Polymerization catalysts and process for producing bimodal polymers in a single reactor

Technical field of the invention

The present invention relates to the field of olefin polymerization catalysts, catalyst compositions, methods for the polymerization and copolymerization of olefins, polyolefins, and film and tubing resins formed therefrom, particularly by the use of a supported catalyst composition. . The present invention also relates to the fields of organic synthesis and organometallic synthesis, which include synthetic methods for semi-metallocenes.

Background of the invention

At present, a variety of polyethylene (PE) resins can be used to produce high rigidity pipe used in water, gas, and other fluid transport applications. Polyethylene pipe classified as PE-100, the typical MRS 10 cell classification, or ASTM D3350 345566C is especially desirable for use in conditions that require higher pressure ratings. To obtain a PE-100 classification, the PE-100 pipe is required to meet certain standards that specify stiffness, resistance to slow crack growth, resistance to chemical attack, and low temperature strength (expressed as rapid crack propagation). In addition, said tuning must comply with a deformation standard that is determined under high temperature pressure. It is also desirable that the PE-100 pipe exhibit rigidity, for example, when the pipe is buried underground or when the pipe is used to transport thick or abrasive suspensions. Accordingly, there is a need for a resin and a PE-100 pipe manufactured therefrom that possesses improved physical properties and impact resistance properties.

With conventional processes and resins formed through the use of metallocene catalyst systems, there is an interrelation between high rigidity and high resistance to environmental stress cracking (ESCR). Although articles of high rigidity or high ESCR can be manufactured, conventional processes do not produce articles that possess both high rigidity and high ESCR.

WO 2004/087770 describes a supported metallocene catalyst where more than two kinds of metallocene transition compounds are supported on a metal oxide such as silicon oxide, a method for preparing the catalyst, and a method for preparing polyolefins by catalyst use.

Hitchcock, et al., Polyhedron, 14 (19), 2745-52 describes redistribution reactions of ligands as a route to cyclopentadienyl- or 1-aza-allylzirconium (IV) trichlorides.

Compendium of the invention

The present invention generally relates to a catalyst composition that includes two metallocene compounds, an activator, and a cocatalyst. The present invention also relates to processes for producing said catalyst composition, polymerization processes, and polymers produced therefrom. The metallocene compounds are combined with an activator, an aluminum alkyl compound, and olefinic monomers to produce a polyolefin having a bimodal molecular weight distribution. The resulting polymers offer a remarkable balance of stiffness and resistance to slow crack growth. Additionally, polymers produced in accordance with the present invention possess excellent impact resistance.

In accordance with the present invention, the compounds of two metallocenes are selected such that the polymers produced therefrom possess two clearly different molecular weights. One of the metallocenes, typically a narrow bridge metallocene containing a substituent that includes a terminal olefin, produces a high molecular weight component. Another metallocene, which typically has no bridge and is often more sensitive to hydrogen than the first metallocene, produces a low molecular weight component of the resin.

In accordance with one aspect of the present invention, a catalyst composition comprises a first metallocene compound, a second metallocene compound, an activating support, and an organoaluminum compound. The first metallocene compound has the formula:

(X1) (X2R12) (X3) (X4) M1;

where (X1) is cyclopentadienyl, indenyl, or fluorenyl, (X2) is fluorenyl, and (X1) and (X2) are connected by a disubstituted bridge group comprising an atom attached to both (X1) and (X2), where the atom is carbon or silicon. A first substituent of the disubstituted bridge group is an aliphatic or aromatic group having 1 to about 20 carbon atoms. A second substituent of the disubstituted bridge group is a saturated or unsaturated aliphatic group having from 3 to about 10 carