalyst compound in the slurry may be supported.

The slurry may contain one or more activators and supports and another catalyst compound.
For example, a slurry can include two or more activators (such as alumoxanes and modified alumoxanes) and catalyst compounds, or a slurry can include a supported activator and two or more catalyst compounds. In one embodiment, the slurry includes a support, an activator, and two catalyst compounds. In another embodiment, the slurry contains a support, an activator, and two different catalyst compounds, which can be added to the slurry separately or in combination. A slurry containing silica and alumoxane can be contacted and reacted with a catalyst compound, after which the slurry is contacted with another catalyst compound, such as in a trim system.

The molar ratio of metal such as aluminum or metalloid such as boron in the catalyst compound to the metal in the activator in the slurry is from 1000:1 to 0.5:1, from 300:1 to 1:1, or 15
It can be from 0:1 to 1:1. The slurry may comprise a carrier material, which may be any inert particulate carrier material known in the art, including silica, fumed silica, alumina, clay, talc, or other carrier materials such as those described above, It is not limited to these. In one embodiment, the slurry contains silica and methylaluminoxane (“MA
O”), containing activators such as modified methylaluminoxane (“MMAO”).

One or more diluents or carriers may be used to facilitate the combination of any two or more components of the catalyst system in the slurry or trim catalyst solution. For example, a single-site catalyst compound and an activator can be combined together in the presence of toluene or another non-reactive hydrocarbon or hydrocarbon mixture to provide a catalyst mixture. In addition to toluene, other suitable diluents are ethylbenzene, xylene, pentane, hexane,
It may include, but is not limited to, heptane, octane, other hydrocarbons, or any combination thereof. The support, either dry or mixed with toluene, can then be added to the catalyst mixture, or the catalyst/activator mixture can be added to the support.

Catalyst Support As used herein, the terms "support" and "carrier" are used interchangeably and refer to any support material, including porous support materials such as talc, inorganic oxides, and inorganic chlorides. Point. One or more of the single-site catalyst compounds of the slurry can be supported on the same or separate support along with the activator, or the activator can be used in unsupported form, or the single-site catalyst compound and may be deposited on different supports or any combination thereof. This can be accomplished by any technique commonly used in the art. There are various other methods in the art for supporting single-site catalyst compounds. For example, single-site catalyst compounds can contain polymer-bound ligands. The slurry single-site catalyst compound may be spray dried. Supports with single-site catalyst compounds can be functionalized.

The support can be or include, for example, one or more inorganic oxides of Groups 2, 3, 4, 5, 13, or 14 elements. Inorganic oxides can include, but are not limited to, silica, alumina, titania, zirconia, boria, zinc oxide, magnesia, or any combination thereof. Exemplary combinations of inorganic oxides are alumina-silica, silica-titania, alumina-silica-titania, alumina-zirconia, alumina-
It may include, but is not limited to, titania and the like. The support can be or include alumina, silica, or combinations thereof. In one embodiment described herein, the support is silica.

A suitable commercially available silica support is ES757 available from PQ Corporation.
, ES70, and ES70W. Suitable commercially available silica-alumina supports are SIRAL® 1 available from SASOL®,
SIRAL®5, SIRAL®10, SIRAL®20
, SIRAL® 28M, SIRAL® 30, and SIRAL® 40. Generally, methylaluminoxane (M
Catalyst supports comprising silica gel with an activator such as AO) are used in the trim systems described because these supports can work well to co-support solution-borne catalysts. Suitable carriers may also be selected from Cab-o-sil® materials available from Cabot corporation and silica materials available from Grace Davison corporation.

Catalyst supports can also include polymers that are covalently bonded to ligands on the catalyst. For example, two or more catalyst molecules can be attached to a single polyolefin chain.

Catalyst Activator As used herein, the term “activator” refers to a supported or non-supported catalyst compound or component capable of activating a single-site catalyst compound or component, such as by creating a cationic species of the catalyst component. It may refer to any compound or combination of compounds that is supported. For example, this may involve abstraction of at least one leaving group (the "X" group in the single-site catalyst compounds described herein) from the metal center of the single-site catalyst compound/component. Activators are sometimes referred to as "cocatalysts."

For example, activators include Lewis acids, or non-coordinating ionic or ionizing activators, or Lewis bases, aluminum alkyls, and/or any other compound including conventional cocatalysts. obtain. In addition to the methylaluminoxanes (“MAO”) and modified methylaluminoxanes (“MMAO”) described above, exemplary activators include aluminoxanes or modified aluminoxanes, and/or neutral or ionic ionizing compounds. , for example, dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(3,5-( _CF ) _2phenyl )borate, triphenylcarbenium tetrakis(3,5-(CF ₃ ) _2phenyl )borate, dimethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis (
perfluoronaphthyl)borate, dimethylanilinium tetrakis(pentafluorophenyl)aluminate, triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate, dimethylaniliniumtetrakis(perfluoronaphthyl)aluminate, triphenylcarbenium Tetrakis(perfluoronaphthyl)aluminate, Tris(perfluorophenyl)boron, Tris(perfluoronaphthyl)boron, Tris(
perfluorophenyl)aluminum, tris(perfluoronaphthyl)aluminum,
or any combination of these, but not limited to these.

These activators may or may not be directly attached to the support surface, or they may be attached to the support surface while still maintaining their compatibility with the polymerization system. recognize that it may be modified as such. Such tethering agents can be derived from groups that are reactive with surface hydroxyl species. Non-limiting examples of reactive functional groups that can be used to create tethers include aluminum halides, aluminum hydrides, aluminum alkyls, aluminum aryls, sulminum alkoxides, electrophilic silicon reagents, alkoxysilanes, Aminosilane and borane can be mentioned.

Aluminoxanes are sometimes described as oligomeric aluminum compounds with -Al(R)-O- subunits, where R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (“MAO”), modified methylaluminoxane (“MMAO
”), ethylaluminoxane, isobutylaluminoxane, or combinations thereof. Aluminoxanes can be produced by hydrolysis of the respective trialkylaluminum compound. MMAO can be produced by hydrolysis of higher trialkylaluminums such as trimethylaluminum and triisobutylaluminum. MMAO is generally more soluble in aliphatic solvents and more stable during storage. There are various methods for preparing aluminoxanes and modified aluminoxanes.

In one or more embodiments, a visually transparent MAO may be used. For example, a cloudy or gelled aluminoxane can be filtered to produce a clear aluminoxane, or a clear aluminoxane can be decanted from a cloudy aluminoxane solution. In another embodiment, cloudy and/or gelled aluminoxanes may be used. Another aluminoxane is
Modified Methylaluminoxane (“MMAO”) Type 3A (Akzo Chemical
als, Inc. from the trade name Modified Methylaluminoxane
commercially available as type 3A). A suitable source of MAO is, for example, about 1
It can be a solution having from wt% to about 50 wt% MAO. Commercially available MAO solutions include 10 wt% and 30 wt% MAO solutions (Albemarle Corporation, of
Baton Rouge, LA. available from ).

As noted above, one or more organoaluminum compounds, such as one or more alkylaluminum compounds, may be used with the aluminoxane. For example, alkylaluminum species that can be used are diethylaluminum ethoxide, diethylaluminum chloride, and/or diisobutylaluminum hydride. Examples of trialkylaluminum compounds include trimethylaluminum, triethylaluminum (“TEAL”), triisobutylaluminum (“TiBAl”), tri-n-hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, etc. include, but are not limited to.

Catalyst Component Solution The catalyst component solution may contain only the catalyst compound or may contain an activator in addition to the catalyst compound. The catalyst solution used in the trim process can be prepared by dissolving the catalyst compound and optional activator in a liquid solvent. The liquid solvent can be an alkane such as a _C5 - _C30 alkane or a _C5 - _C10 alkane. Cyclic alkanes such as cyclohexane and aromatic compounds such as toluene may also be used. Additionally, mineral oil can be used as a solvent. The solutions employed should be liquid under the conditions of polymerization and relatively inert. In one embodiment, the liquid utilized in the catalyst compound solution is different than the diluent used in the catalyst component slurry. In another embodiment, the liquid utilized in the catalyst compound solution is the same diluent used in the catalyst component solution.

When the catalyst solution contains both the activator and the catalyst compound, the ratio of the metal in the activator to the metal such as aluminum or metalloid such as boron in the catalyst compound in the solution is 1000:
It can be 1-0.5:1, 300:1-1:1, or 150:1-1:1. In certain cases, an excess of Having a catalyst compound can be an advantage.
In various embodiments, the activator and catalyst compound are up to about 90 wt%, up to about 50 wt%, up to about 20 wt%, preferably up to about 10 wt%, based on the weight of the solvent and activator or catalyst compound. %, up to about 5% by weight, less than 1% by weight, or 100 ppm to 1% by weight in solution.

The catalyst component solution may contain any one of the soluble catalyst compounds described in the Catalyst section herein. High solubility is desirable when the catalyst is dissolved in solution. Thus, catalyst compounds in catalyst component solutions can often include metallocenes, which can have higher solubilities than other catalysts.

In the polymerization process described below, any of the catalyst component-containing solutions described above are
It can be combined with any of the catalyst component-containing slurry/slurries described above. Additionally, more than one catalyst component solution may be utilized.

Continuity Additives/Static Control Agents In gas phase polyethylene production processes, as disclosed herein, it is desirable to additionally use one or more static control agents to help regulate static levels in the reactor. Sometimes. Static control agents, as used herein, are chemical agents that can affect or move the static charge (negative, positive, or zero) of the fluidized bed when introduced into the fluidized bed reactor. composition. The particular static control agent used may depend on the nature of the static charge, and the choice of static control agent may vary with the polymer being produced and the single-site catalyst compound used.

Control agents such as aluminum stearate may be employed. The static control agent used is
It can be selected for its ability to receive static charges in a fluidized bed without adversely affecting productivity. Other suitable static control agents are aluminum distearate, ethoxylated amines,
and Innospec Inc. under the trade name OCTASTAT. It may also include an antistatic composition such as that provided by For example, OCTASTAT 2000 is a mixture of polysulfone copolymer, polymeric polyamine, and oil soluble sulfonic acid.

Any of the aforementioned control agents may be employed alone or in combination as control agents.
For example, carboxylic acid metal salts can be combined with amine-containing control agents (e.g.,
Carboxylic acid metal salt and KEMAMINE® (Crompton Corpora
) or ATMER® (ICI Americas I
nc. (Available from ) any family belonging to the family of products).

Other useful continuity additives include ethylenimine additives useful in the embodiments disclosed herein, which can include polyethyleneimine having the general formula:
—(CH ₂ —CH ₂ —NH) _n —

wherein n can be from about 10 to about 10,000. Polyethyleneimines can be linear, branched, or hyperbranched (eg, forming dendritic or dendritic polymer structures). They are homopolymers or copolymers of ethyleneimine or mixtures thereof (
hereinafter referred to as polyethyleneimine(s)). Chemical Formula --[CH ₂ -C
A linear polymer represented by H ₂ —NH]— can be used as the polyethyleneimine, but materials with primary, secondary, and tertiary branching can also be used. Commercially available polyethylenimine can be a branched compound of the ethyleneimine polymer. Suitable polyethyleneimines are commercially available from BASF Corporation under the trade name Lupasol. These compounds can be prepared as a wide range of molecular weights and product activities. Examples of commercially available polyethyleneimines sold by BASF suitable for use in the present technology include, but are not limited to, Lupasol FG and Lupasol WF. Another useful continuity additive is a mixture of aluminum distearate and an ethoxylated amine type compound such as Huntsman (formerly Ciba Specialty Ch.
may include IRGASTAT AS-990, available from Microelectronics. A mixture of aluminum distearate and an ethoxylated amine type compound may be added in mineral oil such as Hyd
It can be slurried in a robrite 380. For example, a mixture of aluminum distearate and an ethoxylated amine-type compound may be from about 5% to about 50% by weight, or about 10% by weight.
It can be slurried in mineral oil to have a total slurry concentration ranging from weight percent to about 40 weight percent, or from about 15 weight percent to about 30 weight percent.

Continuity additive(s) or static control agent(s) may be added to the reactor in amounts ranging from 0.05 to 200 ppm based on the weight of the total feed to the reactor excluding recycle. In some embodiments, the continuity additive is in an amount ranging from 2 to 100 ppm, or from 4 to 5
It can be added in amounts ranging from 0 ppm.

Gas Phase Polymerization Reactor FIG. 1 is a schematic diagram of a gas phase reactor system 100 showing the addition of at least two catalysts, at least one of which is added as a trim catalyst. A catalyst component slurry, preferably a mineral oil slurry comprising at least one support and at least one activator, at least one supported activator, and optional catalyst compounds, is placed in a tank or cat pot.
) 102 . In one embodiment, the catalyst pot 102 is a stirred holding tank designed to keep the solids concentration homogeneous. A catalyst component solution, preferably prepared by mixing a solvent with at least one catalyst compound and/or activator, is placed in a separate vessel, which may be referred to as a trimpot 104 . The catalyst component slurry may then be mixed in-line with the catalyst component solution to form the final catalyst composition. silica, alumina,
A nucleating agent 106 such as fumed silica, or any other particulate matter, may be added in-line to the slurry and/or solution, or to vessel 102 or 104 . Similarly, additional activator or catalyst compounds can be added in-line. For example, a second catalyst slurry containing a different catalyst can be introduced from a second catalyst pot. The two catalyst slurries can be used as the catalyst system with or without the addition of solution catalyst from the trimpot.

Catalyst component slurries and solutions may be mixed in-line. For example, solutions and slurries can be mixed by utilizing a static mixer 108 or a stirred vessel (not shown). Mixing the catalyst component slurry and the catalyst component solution moves the catalyst compounds in the catalyst component solution into the catalyst component slurry such that the catalyst components originally in solution migrate to the supported activator originally in the slurry. It should be long enough to disperse inside. The combination forms a uniform dispersion of catalyst compound on the supported activator forming the catalyst composition. The length of time that the slurry and solution are in contact is typically from about 0.01 to about 60 minutes, from about 5 to about 40 minutes.
minutes, or up to about 120 minutes, such as from about 10 to about 30 minutes.

When combining the catalyst, activator, and optional support or additional cocatalyst with the hydrocarbon solvent immediately prior to the polymerization reactor, the combination yields fresh polymerization catalyst in less than 1 hour, less than 30 minutes, or less than 15 minutes. is desirable. Since the new catalyst is ready before it is introduced into the reactor, shorter times are more effective and offer the possibility of higher flow rates.

In another embodiment, aluminum alkyls, ethoxylated aluminum alkyls, aluminoxanes, antistatic agents or borate activators, such as C ₁ -C ₁₅ alkylaluminums (eg, tri-isobutylaluminum, trimethylaluminum, etc.), C ₁
~ _C15 ethoxylated aluminum alkyls or methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, modified aluminoxanes, etc. are added in-line to the slurry and solution mixture. alkyl, antistatic agent, borate activator,
and/or the aluminoxane is added to the solution/slurry combination directly from the alkyl tank 110, or via an additional alkane (such as isopentane, hexane, heptane, and/or octane) carrier stream, to the hydrocarbon tank, for example. 112 can be added.
Additional alkyls, antistatic agents, borate activators, and/or aluminoxanes up to about 500 ppm, from about 1 to about 300 ppm, from 10 to about 300 ppm, or from about 10 to about 1
00 ppm. Carrier streams that may be used include, among others, isopentane and/or hexane. The carrier is typically from about 0.5 to about 60 liters, depending on the size of the reactor.
It can be added to the mixture of slurry and solution at a rate of b/hr (27 kg/hr) or higher. Similarly, a carrier gas 114 such as nitrogen, argon, ethane, propane, etc. can be added in-line to the slurry and solution mixture. Typically, the carrier gas is from about 1 to about 100
lb/hr (0.4-45 kg/hr), or from about 1 to about 50 lb/hr (5-23 kg
/hour), or at a rate of about 1 to about 25 lb/hour (0.4 to 11 kg/hour).

In another embodiment, the liquid carrier stream is introduced into the downwardly moving solution and slurry combination. The solution, slurry, and liquid carrier stream mixture may be passed through a mixing mixer or long tube prior to contact with the gaseous carrier stream.

Similarly, a comonomer 116 such as hexene, another α-olefin, or a diolefin
can be added in-line to the mixture of slurry and solution. The slurry/solution mixture is
It then enters reactor 120 through injection tube 118 . A nucleating agent 122 such as fumed silica may be added directly into the reactor 120 to aid in proper formation of particles in the reactor 120 . In some embodiments, the injection tube may aerosolize the slurry/solution mixture. Any number of suitable tube sizes and configurations may be used to aerosolize and/or inject the slurry/solution mixture. In one embodiment, a gas stream 124 , such as recycle gas, or recycle gas 126 , monomer, nitrogen, or other material is introduced into carrier tube 128 surrounding injection tube 118 .

When metallocene catalysts or other similar catalysts are used in gas phase reactors, oxygen or fluorobenzene can be added directly to reactor 120 or to gas stream 124 to control the rate of polymerization. Thus, a metallocene catalyst (which is sensitive to oxygen or fluorobenzene) is used in a gas phase reactor in combination with another catalyst (which is not sensitive to oxygen), and oxygen affects the polymerization rate of other catalysts. It can be used to modify the metallocene polymerization rate. An example of such a catalyst combination is bis(n-propylcyclopentadienyl)zirconium dichloride and [(2,4,6-Me ₃ C ₆ H ₂ )NCH ₂ CH ₂ ] ₂
NHZrBn ₂ (where Me is methyl), or bis(indenyl)zirconium dichloride and [(2,4,6-Me ₃ C ₆ H ₂ )NCH ₂ CH ₂ ] ₂ NHHfBn ₂ (wherein Me is methyl) Me is methyl). For example, if the oxygen concentration in the nitrogen supply is from 0.1 ppm to 0.1 ppm.
When changed to 5 ppm, significantly less polymer was produced from bisindenyl ZrCl ₂ and the relative amount of polymer produced from [(2,4,6-Me ₃ C ₆ H ₂ )NCH ₂ CH ₂ ] ₂ NHHfBn ₂ increases. WO/1996/09328, for example, discloses the addition of water or carbon dioxide to gas phase polymerization reactors for similar purposes. In one embodiment, the contact temperature of the slurry and solution ranges from 0°C to about 80°C, from about 0°C to about 60°C, from about 10°C to about 50°C, and from about 20°C to about 40°C.

The above examples are not limiting as additional solutions and slurries can be included. For example, a slurry can be combined with two or more solutions having the same or different catalyst compounds and/or activators. Similarly, the solution can combine two or more slurries each having the same or different supports and the same or different catalyst compounds and/or activators with a slurry. Similarly, two or more slurries are combined, preferably in-line, with two or more solutions, each slurry containing the same or different supports and containing the same or different catalyst compounds and/or activators, the solutions being , contain the same or different catalyst compounds and/or activators. For example, a slurry may contain a supported activator and two different catalyst compounds, two solutions each containing one of the catalysts in the slurry, each independently combined in-line with the slurry. .

USE OF CATALYST COMPOSITIONS TO CONTROL PRODUCT PROPERTIES Product polymer properties are determined by the mixing of the solutions, slurries, and any optional additives (nucleating agents, catalyst compounds, activators, etc.) described above. It can be controlled by adjusting the timing, temperature, concentration, and sequence. The MWD, composition distribution, melt index, relative amount of polymer produced by each catalyst, and properties of the polymer produced can also be altered by manipulating process parameters. Any number of process parameters can be adjusted, including manipulating the hydrogen concentration in the polymerization system, changing the amount of the first catalyst in the polymerization system, changing the amount of the second catalyst in the polymerization system. Other process parameters that can be adjusted are changing the relative proportions of the catalysts in the polymerization process (and optionally adjusting their individual feed rates to maintain a steady or constant resin production rate). )including. The concentration of reactants in the reactor 120 affects the amount and/or composition of recovered liquids and/or gases returned to the polymerization process, which alters the amount of liquids or gases withdrawn or purged from the process. The recovered liquid or recovered gas can be adjusted by changing
It can be recovered from the polymer discharged from the polymerization process. Additionally, concentration parameters that can be adjusted include changing the polymerization temperature, changing the ethylene partial pressure in the polymerization process, changing the ratio of ethylene to comonomer in the polymerization process, and changing the ratio of activator to transition metal in the activation sequence. include. changing the relative feed rates of the slurry or solution; changing the mixing time, temperature, and/or extent of in-line slurry and solution mixing; adding different types of activator compounds to the polymerization process; Time dependent parameters such as the addition of other catalyst poisons to the polymerization process can be adjusted. Any combination of these adjustments can be used to control the properties of the final polymer product.

In one embodiment, the composition distribution of the polymer product is measured at regular intervals, temperature, catalyst compound feed rate, ratio of two or more catalysts to each other, ratio of comonomer to monomer,
One of the above process parameters, such as monomer partial pressure and/or hydrogen concentration, is varied as necessary to bring the composition to the desired level. The composition distribution is determined by temperature-rising elution fractionation (TRE
F) or a similar technique, TREF, measures composition as a function of elution temperature.

In one embodiment, polymer product properties are measured in-line and the ratio of combined catalysts is changed accordingly. In one embodiment, the molar ratio of the catalyst compound in the catalyst component slurry to the catalyst compound in the catalyst component solution is from 500:1 to 1:1 after the slurry and solution are mixed to form the final catalyst composition. 500, or 100:1 to 1:1
00, or 50:1 to 1:50, or 10:1 to 1:10, or 5:1 to 1:5. In another embodiment, the molar ratio of the Group 15 catalyst compound in the slurry to the ligand metallocene catalyst compound in solution is 500:1,100 after the slurry and solution are mixed to form the catalyst composition. : 1, 50:1, 10:1, 5:1, 1:5, 1:10, 1:10
0, or 1:500. The product properties measured may include polymer product flow index, melt index, density, MWD, comonomer content, composition distribution, and combinations thereof. In another embodiment, when the ratio of catalyst compounds is changed, the rate of introduction of the catalyst composition into the reactor, or other process parameter, is changed to maintain the desired production rate.

Without being bound or limited by any theory, the processes described herein immobilize a solution catalyst compound in and onto a support, preferably a supported activator.
The in-line fixation techniques described herein preferably have suitable particle morphology, bulk density, or high catalytic activity when introduced into the reactor, and are suitable for introducing catalyst compound solutions into the reactor. to a supported catalyst system that provides suitable polymer properties without the need for additional equipment, particularly gas phase or slurry phase reactors.

Polymerization Process Catalyst systems can be used to polymerize one or more olefins to yield one or more polymer products therefrom. Any suitable polymerization process may be used including, but not limited to, high pressure, solution, slurry, and/or gas phase polymerization processes. In embodiments using other techniques than gas phase polymerization, modifications of the catalyst addition system similar to that discussed with respect to FIG. 1 may be used. For example, the trim system can be used to feed catalyst to a loop slurry reactor for producing polyethylene copolymer.

The terms "polyethylene" and "polyethylene copolymer" refer to polymers having at least 50% by weight ethylene-derived units. In various embodiments, the polyethylene comprises at least 70% by weight ethylene-derived units, at least 80% by weight ethylene-derived units, at least 9
It can have 0 weight percent ethylene-derived units, at least 95 weight percent ethylene-derived units, or 100 weight percent ethylene-derived units. Polyethylene may thus be a homopolymer or copolymer, including terpolymers having one or more other monomeric units. As described herein, polyethylene can include, for example, at least one or more other olefins or comonomers. Suitable comonomers can contain 3 to 16 carbon atoms, 3 to 12 carbon atoms, 4 to 10 carbon atoms, and 4 to 8 carbon atoms. Examples of comonomers are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-
Examples include, but are not limited to, octene, 4-methylpent-1-ene, 1-decene, 1-dodecene, 1-hexadecene, and the like. In addition, to tune the properties of the polymer,
Small amounts of diene monomers such as 1,7-octadiene can be added to the polymerization.

Referring again to FIG. 1, the fluidized bed reactor 120 comprises a reaction zone 130 and a velocity reduction zone 13
2. Reaction zone 130 is a bed containing growing polymer particles, formed polymer particles, and a small amount of catalyst particles fluidized by a continuous flow of gaseous monomer and diluent to remove the heat of polymerization through the reaction zone. 134. Optionally, recycle gas 124
A portion of the can be cooled and compressed to form a liquid that increases the heat removal of the circulating gas stream when re-entered into the reaction zone. A suitable gas flow rate can be readily determined by experimentation. The configuration for the circulating gas stream of gaseous monomer is such that the particulate polymer product and its associated monomer are withdrawn from the reactor and the composition of the gas passing through the reactor maintains an essentially stable gaseous composition within the reaction zone. The speed can be equal to the speed that can be adjusted to maintain. Gas exiting the reaction zone 130 may be sent to a velocity reduction zone 132 where transported particles are removed, for example by decelerating and retreating into the reaction zone 130 . If desired, finer transported particles and dust can be removed with a separation system 136 such as a cyclone and/or fine filter. Gas 124 passes through a heat exchanger 138 that may remove at least a portion of the heat of polymerization.
can pass through. The gas is then compressed in compressor 140 and reacted section 13
It can be set back to 0.

The reactor temperature of the fluid bed process is greater than about 30°C, about 40°C, about 50°C, about 90°C, about 100°C, about 110°C, about 120°C, about 150°C, or more. or more. Generally, the reactor temperature is operated at the highest possible temperature considering the sintering temperature of the polymer product in the reactor. A preferred reactor temperature is 70-95°C. A more preferred reactor temperature is 75-90°C. Thus, in one embodiment, the upper temperature limit is the melt temperature of the polyethylene copolymer produced in the reactor. However, higher temperatures lead to narrow MWD, which can be improved by the addition of MCN, or other cocatalysts, as described herein.

Hydrogen gas can be used in olefin polymerization to control the final properties of the polyolefin. By using certain catalyst systems, increasing the concentration (partial pressure) of hydrogen can increase the flow index (FI) of the polyethylene copolymer produced.
Flow index may thus be affected by hydrogen concentration. The amount of hydrogen in the polymerization is expressed as a molar ratio to total polymerizable monomers, eg, ethylene or blends of ethylene and hexene or propylene.

The amount of hydrogen used in the polymerization process may be that amount necessary to achieve the desired flow index of the final polyolefin resin. For example, the molar ratio of hydrogen to total monomer ( _H2
: monomer) can be greater than about 0.0001, greater than about 0.0005, or greater than about 0.001. Additionally, the molar ratio of hydrogen to total monomer (H ₂ :monomer) may be less than about 10, less than about 5, less than about 3, and less than about 0.10. The range of desirable hydrogen to monomer molar ratios is
Any combination of any upper molar ratio limit and any lower molar ratio limit described herein may be included. Expressed another way, the amount of hydrogen in the reactor at any given time is in another embodiment up to about 5,000 ppm, up to about 4,000 ppm, in another embodiment up to about 3,000 ppm.
pm, or about 50 ppm to 5,000 ppm, or about 50 ppm to 2,000 ppm
can range from The amount of hydrogen in the reactor may range from a lower limit of about 1 ppm, about 50 ppm, or about 100 ppm to an upper limit of about 400 ppm, about 800 ppm, about 1,000 ppm, about 1,000 ppm,
It can range from 500 ppm, or about 2,000 ppm. Furthermore, hydrogen versus total monomer (
H ₂ :monomer) ratio is from about 0.00001:1 to about 2:1, from about 0.005:1 to about 1
. 5:1, or from about 0.0001:1 to about 1:1. One or more reactor pressures (either single stage or two or more stages) in the gas phase process is 690 kPa (100 psig)
~3,448 kPa (500 psig), 1,379 kPa (200 psig) ~2,7
59 kPa (400 psig) range, or 1724 kPa (250 psig) to 2
, 414 kPa (350 psig).

Gas phase reactors can handle about 10 kg of polymer per hour (25 lb/hr) to about 90,90
0 kg/hr (200,000 lb/hr) or greater, and about 455 kg/hr (1,000
lb/hr), greater than about 4,540 kg/hr (10,000 lb/hr), about 11,30
Greater than 0 kg/hr (25,000 lb/hr), about 15,900 kg/hr (35,000
lb/hr), and greater than about 22,700 kg/hr (50,000 lb/hr), and from about 29,000 kg/hr (65,000 lb/hr) to about 45,500 kg/hr (10
0,000 lb/hr).

As noted, slurry polymerization processes may also be used in embodiments. Slurry polymerization processes generally operate at pressures ranging from about 1 atmosphere to about 5,070 kPa (50 atmospheres) or higher, and from about 0°C to about 120°C, more specifically from about 30°C to about 100°C. Temperatures in the °C range are used. In slurry polymerization, a suspension of solid particulate polymer can be formed in a liquid polymerization dilution medium to which ethylene, comonomers, and hydrogen can be added along with the catalyst. A suspension containing diluent can be intermittently or continuously removed from the reactor where the volatile constituents are separated from the polymer and optionally recycled to the reactor after distillation. Liquid diluents employed in the polymerization medium can be alkanes having 3-7 carbon atoms, such as branched alkanes. The medium employed must be liquid and relatively inert under the conditions of polymerization. When propane media are used, the process should be operated above the reaction dilution critical temperature and pressure. In one embodiment, hexane, isopentane, or isobutane media may be employed. The slurry can be circulated in a continuous loop system.

The product polyethylene has a melt index ratio (MIR or I ₂₁ /
I ₂ ). Flow Index (FI, HLMI, or _I21 is ASTM
It can be measured according to D1238 (190°C, 21.6 kg). Melt index (MI
, I ₂ ) can be measured according to ASTM D1238 (2.16 kg weight at 190° C.).

Density can be determined according to ASTM D-792. Density is 1 unless otherwise stated
Expressed as grams per cubic centimeter (g/cm ³ ). Polyethylene has a lower limit of about 0.89 g/cm ³ , about 0.90 g/cm ³ , or about 0.91 g/cm ³ to an upper limit of about 0.95 g/cm ³ , about 0.96 g/cm ³ , or about It can have a density in the range of 0.97 g/cm ³ . The polyethylene may have a bulk density of from about 0.25 g/cm ³ to about 0.5 g/cm ³ measured according to ASTM D1895 B method. For example, polyethylene bulk density has a lower limit of about 0.30 g/cm ³ , about 0.32 g/cm ³ , or about 0.33 g/cm 3 .
g/cm ³ up to about 0.40 g/cm ³ , about 0.44 g/cm ³ , or about 0.48
It can be in the range of g/cm ³ .

Polyethylene is used in articles such as films, fibers, nonwovens and/or wovens, extrudates,
and/or may be suitable for molding. Examples of films include shrink films in food contact and non-food contact applications, cling films, oriented films, sealing films, oriented films, snack packaging, heavy duty bags, shopping bags, baked and frozen food packaging, medical applications. Included are blown or cast films formed by coextrusion or lamination, useful for agricultural films and sheets, such as packaging, industrial liners, and the like. Examples of fibers include melt spinning, solution spinning, and melt blown fiber operations for use in woven or non-woven forms to make filters, diaper fabrics, hygiene products, medical garments, geotextiles, and the like. be done. Examples of extruded articles include tubing, medical tubing, wire and cable coatings, pipes, geomembranes, and pond linings. Examples of molded articles include single and multi-layer structures in the form of bottles, tanks, large hollow articles, rigid food containers, and toys.

To enable a better understanding of the foregoing considerations, the following non-limiting examples are provided.
All parts, ratios and percentages are by weight unless otherwise indicated.

As described herein, comonomers such as C ₄ -C ₈ α-olefins, along with ethylene monomers, are added to the reactants to provide single chain branching (
SCB). Without intending to be bound by theory, SCB can cause long PE chains to exit crystallites and be partially incorporated within other crystallites. Therefore, polymers with SCB on longer chains may exhibit higher toughness.

In contrast, long chain branching (LCB) is the point at which two polymer chains can split from a single polymer chain. LCB can enhance toughness, but makes the polymer more susceptible to orientation and reduces tear strength in the extrusion direction.

The inclusion of short chains can lower the melting temperature of the polymer and enhance processability. However, SCB on short chains pushes these chains out of the crystallite and into the amorphous region,
It reduces the toughness of the resulting polymer product.

Hydrogen may be added to the polymer reactant to control molecular weight. Hydrogen essentially acts as a chain terminator that replaces a monomer or comonomer molecule in the reactants. This stops the formation of current polymer chains and initiates new polymer chains.

Catalyst System Comonomer Uptake vs. MWD Control, Results from 6 Inch Gas Phase Reactor Polymerization Experiments in 6 Inch Diameter Gas Phase Reactor Catalysts AJ shown in Table 1 were used as described herein. prepared. All catalysts prepared were equipped with devices for temperature control, catalyst feed or injection equipment, gas chromatography (GC) analyzers to monitor and control the monomer and comonomer gas feeds, and polymer sampling and recovery. Screened in an instrumented fluid bed reactor. The reactor is 6 inches (1 cm) in diameter, which increases to 10 inches (25.4 cm) at the top of the reactor.
5.24 cm) floor. Gas enters through a perforated distribution plate that allows fluidization of the bed contents, and the polymer sample is discharged at the top of the reactor. The comonomer in the exemplary polymerizations herein is 1-hexene. Polymerization parameters are outlined in Table 1 below and plotted in FIGS.

The reaction bed of growing polymer particles is maintained in a fluidized state by continuously flowing make-up water and recycle gas through the reaction zone at superficial gas velocities of 1-2 feet/second (0.3-0.6 m/second). maintained at The reactor had a temperature of 175°F (79°C) and a total pressure of 300 psig (2274
kPa gauge) and contained 35 mol % ethylene.

FIG. 2 is a series of polymers prepared to test the relative ability of a series of metallocene catalysts to prepare resins having a melt index (MI) of about 1 and a density (D) of about 0.92. is a plot 200 of . Polymerizations were carried out in a 6 inch continuous gas phase reactor (LGPR) as described herein. The left axis 202 is parts per _million (m
ol) in units of H ₂ (ppm/mol%), representing the gas phase ratio of hydrogen to ethylene monomer (H ₂ /C ₂ ) used to achieve the target properties. The right-hand axis 204, in units of moles per mole, is the comonomer to ethylene ratio ( _C6 /
C ₂ ).

A comparison of the _C6 / _C2 levels used to achieve the property targets indicates the relative ability of the catalyst to incorporate comonomer. For example, C ₆ of (1-EtInd) ₂ ZrCl ₂ (B)
Comparing the /C ₂ level 206 with the C ₆ /C ₂ level 208 of (PrCp) ₂ HfF ₂ (I) yields a ratio of about 36/9 or about 4. This suggests that for a given _gas ratio of _C6 / _C2 , the polymer prepared with (PrCp) _2HfF2 is (1-EtInd) ₂
It shows that it has about four times more single-chain branches (SCB) than the polymer prepared with _ZrCl2 . This data is useful for controlling the compositional distribution of polymers made as in-situ blends using catalyst mixtures, for example, as co-supported catalysts on a single support.
The data are also useful in determining which catalysts should be combined to have a composition distribution containing both comonomer-rich (low density) and comonomer-poor (high density) components.

The effect of the steady state gas ratio of H ₂ /C ₂ (ppm/mol) 202 is indicated by the bars. These bar levels are approximately a function of the relative molecular weight of the catalyst. For example, (C
H ₂ ) ₃ Si(CpMe ₄ )CpZrCl ₂ (J) requires a H ₂ /C ₂ ratio 210 of about 23.4 ppm/mol to achieve a target melt index of about 1, and (CpM
e ₅ ) (1-MeInd)ZrCl ₂ (A) requires a H ₂ /C ₂ ratio 212 of about 0.4 ppm/mol to achieve the same target melt index. These results are
At the same _H2 /C2 _ratio , ( _CH2 ) _3Si ( _CpMe4 ) _CpZrCl2 (J) becomes (CpM
e ₅ ) (1-MeInd)ZrCl ₂ (A) yields a higher Mw polymer. _In this example, the data _are
is an approximation.

FIG. 3 is a plot 300 of the series of polymers of FIG. 2, showing different metallocene (MCN)
Figure 3 shows the melt index ratio (MIR) of a series of catalyst-made polymers. As used herein, the terms Melt Index Ratio (MIR), Melt Flow Ratio (MFR
), and “I ₂₁ /I ₂ ” are interchangeably the flow indices (“FI” or “I ₂₁
”) to the melt index (“MI” or “I ₂ ”). MI(I ₂ ) is A
It can be measured according to STM D1238 (2.16 kg weight at 190°C). FI ( _I2
1 ) can be measured according to ASTM D1238 (21.6 kg weight at 190°C).
Similarly numbered items are as described with respect to FIG. This plot 300
, the left axis 302 represents the MIR. MIR (which may also be referred to as melt flow ratio or MFR) is the ratio of the _I21 and _I2 melt indices and can indicate the presence of long chain branching. For linear resins, without LCB, the ratio is about 25 or less. Higher MIR values can indicate the presence of LCB, which can be detrimental to film properties, as noted above. Maximum M
An IR ratio of 304 is for (CH ₂ ) ₃ Si(CpMe ₄ )CpZrCl ₂ (J), indicating that the polymer produced by this catalyst has the most LCB. in contrast,
Blending the resin with two different catalysts forms a final product with a higher MIR.

Using the results shown in Figures 2 and 3, five catalysts were selected to determine the dependence of molecular weight (Mw) on _H2 ratio. These catalysts are used for low Mw polyethylene (CpMe
₅ ) (1-MeInd)ZrCl ₂ (A) 306, (1-EtInd) ₂ ZrCl ₂ (B
) 308, and (Me ₄ Cp)(1,3-Me ₂ Ind)ZrCl ₂ (E) 310. The catalyst is (PrCp) ₂ HfF ₂ (I) of medium Mw polyethylene
A catalyst to produce 312 was also included. Table 2 contains data on the dependence of Mw on _H2 / _C2 levels.

These results were used to generate a series of plots that could be used to determine the sensitivity of Mw to _H2 / _C2 ratio. Table 3 shows the slope and intercept of the reciprocal plot. Low Mw catalysts have a greater slope, indicating a greater impact of _H2 / _C2 ratio on Mw. The second catalyst, (1-EtInd) ₂ ZrMe ₂ , had the greatest Mw dependence on the H ₂ /C ₂ ratio. Slopes can be used to select catalysts with widely different responsiveness to hydrogen.

The data shown in Figures 2 and 3 and Tables 2 and 3 are for (1-EtInd) ₂ ZrCl ₂
Combination of (B) with (PrCp) ₂ HfF ₂ (I) broad MWD without LCB
and lead to polymers with SCBD. As shown in plot 300 of FIG. 3, resins made with these two catalysts have MIRs close to 20 and are thus essentially free of LCB. The information in Tables 2 and 2 indicates that (1-EtInd) ₂ ZrCl ₂ is about 4.
At 2 ppm/mol H ₂ /C ₂ , it has a Mw approximately one-third that of (PrCp) ₂ HfF ₂ . The information in plot 200 shown in _{FIG .}
has about four times lower SCB than (PrCp) ₂ HfF ₂ under comparable conditions.

The equations from Table 3 are required in combination with the catalyst (PrCp) ₂ HfF ₂ to make a resin with an overall Mw of 100 Kg/mol at four different H ₂ levels (1-EtInd ) ₂ can be used to predict the amount of ZrCl ₂ . These values are
For example, (PrCp) ₂ HfF ₂ is used as a supported catalyst component and (1-EtInd
) ₂ ZrCl ₂ can be used to set the initial control point when 2 ZrCl 2 is a solution catalyst component added as a trim catalyst. In this embodiment, the added (1-EtInd) ₂
The amount of _ZrCl2 catalyst can be controlled to achieve Mw and other performance targets. Results for various combinations are shown in Table 4.

Pilot Plant Run with Trim Feed The use of catalyst trim feed was tested in a pilot plant to control molecular weight and molecular weight distribution, and the results are detailed in Table 5. In Table 5, the catalyst types correspond to the numbered catalyst structures shown in the detailed description. Five of the catalyst runs (AE) were control runs performed without the trim catalyst.

Controlling molecular weight and compositional distributions using co-supported catalysts in combination with (CpPr) ₂ HfF ₂ .

Tests were carried out with a first catalyst comprising (CpPr) ₂ HfMe ₂ (HfP, structure III). HfP is capable of polymerizing ethylene and mixtures of ethylene and comonomers in the presence of an activator and support, cocatalyst, or both. Activator and carrier may be the same or different. Multiple activators, supports, and/or cocatalysts may be used simultaneously. Co-catalysts may be added to modify any of the components. descriptor catalyst, HfP
, activator, support, and/or cocatalyst also refer to the actual compounds and solutions of these compounds in hydrocarbon solvents.

For use as a cocatalyst, especially in trim systems, the catalyst should be soluble in alkane solvents such as hexane, paraffinic solvents, and mineral oil. Solubility is 0.000
It may be greater than 1 wt%, greater than 0.01 wt%, greater than 1 wt%, or greater than 2 wt%. Toluene may be used as a solvent when the catalyst may be more soluble in aromatic solvents.

As described herein, a combination of HfP, activator (MAO), and support (silica) reacts with the trim catalyst in a hydrocarbon solvent, yielding the expected resulting in polymerization catalysts with different polymerization behavior. More specifically, the molecular weight distribution of the polymer produced by the co-supported cocatalyst is broader than can be achieved with a mixture of polymers formed from the individual component catalysts. This change in polymerization behavior is associated with MWD
, CD, or MW of polymers formed by mixtures of HfP and selected cocatalysts
Exemplified by changes in D and CD. Thus, in an in-line mixer immediately prior to the polymerization reactor, catalyst, HfP, activator, and optionally support, additional cocatalyst, in a hydrocarbon solvent,
Or by combining both, a new polymerization catalyst is obtained.

Any series of catalysts, HfP, activators, and optionally supports, additional co-catalysts, or a combination of both in hydrocarbon solvents can be used. For example, the catalyst can be added to a mixture containing HfP, activator, and optionally support, additional cocatalyst, or both. Additionally, the catalyst and co-catalyst can be added to the {HfP, activator, and optionally support} mixture. Additionally, the catalyst and HfP may be added to a mixture comprising {activator and optionally support and cocatalyst}.

It is desirable to combine the catalyst, HfP, activator, and optionally support, additional cocatalyst, or both in a hydrocarbon solvent and obtain a dry catalyst from the mixture. The dry mixture can be fed directly into the polymerization reactor or as a slurry.

Changes in MWD and CD when using catalyst and HfP can be controlled by changing the ratio of catalyst to HfP. If no catalyst is employed, MWD and CD are those of HfP. When a single catalyst is employed, MWD and CD are produced by the catalyst itself. By changing the catalyst ratio, the MWD and CD are changed from those of the parent. The ratio can be altered to target specific MWD and CD targets.

Catalysts can be selected to control the change in MWD or CD of the polymer formed. By employing catalysts that yield lower or higher molecular weight polymers than HfP,
Broadens the molecular weight distribution. The Mw versus _H2 / _C2 response of polymers made from a single component can be used to guide selection. For example, catalysts that are less responsive to hydrogen than HfP yield higher Mw than polymers produced with HfP alone, as shown in FIG. Furthermore, a catalyst more responsive to hydrogen than HfP is HfP
yields a lower Mw than alone.

In addition to selecting catalysts to broaden the MWD, catalysts can be selected to modify the compositional distribution. For example, employing a catalyst that incorporates less or more comonomer than HfP broadens the compositional distribution. As discussed further below, a rough guide to this effect is the relative gas _C6 / _C2 ratios required to prepare about 0.92D resins from different catalysts. These catalysts, which provide a greater difference in the _C6 / _C2 gas ratio than HfP, broaden the CD. The molecular weight distribution can also be altered by employing a catalyst that yields a different MWD than HfP, but similar average molecular weight.

Combining the catalyst and HfP can result in a MWD greater than expected from the theoretical combination of the individual catalysts. Desirable materials based on HfP base catalysts are made when the catalyst's Mw and comonomer incorporation capacity are both higher than HfP.
Similarly, desirable materials are also formed when the Mw and comonomer incorporation capacity of the catalyst are both lower than HfP. Furthermore, desirable materials are made when the Mw and the comonomer incorporation capacity of the catalyst are equal to and lower than HfP.

Preparation of Co-Supported Polymerization Catalysts FIG. 4 shows a flowchart of a method 400 for preparing co-supported polymerization catalysts. Method 4
00 begins at block 402 with plot generation of the hydrogen/ethylene ratio versus the reciprocal molecular weight of the polymer produced by each one of several catalysts. As discussed herein, the slope of each plot indicates the response of the corresponding catalyst to hydrogen level.

At block 404, a value is determined for each comonomer/ethylene ratio of the catalyst that can be used to achieve a single target density such as 0.92. The ratio value used to achieve the target density indicates the ability of the catalyst to incorporate comonomer. At block 406, the first
of catalysts are selected for co-supported polymerization catalysts. For example, the first catalyst can typically be a commercially available catalyst or can be selected to have low or high ability to incorporate comonomer and high or low response to hydrogen.

At block 408, a second catalyst is selected for the co-supported polymerization catalyst. The second catalyst is the first
can be selected to have a slope of the hydrogen/ethylene ratio versus reciprocal molecular weight plot that is at least about 1.5 times the magnitude of the slope of the plot of the catalyst of . Furthermore, the second catalyst is
It may be selected to have a comonomer/ethylene ratio value that is less than about 0.5 of the magnitude of the comonomer/ethylene ratio of the first catalyst. At block 410, the first catalyst and the second catalyst may be co-supported on a single support, for example, to create a co-supported polymerization catalyst using the trim technology specifically described herein.

General Procedure for Forming Catalyst Components Catalyst

Experimental All manipulations were performed in a N2 _- purged glovebox using standard or Schlen
was performed using the k-technique. All anhydrous solvents were purchased from Sigma-Aldrich and
Degassed and dried over calcined Al ₂ O ₃ beads or molecular sieved before use. Toluene for catalyst preparation was pre-dried over Al ₂ O ₃ beads and then treated with SMAO before use.
757 to dry. Deuterated solvents were obtained from Cambridge Isotope Lab.
It was purchased from ratories, degassed, dried over alumina beads, or molecular sieved prior to use. ZrCl ₄ 99 purchased from Strem Chemicals
+%, and Boulder Scientific (lot number BSC3220-8-0
002), with the exception of bis(n-propyl-cyclopentadienyl)hafnium dimethyl (HfPMe ₂ ), which was purchased from Sigma-Aldrich.
¹ H NMR measurements were recorded on 250 Mz Bruker and 500 Mz Bruker spectrometers.

Rac-meso-bis(1-ethyl-indenyl)zirconium dimethyl(1-Et
Synthesis of Ind) ₂ ZrMe ₂ (IV-A/IV-B) Indenyllithium. Freshly distilled indene (50.43 g, 434.1 mmol)
was dissolved in 1 L of pentane. Et ₂ O (25 mL) followed by 1.6 M n-
Butyllithium (268.5 mL, 429.6 mmol) was added to the clear stirring solution over 5 minutes. A white solid precipitated and the supernatant became pale yellow. After stirring overnight, the suspension was filtered and then dried in vacuo to give a white solid (46.51 g, 381.0 mmol, 88
. 7%) was obtained. ¹ H NMR (THF-d ₈ ): δ 5.91 (d, 2H), 6.44 (
m, 2H), 6.51 (t, 1H), 7.31 (m, 2H).

1-ethylindene. 46.51 g (380.95 mmol) _of indenyl lithium was dissolved in 250 mL of Et ₂ O and the separated solution was 95.94 g (61
5.12 mmol) of ethyl iodide. The ethyl iodide solution was cooled to -30°C in a dry ice/acetone bath, which was used to cool the indenyllithium solution to 0-10°C. Indenyllithium was added to the clear stirring solution of ethyl iodide via cannula transfer. The solution turned pale yellow to yellow upon addition of the indenyllithium solution. The reaction was stirred overnight, slowly warming to room temperature. After stirring overnight, the flask was placed in a box and the _Et2O was reduced in vacuo. Once LiI started to precipitate, 300 mL of pentane was added and the white suspension was filtered to give a pale orange solution. When more LiI precipitated, the pentane was evaporated to give a pale orange oily liquid. The crude product was distilled under reduced pressure to a pale yellow, clear liquid using a rotary vacuum pump. ¹ H NMR showed ~90% 1-ethylindene and ~10% 3-ethylindene. Potential isomerization may have arisen from the small amount of acid present during the distillation, as none were present in the crude ¹ H NMR spectrum.
44.27 g (306.96 mmol) of product were isolated for a yield of 80.6%. ¹ H NMR (CD ₂ Cl ₂ ): δ 0.96 (3H, t), 1.59 (1H, q), 1
. 99 (1H, q), 3.41 (1H, m), 6.58 (1H, d), 6.59 (1H
, d), 7.24 (2H, m), 7.41 (2H, dd).

1-ethylindenyl lithium. 44.27 containing ~10% 3-ethylindene
g (306.98 mmol) of 1-ethylindene in 500 mL of pentane and about 3 mL
of Et ₂ O. 188.28 mL (301.25 mL) in hexane was added to the clear stirring solution.
mol) of 1.6 M n-butyllithium was added over 10 minutes. Immediately, a flaky white precipitate formed and stirring was stopped. The mixture was stirred manually to ensure proper uptake of the reagents and the suspension was left overnight. The suspension was filtered and the white solid dried in vacuo. 43.27 g (288.18 mmol) of product was obtained with a yield of 95.7%. ¹ H NMR (THF-d8): δ 1.26 (3H, triplet), 2.86 (2
H, quartet), 5.72 (doublet, 1H), 6.38 (dd 1H),
6.43 (2H, m), 7.26 (1 H, t), 7.30 (1 H, m).

Rac-meso-bis(1-ethyl-indenyl)zirconium dimethyl(1-Et
Ind) ₂ ZrMe ₂ (IV-A/B)
Add 7.00 g (46.65 mmol) of 1-ethyl-indenyllithium to 74 mL of 1
, 2-dimethoxyethane (DME), and the isolated solution was 5.43 g in 75 mL of DME.
(23.30 mmol) of _ZrCl4 . A bright yellow solution of 1-ethyl-indenyllithium was added to the clear ZrCl ₄ solution via pipette over 15 minutes. The solution took on a yellow tint when first added and a precipitate formed 5 minutes after the addition, followed by an orange-yellow color. Ten minutes after addition, the supernatant turned orange with a yellow precipitate and all 1-ethyl-
The mixture returned to a yellow color when the indenyllithium solution was added. The reaction was stirred overnight. A crude ¹ H NMR spectrum of the slurry showed a meso/rac ratio of ~1.1:1, which may be misleading as the rac isomer is more soluble than the meso isomer in DME. . _15.61 mL (46.83 m
mol) of 3.0 M CH ₃ MgBr was added in 1 mL portions over 10 minutes. 10
After the second addition, the yellow mixture turned orange. After the final addition of Grignard reagent, the mixture turned brown and the reaction was stirred overnight. The ¹ H NMR spectrum of the crude mixture is 1.1
A meso/rac ratio of :1 was determined. Evaporate the DME and leave a brown solid on 3 x 20 m
L of toluene followed by an additional 10 mL. The light brown solid obtained after removing the solvent was washed with 10 mL of pentane and dried in vacuo. 8.26 g (2
0.26 mmol) of an off-white solid was obtained.

Dichloride spectral data: ¹ H NMR (CD ₂ Cl ₂ ): δ 1.16 (6.34 H
, t, rac), 1.24 (6H, t, meso), 2.73-2.97 (8H, overlap q
), 5.69 (1.82H, dd, meso), 5.94 (1.92H, dd, rac)
, 6.06 (1.99 H, d, rac), 6.35 (1.84 H, d, meso), 7.
22-7.65 (16H, m).

Dimethyl spectral data: ¹ H NMR (C ₆ D ₆ ): δ -1.40 (3.33 H,
s, meso), −0.895 (6H, s, rac), −0.323 (3.34H, s,
meso), 1.07 (13H, overlap t), 2.47 (4H, overlap q), 2.72 (4H
, q), 5.45-5.52 (8H, m), 6.91 (8H, m), 7.06-7.13
(4H, m), 7.30 (4H, m).

Rac-meso-bis(1-ethyl-indenyl)zirconium dimethyl(1-Et
Synthesis of Ind) ₂ ZrMe ₂ (IV-A/B) ZrCl ₄ (20.8 g; 89.3 mmol) in 1,2-dimethoxyethane (DME)
) in about 100 mL of a solution of 1-ethyl-indenyllithium (26.8 g; 178 mmol) dissolved in 1,2-dimethoxyethane (DME) (about 200 mL) divided into about 5 mL to give 15 added over a period of minutes. Add more DME as needed to
The reaction was prevented from thickening with stirring. The final total volume of additions was approximately 425 mL. Just before and about halfway through the addition of the 1-ethyl-indenyllithium solution, pentane (about 1
0 mL) was added to the reaction mixture and removed under vacuum to lower the temperature. After stirring for about 4 hours at room temperature, an aliquot of the slurry was removed and dried. ¹ H NMR of the solid thus obtained was taken in CD ₂ Cl ₂ and showed a rac/meso ratio of 0.7:1.

Approximately 100 mL of solvent is evaporated from the reaction and methyllithium solution (1.6 M in ether
111 mL; 178 mmol) was added in portions (approximately 20 mL) over approximately 1 hour. After stirring overnight, the rac/meso ratio was 0.7:1.0. Additional MeLi solution (1.6 M in ether; 7.0 mL; 11.2 mmol) was added and the reaction was stirred at room temperature for 3 days. The rac/meso ratio was 0.9:1 as determined by ¹ H NMR. The solvent was removed under vacuum and the residue was extracted with warm hexanes (approximately 300 mL; 60° C.), filtered, concentrated to a total volume of approximately 100 mL and cooled to −20° C. overnight. Isolate the solid by filtration, wash with cold pentane (2 x 50 mL), dry under vacuum and give a rac/meso
29.2 g of solid was obtained with a ratio of 0.94:1. The isolated solid was washed with warm hexane (approximately 15
0 mL) and filtered from a small amount of pink solid. Reduce the volume to about 125 mL,
The solution was treated with trimethylsilyl chloride (2.0 mL). The solution was filtered, concentrated to approximately 100 mL, heated to redissolve the precipitated product, and slowly cooled. After stirring overnight, the flask was cooled to -20°C, which precipitated some pink solid. The flask was warmed to 55° C. and additional hexane (approximately 75 mL) was added to trimethylsilyl chloride (5.0 mL).
). This was maintained at 55° C. for 2 hours and the reaction was filtered to give a yellow solution.
The solution was filtered, concentrated to approximately 100 mL, heated to redissolve the precipitated product, and slowly cooled. The precipitated solid was isolated by filtration, washed with cold pentane (2 x 30 mL) and dried under vacuum at 55°C. Yield is 21.1 g with a rac/meso ratio of 1.1
It was 9/1.

Synthesis of meso-(1-EtInd) ₂ ZrCl ₂ 1-Ethylindenyl lithium (1.0 g; 6.7 mmol) was treated with dimethoxyethane (D
ME) (7.7 mL) and cooled to -20°C. Solid _ZrCl4 (0.781 g;
3.35 mmol) was added in portions over 5 minutes and the reaction was allowed to continue overnight. After removing the volatiles, the yellow solid thus obtained is treated with CH ₂ Cl ₂ until the yellow color disappears.
extracted with CH ₂ Cl ₂ was removed under vacuum to give a yellow solid. Yield = 1.14 g,
The meso/rac ratio was 19:1.

meso-(1-EtInd) ₂ ZrM of meso-(1-EtInd) ₂ ZrCl ₂
Conversion to e ₂ meso-(1-EtInd) ₂ ZrCl ₂ (1:19 rac/meso; 307 mg
; 0.68 mmol) was slurried in Et ₂ O (approximately 10 mL) and MeMgBr (Et
3.0 M in ₂ O; 0.47 mL; 1.41 mmol) was added. The reaction was dried, extracted with warm hexane (~18 mL at 60°C), filtered and dried to give a pale yellow solid (2
40 mg). ¹ H NMR of C ₆ D ₆ was maintained which indicated a rac/meso ratio of 1:19.

1:1 rac/me of 1:1 rac/meso-(1-EtInd) ₂ ZrCl ₂
Conversion to so-(1-EtInd) ₂ ZrMe ₂ (1-EtInd) ₂ ZrCl ₂ (1:1 rac/meso; 12.2 g; 27.2
mmol) was slurried in Et ₂ O (approximately 80 mL) and MeMgBr ( ₂ .
6M; 23.2 mL; 60.3 mmol) was added. Stir the reaction overnight, dry the reaction, extract with warm hexanes (~300 mL), filter, dry ~1 mL of the solution, ¹ H NMR of C ₆ D ₆ is (1-EtInd) ₂ ZrMe ₂ very clean 1:1
of the meso/rac ratio.

₁ : ₁ rac/meso(1-Et
Ind) ₂ ZrMe ₂ near conversion meso-(1-EtInd) ₂ ZrCl ₂ (1:5 rac/meso; 244 mg
0.54 mmol) was slurried in Et ₂ O (˜5 mL) and MeLi (1.6 M in Et ₂ O; 0.69 mL; 1.10 mmol) was added. The reaction was stirred overnight, filtered, and an aliquot of the filtered reaction mixture was dried. ¹ H NMR of C ₆ D ₆ is 1:1.
It showed a rac/meso ratio of 24.

Methylation of (EtInd) ₂ ZrCl ₂ The methylation results found in the procedures discussed herein were further explored to determine the conditions under which stereochemical orientation could reset known levels. A series of tests using the procedures detailed below were performed with the results shown in Tables 6A and 6B. Me in ether
The use of MgBr is the only condition where substantially no isomerization occurs. The best conditions for isomerization were excess MeLi in ether or excess Grignard in DME. Furthermore, D
The use of excess MeLi in ME leads to a new species, presumably (EtInd) _ZrMe3 .

(1-EtInd) ₂ ZrCl ₂ (0.6 g; 1.34 mmol) was placed in a 50 ml round bottom flask and Et ₂ O or DME (20 mL) was added. MeLi (1.57 M in ether) or MeMgBr (3.0 M in ether) was added with stirring. The ratio of methylating agent to zirconium compound was either 2.0-1 or 2.3-1. To determine the meso/rac ratio, remove approximately 1/2 mL of the reaction mixture,
Short drying removed most of the solvent and the solid was dissolved in about 0.75 mL of C ₆ D ₆ . ¹
H NMR was taken at 400 MHz. The sum of the integrals of the two Zr-Me resonances of the meso species (
δ=−0.31 and −1.40) were used as the integral values of the Zr—Me resonances of the rac species (δ=−0.
89) to give the meso/rac ratio.

The procedures described allow bis-indenyl polymerization catalysts to be formed with unbalanced stereochemical compositions without bridging groups between the indenyl rings. For example, one enantiomer may be formed in a 3-fold or greater ratio relative to the other entantiomer. Furthermore, the conditions provide a methylation procedure that resets the stereochemistry to a substantially uniform composition.

(1-methylindenyl)(pentamethylcyclopentadienyl)zirconium (IV)
) synthesis of dimethyl (IV-C)

(1-methylindenyl)(pentamethylcyclopentadienyl)zirconium (IV)
) dichloride In a drybox, 1-methyl-1H-indene oil (1.85 g, 14.2 mmol
) was weighed into a 250 ml round bottom flask and dissolved in 25 ml of dry diethyl ether. n-Butyl lithium (1.6 in hexane) dropwise from a 20 ml needle/syringe
M, 12.0 ml, 19.2 mmol) is added, forming a yellow solution. Stir at room temperature for 60 minutes.

Cp*ZrCl ₃ (4.51 g,
13.5 mmol, used as received from Aldrich-475181) was added quickly in one portion as a yellow crystalline solid. The yellow-orange slurry was stirred overnight at room temperature.

The mixture was allowed to settle for 30 minutes. The dark brown solution was decanted from the pale yellow solid and the solid was rinsed with 100 ml of dry ether on the glass frit. Extract the solids on a frit with 100 ml of dichloromethane to give a yellow suspension. Filtered on a frit through a celite plug and evaporated the volatiles to give a yellow solid. Recrystallization from ether/pentane gave 2.70 g (47%). Additional material was obtained from the mother liquor: 1.19 g (20%).

¹ H NMR ( _C6D6 , 500 MHz, 35°C): _δ 1.70 (15H, s, Cp*
), 2.30 (3H, s, indenyl _CH3 ), 5.56 (2H, ABq, indenyl CH, CH), 7.05 (1H, dd, indenyl CH), 7.10 (1H, dd,
indenyl CH), 7.24 (1H, dt, indenyl CH), 7.56 (1H, d
q, indenyl CH).

(1-methylindenyl)(pentamethylcyclopentadienyl)zirconium (IV)
) dimethyl (IV-C)
(1-Methylindenyl)(pentamethylcyclopentadienyl)zirconium dichloride (4.92 g, 11.5 mmol) was slurried in 50 mL of diethyl ether,
Cooled to -50°C. To this was added a solution of MeLi (14.8 mL of 1.0 mL in diethyl ether).
71 M solution, 25.4 mmol) was added slowly via syringe. The mixture was allowed to slowly warm to room temperature while stirring to give a pink slurry. After 16 hours the solvent is removed under vacuum and
The residue was extracted with toluene. The insolubles were removed by filtration through a frit covered with celite and the solvent was removed to give an orange oily solid. The solid was washed with pentane and dried under vacuum (3.89 g, 88% yield). ^1H NMR δ ( _C6D6 ): 7.53 (d _, 1H
, 8-IndH), 7.13-6.99 (m, 3H, 5,6,7-IndH), 5.21
(d, 1H, 2-IndH), 5.11 (d, 1H, 3-IndH), 2.20 (s, 3
H, 1-MeInd), 1.69 (s, 15H, CpMe ₅ ), −0.51 (s, 3H,
ZrMe), −1.45 (s, 3H, ZrMe).

Synthesis of (1,3-dimethylindenyl)(tetramethylcyclopentadienyl)zirconium dimethyl[(1,3-Me ₂ Ind)(CpMe ₄ )]ZrMe ₂ (IV-D) 2,3,4,5 -tetramethyl-1-trimethylsilyl-cyclopenta-2,4-diene:

In a 2 liter Erlenmeyer flask, yellow oil tetramethylcyclopentadiene (50 g, 409 mmol—obtained from Boulder Scientific) was dissolved in 1 liter of anhydrous THF. n-Butyllithium (175 ml, 437 ml) was passed through a 60 ml plastic syringe fitted with a 20 gauge needle to control the dropwise flow.
mol) while stirring at room temperature. Formation of a pale yellow precipitate was observed. When the lithium reagent addition is complete, the reaction is a yellow slurry. Stir at room temperature for 1 hour, then add chlorotrimethylsilane (60 ml, 470 mmol) with vigorous stirring,
The reaction was stirred overnight at room temperature. After stirring for 15 hours at room temperature, the mixture is a yellow solution.
The THF solvent was removed under a stream of _N2 to give an oily residue, which was then extracted with 1 liter of dry pentane and filtered through a celite pad on a coarse frit. Volatiles were removed under vacuum to give the product as a yellow oil product: 62.9g, 79%. ¹ H _NMR ( _C6D6
, 250 MHz): δ−0.04 (s, Si(CH ₃ ) ₃ ), δ 1.81, (s, CH ₃
), δ 1.90 (s, CH ₃ ), δ 2.67 (s, CH).

Synthesis of (tetramethylcyclopentadienyl)zirconium trichloride

Inside the drybox, solid ZrCl ₄ (30.0 g, 129 mmol) was charged to a 450 ml Chemglass pressure vessel equipped with a magnetic stir bar and suspended in 100 ml dry toluene. 2,3,4,5-Tetramethyl-1-trimethylsilyl-cyclopenta-2,4-diene was dispensed as a yellow oil (27.5 g, 142 mmol) and an additional 100
Washed with 1 ml dry toluene. The pressure vessel was sealed with a screw-on cap with a Viton o-ring and heated to 110° C. for 90 minutes on an attached aluminum heating mantle. The solution darkened with time and insolubles were present during the reaction. The vessel was stirred overnight and cooled to room temperature. The vessel was opened and the solvent was reduced under a stream of _N2 to give a thick red sludge. 2
x50 ml of dry pentane and then with 100 ml of dry ether. Remove the red solution and recover the product as a pale red solid: 35.4 g, 85%. ¹ H NMR (C
₆ D ₆ , 250 MHz): δ 1.89 (br s, CH ₃ ), δ 2.05 (br s, C
H ₃ ), δ 5.78 (br s, CH)

Synthesis of 1,3-dimethylindene

1-methyl-indenyl lithium: freshly distilled 3-methylindene (33.75 g
259.24 mmol) was dissolved in pentane (1 L). Et ₂ O (10 ml) was added to the clear stirring solution, followed by 1.6 M n-butyllithium in hexanes (107 mL, 171.2 mmol) and 2.5 M n-butyl lithium in hexanes (34.2 mL, 85.5 mmol). bottom. A flaky white solid immediately precipitated. After stirring overnight, the suspension was filtered and the white solid was dried in vacuo (33.88 g, 248.90 mmol, 9
7%). ¹ H NMR (THF-d8): δ 2.41 (s, 3H), 5.68 (d, 1H
), 6.31 (d, 1H), 6.41 (m, 2H), 7.22 (m, 2H).

In a drybox, iodomethane (2.0 ml, 32.1 mmol) was dissolved in 80 ml of dry diethyl ether in a 250 ml round bottom flask equipped with a magnetic stir bar. The flask was placed in a wide mouth Dewar hexane cold bath (-25°C). Another 100ml Er
A room temperature solution of 1-methylindenyllithium (3.50 g
, 25.7 mmol) was prepared in 50 ml of dry diethyl ether to give a yellow solution. Slow dropwise addition of the indenyllithium solution to a stirred solution of cold iodomethane was carried out over 15 minutes. Continue stirring at low temperature for 30 minutes, then remove cold bath,
The reaction was allowed to warm to room temperature overnight. After stirring for 15 hours at room temperature, the solution is opaque white. The solution volume was reduced under a stream of nitrogen and then volatiles were evaporated under high vacuum. The solids were extracted with 2 x 80ml isohexane and filtered through a celite pad on a coarse frit. Evaporation of the filtrate under high vacuum gave a brown oil. Dissolved in 5 ml of dichloromethane, loaded via pipette onto a silica gel column (Biotage SNAP 100 g) and eluted with dichloromethane:isohexane (gradient, 2-20%). Fractions were combined and evaporated to give a clear oil. Recovered 2.54 g, 68%.

¹ H NMR (C ₆ D ₆ , 500 MHz): δ 1.11 (d, J=7.5 Hz, -CH
_CH3 ), ?1.96 (s, CH= _CCH3 ), ?3.22 (m, _CHCH3 ), ?5.
91 (m, CH═CCH ₃ ), δ 7.15-7.27 (aromatic CH). The mixture contained the desired product and traces of the isomeric 3,3-dimethylindene in a 1:10 ratio. δ1.17
(s, _CH3 ), δ 6.14 (d, J = 5.5 Hz, CHH), δ 6.51 (d, J = 5
. 5 Hz, CHH).

Synthesis of 1,3-dimethylindenyllithium

2.54 g (17.6 mmol) of 1,3-dimethylindene, a clear oil, and 3,
A 10:1 mixture of 3-dimethylindene was dissolved in 35 ml of dry pentane. 6.2m
1 of a 2.5 M hexane solution of n-butyllithium (15.5 mmol) was slowly added dropwise while stirring at room temperature. A white precipitate formed immediately. Stirred for 45 minutes at room temperature, then filtered the supernatant via cannula. The residue was suspended in 30 ml of dry pentane and cooled in a drybox freezer (-27°C) for 60 minutes. The supernatant was filtered, dried in vacuo to 2.34 g (88%) of white powder and used as such in subsequent reaction steps without characterization.

Synthesis of [(1,3-dimethylindenyl)(tetramethylcyclopentadienyl)]zirconium dichloride:

3.50 g (10.98 mmol) of tan (tetramethylcyclopentadienyl)
The zirconium trichloride powder was weighed into a 100 ml round bottom glass bottle equipped with a magnetic stirrer. Suspended in 80 ml of dry diethyl ether. 1,3- as a powder over several minutes
Stir while adding dimethylindenyllithium (1.65 g, 10.99 mmol). Rinse with an additional 20 ml of ether. The jar was capped and stirred overnight at room temperature. 1 at room temperature
After stirring for 5 hours, the mixture is a yellow slurry. evaporate volatiles under high vacuum,
The residue was extracted with 2 x 80 ml of dichloromethane. Filtered through a celite pad on a coarse frit. Concentrate in vacuo and filter again through fresh celite on a coarse frit.
Dried in vacuum to 3.6 g (77%) of yellow free-flowing powder. ¹ H NMR (CD
₂ Cl ₂ , 500 MHz): δ 1.89 (s, ^CpMe4 in CH ₃ ), δ 1.90 (s,
^CpMe4 of _CH3 ), δ2.40 (s, _C9 fragment of _CH3 ), δ5.67 (s, ^CpMe4 of CH), δ6.33 (s, _C9 fragment of CH), δ7.24 ( AA'BB', _C9 fragment of aromatic CH), δ 7.52 (AA'BB', _C9 fragment of aromatic CH). It contains about 15% diethyl ether.

Synthesis of [(1,3-dimethylindenyl)(tetramethylcyclopentadienyl)]zirconium dimethyl (IV-D)

In the drybox, bright yellow (1,3-Me ₂ Ind)( _CpMe )ZrCl
A powder of ₂ (3.6 g, 8.4 mmol) was suspended in 75 ml of dry diethyl ether in an amber glass flat-bottom bottle equipped with a 100 ml magnetic stir bar. Place the bottle in an isohexane bath-
Cooled to 10° C. and stirred while a solution of methyllithium (1.6 M in ether) was delivered via syringe in portions (4×3 ml, 19.2 mmol). Cap the jar with a septum and
Stir overnight allowing the cold bath to slowly warm to room temperature. The slurry was evaporated under high vacuum to dryness. Extracted with 3×50 ml of dichloromethane and filtered through celite on a coarse frit. Concentrate under a stream of nitrogen and then add pentane. Stirred for 15 minutes then evaporated the volatiles. The solid was washed with cold pentane and dried in vacuo. Recovered as 1.67 g of a tan powder. A second crop of 0.52 g was recovered from the filtrate. total yield is 2
. 19g, 67%. ¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ −1.22 (s,
_ZrCH3 ), 1.78 (s, Cp ^Me4 fragment of _CH3 ), 1.87 (s, Cp of _CH3
^Me4 fragment), 2.25 (s, _C9 fragment of _CH3 ), 4.92 (s, Cp ^Me4 fragment of CH), 5.60 (s, _C9 fragment of CH), 7.14 (AA′ BB', _C9 fragment of aromatic CH), 7.44 (AA'BB', _C9 fragment of aromatic CH). ¹³ C{ ¹ H} NMR (CD
₂ Cl ₂ , 125 MHz): δ 11.64 (Cp ^Me4 fragment of CH ₃ ), 12.91 (C
_C9 fragment of _H3 ), 13.25 (Cp ^Me4 fragment of _CH3 ), 37.23 ( _ZrCH3
), 106.34 (Cp ^Me4 fragment of CH), 115.55 ( _C9 fragment of CH); quaternary
¹³ C resonances 107.36, 117.51, 122.69, 125.06.

Synthesis of Meso-O(1-SiMe ₂ indenyl)2 zirconium dimethyl (VA) meso-O-(SiMe ₂ indenyl) ₂ Zr in about 300 mL of ether at room temperature
Cl ₂ (purchased from Sud-Chemie Catalytica; 40.0 g; 83.2
mmol) to a slurry of 54.0 mL of MeMgBr (3.0 M/ether; 162 m
mol) was added. After stirring the slurry for 1.5 hours, the volatiles were removed. Heptane (approximately 300 mL) was added to the resulting solid and heated to 80° C. for 30 minutes. The slurry was filtered and the supernatant cooled to −30° C. resulting in the formation of a crystalline solid which was isolated by filtration, washed with pentane and dried under vacuum. Yield was 26.0 g. ^1H NMR
δ( _C6D6 ): 7.57 (m, 2H) _, 7.42 (m, 2H), 7.02 (m, 2H
), 6.94 (m, 2H), 6.31 (d, 2H), 5.82 (d, 2H), 0.44 (
s, 6H), 0.34 (s, 6H), 0.00 (s, 3H), −2.07 (s, 3H).

Catalyst Preparation Dehydration of Silica at 610° C. Ineos ES757 silica (3969 g) was loaded into a dehydrator (6 feet long, 6.25 inches diameter) equipped with a 3-zone heater and dried at a flow rate of 0.12 ft3 ^/ sec. N.
Fluidized with ₂ gases. Afterwards the temperature was increased to 200° C. during 2 hours. After holding at 200°C for 2 hours, the temperature was increased to 610°C during 6 hours. After holding at 610° C. for 4 hours, the temperature was cooled to ambient over a period of 12 hours. The silica was transferred to an APC can under _N2 and then stored under _N2 pressure (20 psig).

Preparation of Silica Supported Methylaluminoxane (SMAO) In a typical procedure, Ineos ES757 silica (741
g) was combined with toluene (2 L) and a solution of 30% by weight methylaluminoxane in toluene (87
4 g, 4.52 mol) was added to a stirred (overhead mechanical cone stirrer) mixture. The silica was chased with toluene (200 mL), then the mixture was heated to 90° C. for 3 hours. Volatiles are then removed by applying vacuum and mild heat (40° C.) overnight,
The solid was then cooled to room temperature.

Typical Small Scale Catalyst Preparation for a Laboratory Salt Bed Reactor In a N2 purged drybox, 3.00 grams of SMAO (4.5 mmol M
AO/g SMAO) was transferred to a 125 ml Cel-Stir mixer. Pentane (50 mL) was added to create a slurry. The slurry was stirred at ambient temperature. The metallocene (0.11 mmol) was dissolved in a minimal amount of toluene (~2 mL). This solution was then added to the stirred slurry. The mixture was stirred for 1 hour. After the allotted time, the mixture was filtered onto a glass frit, washed with fresh pentane (2 x 10 mL), then dried for at least 1 hour.

Description of the Laboratory Salt Bed Reactor A 2 L autoclave was charged with dry salt (200 g) and SMAO (3 g) under _N2 atmosphere. Dry, degassed 1-hexene (see Table 7) was added to the reactor via syringe at a pressure of ₂ psig of N2. The reactor is sealed and the bed is heated to 80° C. with agitation and then N
₂ to a pressure of 20 psig. The solid catalyst was then injected into the reactor with ethylene at a pressure of 220 psig. Ethylene was flushed while running. The temperature was raised to 85°C. Hexene was fed into the reactor as a ratio to the ethylene flow (0.08 g/g).
Hydrogen was fed into the reactor as a ratio to the ethylene flow as indicated in the table. The hydrogen to ethylene ratio was determined by on-line GC analysis. The polymerization was interrupted after 1 hour by venting the reactor, cooled to room temperature and exposed to air. Salts were removed by stirring the crude product in water. The polymer was obtained by filtration and then dried in a vacuum oven with the results shown in Table 8.

Large Scale Catalyst Preparation for Gas Phase Pilot Plant Trials 24 Inch Diameter A 5 L 3 neck Morton flask was charged with pentane (4 L) followed by
75 g) was stirred with a mechanical stirrer (140 rpm). for an hour,
(1-EtInd) ₂ ZrMe ₂ (IV-A/B), HfPMe ₂ (III) in addition funnel
and toluene were added. The slurry turned green and was stirred for an additional hour. The mixture was then filtered and dried in vacuum for a total of 8 hours. Results are shown in Table 9.

75% HfPMe ₂ /25% (1-EtInd) ₂ ZrMe ₂ Catalyst Preparation Batch 2 A procedure similar to that described above was employed for a second 75/25 catalyst batch. 204.15g from UT-331-142, 176.17g from UT-331-101, UT-331-124
and 160.19 g from UT-331-143. For the second batch, 4 initially to avoid agglomeration
L of pentane was added to the Morton flask followed by SMAO. 2.87 g (7.09 mmol) of (1-EtInd) ₂ ZrMe ₂ and 8.94 g (
20.95 mmol) of _HfPMe2 , two separate solutions were made.

50% HfPMe ₂ /50% (1-EtInd) ₂ ZrMe ₂ catalyst preparation batches 1 and 2
The same procedure used to prepare the second batch of 75/25 catalyst was used for both 50/50 catalyst sets. Batch 1 is SMAO from UT-331-143, 5.75 g
(14.10 mmol) of (1-EtInd) ₂ ZrMe ₂ and 5.97 g (14.1
1 mmol) of HfPMe ₂ was used. Batch 2 is SM from UT-331-144
AO, 5.75 g (14.09 mmol) of (1-EtInd) ₂ ZrMe ₂ and5.
97 g (14.11 mmol) of _HfPMe2 were used.

Catalyst Mixing Two 75/25 batches were combined in a 4 L Nalgene bottle and mixed by rotating and shaking the bottle by hand. Two 50/50 batches were also mixed in the same manner.

Spray-dried catalyst preparation Spray-dried HfP Low (SD-(III)). First 10 wt% MAO (24.7
lb), toluene (35.8 lb), and Cabosil TS-610 (3.4 lb)
A feedstock slurry was prepared by adding to a 10 gallon feed tank. The mixture was stirred overnight at room temperature. HfP(III) (28.75 g, 0.06798 mol) was added, then the resulting slurry was mixed for an additional hour at ~38-40°C before spraying.
The catalyst was spray dried at a slurry feed rate of 93 lb/hr, 90% atomizer rate, and an exit temperature of 80°C. Yield was 2289 g (85%). Analytical data are reported in Table 10.

Description of 24 inch diameter gas phase reactor Reactor and a maximum width of 4.2 feet (1.3
m) expansion in a continuous gas-phase fluidized bed reactor. The fluidized bed consists of polymer granules. The gaseous feed streams of ethylene and hydrogen along with liquid 1-hexene were mixed together in a mixed tee configuration and introduced into the recycle gas line below the reactor bed. Individual flow rates of ethylene, hydrogen, and 1-hexene were controlled to maintain fixed composition targets. Ethylene concentration was controlled to maintain a constant ethylene partial pressure. The hydrogens were controlled to maintain a constant hydrogen to ethylene molar ratio. All gas concentrations were measured by on-line gas chromatography to ensure a relatively constant composition in the recycle gas stream.

The solid catalyst was injected directly into the fluidized bed using purified nitrogen as carrier. The injection rate was adjusted to maintain a constant production rate of polymer. The reaction bed of growing polymer particles is fluidized by continuously flowing make-up water and recycle gas through the reaction zone at superficial gas velocities of 1-3 feet/second (0.3-0.9 m/second). maintained. The reactor is 3
It was operated at a total pressure of 00 psig (2068 kPa gauge). In order to keep the reactor temperature constant, the temperature of the recycle gas was constantly adjusted up and down to account for any changes in the heat release rate due to the polymerization.

A solution of an antistatic agent in hexane (1:1 aluminum stearate:N-nonyldiethanolamine at 20% by weight) was used to obtain about 30 ppm antistatic in a fluidized bed using a mixture of iso-pentane and nitrogen. was fed into the reactor at a rate to maintain the agent.

The fluidized bed was maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of particulate product formation. Semi-continuous product removal into a fixed volume chamber through a series of valves and simultaneous venting of this back to the reactor allows for highly efficient product removal while simultaneously A portion of the unreacted gas is recycled back to the reactor. The product was purged to remove transport hydrocarbons and treated with a small stream of humidified nitrogen to deactivate any traces of residual catalyst and cocatalyst.

Run Summary An example of run conditions for the polymerization is shown in Table 11.

13.25 inch diameter gas phase reactor description
2 shows the results. The fluidized bed consisted of polymer granules and a gaseous feed stream of ethylene and hydrogen along with liquid 1-hexene comonomer was introduced into the recycle gas line below the reactor bed.
Individual flow rates of ethylene, hydrogen, and 1-hexene were controlled to maintain fixed composition targets. Ethylene concentration was controlled to maintain a constant ethylene partial pressure. Hydrogen was controlled to maintain a constant hydrogen to ethylene molar ratio. All gas concentrations were measured by on-line gas chromatography to ensure a relatively constant composition in the recycle gas stream. The reaction bed of growing polymer particles was maintained in a fluidized state by continuously flowing make-up water and recycle gas through the reaction zone. To achieve this, 0.6~
A superficial gas velocity of 0.9 meters/second was used. The fluidized bed was maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of particulate product formation. Polymer production rates ranged from 15 to 25 kg/hr. Product was removed semi-continuously into a fixed volume chamber through a series of valves. The product was purged to remove transport hydrocarbons and treated with a small stream of humidified nitrogen to deactivate any traces of residual catalyst.

Dispersing the solid catalyst in degassed and dried mineral oil as a nominally 18 wt% slurry, adding purified nitrogen as a carrier and Isopentane was used to contact the trim catalyst solution for seconds to minutes before injecting directly into the fluidized bed. The trim catalyst was initially provided as a solution and was substantially diluted with isopentane to a concentration of about 0.015 wt. . The relative feeds of the slurry and trim catalysts are controlled to achieve the target target feed ratios of their active polymerized metals, the feeds affecting the overall polymer production rate and, to some extent, the polymer flow index MFR and density. is adjusted according to the relative amount of polymer produced by each catalyst based on , while the reaction temperature and gas composition in the reactor are also manipulated. The reaction bed of growing polymer particles is about 2.0-2
. Fluidization was maintained by continuous flow of make-up water and recycle gas through the reaction zone at superficial gas velocities in the range of 2 ft/sec (0.61-0.67 m/sec). The reactor was operated at a total pressure of approximately 350 psig (2413 kPa gauge). In order to maintain a constant fluidized bed temperature in the reactor, the temperature of the recycle gas is adjusted between the tubes of the shell and tube heat exchanger together with cooling water on the shell side to account for any changes in the heat release rate due to the polymerization. was constantly adjusted up and down by passing circulating gas through the

A degassed and dried slurry mixture of antistatic agent in mineral oil (1:1 aluminum stearate:N-nonyldiethanolamine at a concentration of 20 wt.
A mixture of iso-pentane and nitrogen was fed into the reactor at a rate to achieve an antistatic concentration of 3 ppmw. (Column 128) Isopentane and/or nitrogen are optionally added to the antistatic agent through a 1/8 inch to 3/16 inch OD injection tube strut that extends several inches into the bed from the side wall of the reactor. of the slurry mixture into the fluidized bed of the reactor,
Adopted to help disperse.

The fluidized bed was maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of particulate product formation. The product was removed semi-continuously into a fixed volume discharge chamber through a series of valves. The product is purged to remove transport hydrocarbons and placed in a receiving fiber pack drum to deactivate any traces of residual catalyst and cocatalyst.
It was treated with a small stream of humidified nitrogen that was immediately discharged into an iberpak drum.

All numerical values are "about" or "approximately" the value indicated, and take into account experimental error and variations that would be expected by one of ordinary skill in the art. Additionally, various terms have been defined above. For the scope of terms used in the claims, as reflected in at least one publication or issued patent, the broadest definition given to that term by one of ordinary skill in the relevant art should be given. All patents, testing procedures, and other documents cited in this application are fully incorporated by reference to the extent that such disclosure is consistent with this application and all rights to which such incorporation is permitted.

を含み、前記ｍｅｓｏ鏡像異性体の前記ｒａｃ鏡像異性体に対する比率が、アルキル化中に、約１．０～約１．２へと実質的に標準化され、各Ｒ^３が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、Ｒ^４が、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、各Ｒ^５が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、Ｒ^３、Ｒ^４、及びＲ^５が、同じであっても異なってもよく、各Ｘが、メチル基である、前記触媒組成物。
［８］前記第２の触媒化合物が、次の式を有する化合物を含む、上記［７］に記載の前記触媒組成物。

［９］前記第２の触媒化合物が、次の式を有する少なくとも１つの化合物を含む、上記［７］に記載の前記触媒組成物。

［１０］前記第２の触媒化合物が、次の式、

を有する少なくとも１つの化合物を含み、式中、各Ｒ^４Ａが独立して、メチル、エチル、プロピル、ペンチル、ヘキシル、オクチル、ノニル、ドデシル、フェネチル、または他のヒドロカルビルである、上記［７］に記載の前記触媒組成物。
［１１］前記第２の触媒化合物が、次の式を有する少なくとも１つの化合物を含む、上記［７］に記載の前記触媒組成物。

［１２］第３の触媒を含む、上記［７］に記載の前記触媒組成物。
［１３］オレフィンを重合して、多峯性の組成分布を有するポリオレフィンポリマーを生成する方法であって、エチレン及びコモノマーを触媒系と接触させることを含み、前記触媒系が、共担持されて共通担持触媒系を形成する第１の触媒化合物及び第２の触媒化合物を含み、前記第１の触媒化合物が、次の式、
（Ｃ_５Ｈ_ａＲ^１ _ｂ）（Ｃ_５Ｈ_ｃＲ^２ _ｄ）ＨｆＸ_２
を含み、式中、各Ｒ^１が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、各Ｒ^２が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、ａ及びｃが、≧３であり、ａ＋ｂ＝ｃ＋ｄ＝５であり、少なくとも１つのＲ^１及び少なくとも１つのＲ^２が、ヒドロカルビルまたは置換ヒドロカルビル基であり、隣接する基であるＲ^１及びＲ^２基が結合して環を形成してもよく、各Ｘが独立して、不安定なヒドロカルビル、置換ヒドロカルビル、またはヘテロ原子基から選択される脱離基であり、前記第２の触媒化合物が、次の鏡像異性体の混合物、

を含み、前記ｍｅｓｏ鏡像異性体が、前記混合物中で少なくとも約１５部であり、前記ｒａｃ鏡像異性体が、前記混合物中で約５部未満であり、式中、各Ｒ^３が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、Ｒ^４が、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、各Ｒ^５が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、Ｒ^３、Ｒ^４、及びＲ^５が、同じであっても異なってもよく、各Ｘが独立して、不安定なヒドロカルビル、置換ヒドロカルビル、ヘテロ原子基、またはＲ^３、Ｒ^４、もしくはＲ^５基に結合する二価ラジカルから選択される脱離基である、前記方法。
［１４］前記Ｘ基が、メチルであり、前記ｍｅｓｏ／ｒａｃ比率が、メチル化によって調整され、前記触媒化合物に対して約２．３当量のエーテル中のＭｅＬｉ溶液をもたらす、上記［１３］に記載の前記方法。
［１５］前記ポリオレフィンポリマーから生成物を形成することを含む、上記［１３］に記載の前記方法。
［１６］触媒構成成分スラリーを触媒構成成分溶液と継続的に組み合わせて、前記共通担持触媒系を形成することを含む、上記［１３］に記載の前記方法。
［１７］前記触媒構成成分スラリーが、前記第１の触媒化合物を含み、前記触媒構成成分溶液が、前記第２の触媒化合物を含む、上記［１６］に記載の前記方法。
［１８］前記ポリオレフィンポリマーの組成分布、分子量分布、メルトインデックス（Ｉ_２）、もしくは２つのメルトインデックスの比率、またはこれらの任意の組み合わせを制御するために、重合反応器内で前記コモノマーのエチレンに対する比率を調整することを含む、上記［１３］に記載の前記方法。
［１９］前記ポリオレフィンポリマーの組成分布、分子量分布、メルトインデックス（Ｉ_２）、もしくは２つのメルトインデックスの比率、またはこれらの任意の組み合わせを制御するために、重合反応器内で水素のエチレンに対する比率を調整することを含む、上記［１３］に記載の前記方法。
［２０］エチレン及び４～２０個の炭素原子を有するα－オレフィンを含むポリオレフィンポリマーであって、前記ポリオレフィンポリマーが、共担持されて共通担持触媒系を形成する第１の触媒化合物及び第２の触媒化合物を含む触媒ブレンドを用いて形成され、前記第１の触媒化合物が、次の式、
（Ｃ_５Ｈ_ａＲ^１ _ｂ）（Ｃ_５Ｈ_ｃＲ^２ _ｄ）ＨｆＸ_２
を含み、式中、各Ｒ^１が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、各Ｒ^２が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、ａ及びｃが、≧３であり、ａ＋ｂ＝ｃ＋ｄ＝５であり、少なくとも１つのＲ^１及び少なくとも１つのＲ^２が、ヒドロカルビルまたは置換ヒドロカルビル基であり、隣接する基であるＲ^１及びＲ^２基が結合して環を形成してもよく、各Ｘが独立して、不安定なヒドロカルビル、置換ヒドロカルビル、またはヘテロ原子基から選択される脱離基であり、前記第２の触媒化合物が、次の鏡像異性体の混合物、

を含み、一方の鏡像異性体の他方の鏡像異性体に対する比率が、少なくとも約３であり、式中、各Ｒ^３が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、Ｒ^４が、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、各Ｒ^５が独立して、Ｈ、ヒドロカルビル基、置換ヒドロカルビル基、またはヘテロ原子基であり、Ｒ^３、Ｒ^４、及びＲ^５が、同じであっても異なってもよく、各Ｘが独立して、メチル基またはベンジル基から選択される脱離基である、前記ポリオレフィンポリマー。
［２１］前記ｍｅｓｏ鏡像異性体が、前記混合物中で約１９部であり、前記ｒａｃ鏡像異性体が、前記混合物中で約１部である、上記［２０］に記載の前記ポリオレフィンポリマー。
［２２］触媒組成物を形成する方法であって、
１－エチルインデニルリチウムをジメトキシエタン中に溶解させて、前駆体溶液を形成することと、
前記前駆体溶液を約－２０℃まで冷却することと、
固体ＺｒＣｌ_４を約５分間にわたって添加して、反応を開始することと、
前記反応を一晩継続することと、
揮発性物質を除去して、原料生成物を形成することと、
前記原料生成物をＣＨ_２Ｃｌ_２で抽出することと、
前記ＣＨ_２Ｃｌ_２を真空下で除去して、約１９部のｍｅｓｏ－（１－ＥｔＩｎｄ）_２ＺｒＣｌ_２及び約１部のｒａｃ－（１－ＥｔＩｎｄ）_２ＺｒＣｌ_２を含む混合物を形成することと、を含む、前記方法。
［２３］前記混合物をＥｔ_２Ｏ中でスラリー化することと、
エーテル中に溶解した少なくとも約２．３当量のＲＭｇＢｒであって、式中、Ｒが、ベンジル基、メチル基、またはこれらの混合物である、ＲＭｇＢｒを、前記スラリーに添加することと、
前記スラリーを乾燥させることと、
温かいヘキサンで抽出することと、
濾過して、約１９部のｍｅｓｏ－（１－ＥｔＩｎｄ）_２ＺｒＲ_２及び約１部のｒａｃ－（１－ＥｔＩｎｄ）_２ＺｒＲ_２を含む触媒構成成分を形成することと、を含む、上記［２２］に記載の前記方法。
［２４］触媒担体を不活性ガスで流動化することと、
前記担体を加熱していずれの吸着水も除去して、乾燥した担体を形成することと、
前記乾燥した担体を不活性ガス下で保管することと、を含む、上記［２３］に記載の前記方法。
［２５］前記乾燥した担体のスラリーをトルエン及びメチルアルミノキサンの混合物中で形成することと、
前記混合物を乾燥させて、シリカ担持メチルアルミノキサン（ａｍｌｕｍｉｎｏｘａｎｅ）（ＳＭＡＯ）を形成することと、を含む、上記［２４］に記載の前記方法。
［２６］ペンタンを前記ＳＭＡＯに添加して、スラリーを形成することと、
前記触媒構成成分をトルエン中に溶解させて、トルエン溶液を形成することと、
前記トルエン溶液を前記スラリーに添加して、触媒を形成することと、
前記触媒を前記スラリーから濾過することと、
前記触媒を乾燥させることと、を含む、上記［２５］に記載の前記方法。
While the foregoing is directed to embodiments of the invention, other and further embodiments of the invention are conceived without departing from its basic scope, which scope is determined by the following claims. . The present invention includes the following aspects.
[1] A method of forming a catalyst composition with substantially standardized stereochemical configuration, comprising:
slurrying the organometallic compound in dimethoxyethane (DME);
adding a solution of RMgBr in DME, wherein R is a methyl or benzyl group, and wherein said RMgBr is greater than about 2.3 equivalents relative to said organometallic compound;
mixing for at least about 4 hours to form an alkylated organometallic compound;
isolating said alkylated organometallic, wherein said alkylated species has a meso/rac enantiomeric ratio of from about 0.9 to about 1.2.
[2] dissolving 1-ethylindenyllithium in dimethoxyethane to form a precursor solution;
cooling the precursor solution to about −20° C.;
adding solid ZrCl ₄ over about 5 minutes to initiate the reaction;
continuing the reaction overnight;
removing volatiles to form a raw product;
extracting the raw product _{with CH2Cl2} ;
removing the CH ₂ Cl ₂ under vacuum to form the organometallic compound.
[3] Fluidizing the catalyst support with an inert gas;
heating the support to remove any adsorbed water to form a dry support;
The method according to [1] above, comprising storing the dried carrier under an inert gas.
[4] forming a slurry of the dried carrier in a mixture of toluene and methylaluminoxane;
drying the mixture to form silica-supported methylaluminoxane (SMAO).
[5] adding pentane to the SMAO to form a slurry;
dissolving the alkylated organometallic component in toluene to form a toluene solution;
adding the toluene solution to the slurry to form a catalyst;
filtering the catalyst from the slurry;
The method according to [4] above, comprising drying the catalyst.
[6] A method of alkylating an organometallic compound while substantially standardizing stereochemical configuration, comprising:
slurrying the organometallic compound in ether;
adding a solution of RLi in ether, wherein R is a methyl or benzyl group and said RLi is greater than about 2.3 equivalents relative to said organometallic compound and
mixing for at least about 4 hours to form an alkylated organometallic compound;
isolating said alkylated organometallic, wherein said alkylated species has a meso/rac ratio that is from about 0.9 to about 1.2.
[7] A catalyst composition comprising a first catalyst compound and a second catalyst compound co-supported to form a co-supported catalyst system, wherein the first catalyst compound is represented by the formula:
_{( C5HaR1b )} ^{( C5HcR2d} _{) HfX2 _ _}
wherein each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group and each R ² is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom a and c are ≧3, a+b=c+d=5, at least one R ¹ and at least one R ² is a hydrocarbyl or substituted hydrocarbyl group, and an adjacent group R ¹ and R ² groups may be joined to form a ring, each X is independently a leaving group selected from labile hydrocarbyl, substituted hydrocarbyl, or heteroatom groups, and said second catalyst The compound is a mixture of the following enantiomers,

wherein the ratio of said meso to said rac enantiomer is substantially normalized during alkylation to about 1.0 to about 1.2, and each R ³ independently represents H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, R ⁴ is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, and each R ⁵ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or Said catalyst composition, which is a heteroatom group, R ³ , R ⁴ and R ⁵ may be the same or different and each X is a methyl group.
[8] The catalyst composition according to [7] above, wherein the second catalyst compound comprises a compound having the formula:

[9] The catalyst composition of [7] above, wherein the second catalyst compound comprises at least one compound having the formula:

[10] The second catalyst compound has the formula:

wherein each ^R4A is independently methyl, ethyl, propyl, pentyl, hexyl, octyl, nonyl, dodecyl, phenethyl, or other hydrocarbyl The catalyst composition described.
[11] The catalyst composition according to [7] above, wherein the second catalyst compound comprises at least one compound having the formula:

[12] The catalyst composition according to [7] above, which contains a third catalyst.
[13] A method of polymerizing olefins to produce a polyolefin polymer having a multimodal composition distribution comprising contacting ethylene and a comonomer with a catalyst system, said catalyst system being co-supported and co- comprising a first catalyst compound and a second catalyst compound forming a supported catalyst system, said first catalyst compound having the formula:
⁽ _{C5HaR1b ) (} ^C5HcR2d _{) HfX2 _ _}
wherein each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group and each R ² is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom a and c are ≧3, a+b=c+d=5, at least one R ¹ and at least one R ² is a hydrocarbyl or substituted hydrocarbyl group, and an adjacent group R ¹ and R ² groups may be joined to form a ring, each X is independently a leaving group selected from labile hydrocarbyl, substituted hydrocarbyl, or heteroatom groups, and said second catalyst The compound is a mixture of the following enantiomers,

wherein the meso enantiomer is at least about 15 parts in the mixture and the rac enantiomer is less than about 5 parts in the mixture, wherein each R ³ independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, ^R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, and each ^R5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group , or a heteroatom group, wherein R ³ , R ⁴ , and R ⁵ may be the same or different, and each X is independently a labile hydrocarbyl, substituted hydrocarbyl, heteroatom group, or R is a leaving group selected from divalent radicals attached to the ³ , ^R4 , or ^R5 groups.
[14] to [13] above, wherein the X group is methyl and the meso/rac ratio is adjusted by methylation to give a MeLi solution in ether of about 2.3 equivalents to the catalyst compound; The method described above.
[15] The method of [13] above, comprising forming a product from the polyolefin polymer.
[16] The method of [13] above, comprising continuously combining a catalyst component slurry with a catalyst component solution to form the co-supported catalyst system.
[17] The method of [16] above, wherein the catalyst component slurry comprises the first catalyst compound and the catalyst component solution comprises the second catalyst compound.
[18] to control the composition distribution, molecular weight distribution, melt index (I ₂ ), or ratio of two melt indices, or any combination thereof, of the polyolefin polymer by The method according to [13] above, comprising adjusting the ratio.
[19] to control the compositional distribution, molecular weight distribution, melt index (I ₂ ), or ratio of two melt indices, or any combination thereof , of the polyolefin polymer; The method according to [13] above, comprising adjusting the ratio.
[20 ] A polyolefin polymer comprising ethylene and an α-olefin having from 4 to 20 carbon atoms , said polyolefin polymer being co-supported to form a co-supported catalyst system, a first catalyst compound and a second wherein the first catalyst compound has the formula:
_{( C5HaR1b )} ^{( C5HcR2d} _{) HfX2 _ _}
wherein each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group and each R ² is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom a and c are ≧3, a+b=c+d=5, at least one R ¹ and at least one R ² is a hydrocarbyl or substituted hydrocarbyl group, and an adjacent group R ¹ and R ² groups may be joined to form a ring, each X is independently a leaving group selected from labile hydrocarbyl, substituted hydrocarbyl, or heteroatom groups, and said second catalyst The compound is a mixture of the following enantiomers,

wherein the ratio of one enantiomer to the other enantiomer is at least about 3, wherein each R ³ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group , R ⁴ is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, each R ⁵ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, R ³ , R ⁴ , and Said polyolefin polymer wherein ^R5 may be the same or different and each X is independently a leaving group selected from methyl or benzyl.
[21] The polyolefin polymer of [20] above, wherein the meso enantiomer is about 19 parts in the mixture and the rac enantiomer is about 1 part in the mixture.
[22] A method of forming a catalyst composition comprising:
dissolving 1-ethylindenyllithium in dimethoxyethane to form a precursor solution;
cooling the precursor solution to about −20° C.;
adding solid ZrCl ₄ over about 5 minutes to initiate the reaction;
continuing the reaction overnight;
removing volatiles to form a raw product;
extracting the raw product _{with CH2Cl2} ;
removing the CH ₂ Cl ₂ under vacuum to form a mixture comprising about 19 parts meso-(1-EtInd) ₂ ZrCl ₂ and about 1 part rac-(1-EtInd) ₂ ZrCl ₂ ; .
[23] slurrying the mixture in Et ₂ O;
adding to the slurry at least about 2.3 equivalents of RMgBr dissolved in ether, wherein R is a benzyl group, a methyl group, or a mixture thereof;
drying the slurry;
extracting with warm hexane;
filtering to form a catalyst component comprising about 19 parts meso-(1-EtInd) ₂ ZrR ₂ and about 1 part rac-(1-EtInd) ₂ ZrR ₂ , above [22 ] The method described in .
[24] Fluidizing the catalyst support with an inert gas;
heating the support to remove any adsorbed water to form a dry support;
and storing the dried carrier under an inert gas.
[25] forming a slurry of the dried carrier in a mixture of toluene and methylaluminoxane;
drying the mixture to form silica-supported methylaluminoxane (SMAO).
[26] adding pentane to the SMAO to form a slurry;
dissolving the catalyst component in toluene to form a toluene solution;
adding the toluene solution to the slurry to form a catalyst;
filtering the catalyst from the slurry;
The method of [25] above, comprising drying the catalyst.

Claims (15)

A catalyst composition comprising a first catalyst compound and a second catalyst compound co-supported to form a co-supported catalyst system, wherein the first catalyst compound is represented by the formula:
⁽ _{C5HaR1b ) (} ^C5HcR2d _{) HfX2 _ _}
wherein each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group and each R ² is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom a and c are ≧3, a+b=c+d=5, at least one R ¹ and at least one R ² is a hydrocarbyl or substituted hydrocarbyl group, and an adjacent group R ¹ and R ² groups may be joined to form a ring, each X is independently a leaving group selected from hydrocarbyl, substituted hydrocarbyl, or a heteroatom group, and said second catalyst compound is a mixture of the following enantiomers,

wherein the ratio of said meso enantiomer to said rac enantiomer is at least 3, each R ³ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; ⁴ is a hydrocarbyl group, substituted hydrocarbyl group, or heteroatom group, each R ⁵ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, and R ³ , R ⁴ , and R ⁵ may be the same or different and each X is a methyl group. 2. The catalyst composition of claim 1, wherein the second catalyst compound comprises a compound having the formula:

2. The catalyst composition of claim 1, wherein said second catalyst compound comprises at least one compound having the formula:

The second catalyst compound has the formula:

wherein each ^R4A is independently methyl, ethyl, propyl, pentyl, hexyl, octyl, nonyl, dodecyl, phenethyl, or other hydrocarbyl The catalyst composition of 2. The catalyst composition of claim 1, wherein said second catalyst compound comprises at least one compound having the formula:

The catalyst composition according to any one of claims 1-5, comprising a third catalyst. 1. A method of polymerizing olefins to produce a polyolefin polymer having a multimodal composition distribution comprising contacting ethylene and a comonomer with a catalyst system, said catalyst system being co-supported to form a co-supported catalyst system. wherein the first catalyst compound comprises a first catalyst compound and a second catalyst compound that form:
_{( C5HaR1b )} ^{( C5HcR2d} _{) HfX2 _ _}
wherein each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group and each R ² is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom a and c are ≧3, a+b=c+d=5, at least one R ¹ and at least one R ² is a hydrocarbyl or substituted hydrocarbyl group, and an adjacent group R ¹ and R ² groups may be joined to form a ring, each X is independently a leaving group selected from hydrocarbyl, substituted hydrocarbyl, or a heteroatom group, and said second catalyst compound is a mixture of the following enantiomers,

wherein the meso enantiomer is at least 15 parts in the mixture and the rac enantiomer is less than 5 parts in the mixture, wherein each R ³ independently represents H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, R ⁴ is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, and each R ⁵ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, wherein R ³ , R ⁴ , and R ⁵ may be the same or different, and each X is independently hydrocarbyl, substituted hydrocarbyl, a heteroatom group, or R ³ , R ⁴ , or a leaving group selected from divalent radicals attached to the ^R5 group. The X group of the second catalyst compound is methyl and the meso/rac ratio is adjusted by methylation to give a MeLi solution in ether of 2.3 equivalents to the second catalyst compound. 8. The method of claim 7. 9. The method of claim 7 or 8, comprising forming a product from the polyolefin polymer. 10. The method of any one of claims 7-9, comprising continuously combining a catalyst component slurry with a catalyst component solution to form the co-supported catalyst system. 11. The method of claim 10, wherein the catalyst component slurry comprises the first catalyst compound and the catalyst component solution comprises the second catalyst compound. Adjusting the ratio of the comonomer to ethylene in the polymerization reactor to control the compositional distribution, molecular weight distribution, melt index ( _I2 ), or ratio of two melt indices, or any combination thereof, of the polyolefin polymer. The method of any one of claims 7-11, comprising: Adjusting the ratio of hydrogen to ethylene in the polymerization reactor to control the compositional distribution, molecular weight distribution, melt index ( _I2 ), or ratio of two melt indices, or any combination thereof, of said polyolefin polymer. The method according to any one of claims 7 to 12, comprising A polyolefin polymer comprising ethylene and an α-olefin having from 4 to 20 carbon atoms, said polyolefin polymer being co-supported to form a co-supported catalyst system comprising a first catalyst compound and a second catalyst compound. The first catalyst compound is formed using a catalyst blend comprising:
_{( C5HaR1b )} ^{( C5HcR2d} _{) HfX2 _ _}
wherein each R ¹ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group and each R ² is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom a and c are ≧3, a+b=c+d=5, at least one R ¹ and at least one R ² is a hydrocarbyl or substituted hydrocarbyl group, and an adjacent group R ¹ and R ² groups may be joined to form a ring, each X is independently a leaving group selected from hydrocarbyl, substituted hydrocarbyl, or a heteroatom group, and said second catalyst compound is a mixture of the following enantiomers,

wherein the ratio of said meso enantiomer to said rac enantiomer is at least 3, wherein each R ³ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group R ⁴ is a hydrocarbyl group, substituted hydrocarbyl group, or heteroatom group, each R ⁵ is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, and R ³ , R ⁴ , and R ⁵ may be the same or different and each X is independently a leaving group selected from methyl or benzyl. 15. The polyolefin polymer of claim 14, wherein the meso enantiomer is 19 parts in the mixture and the rac enantiomer is 1 part in the mixture.

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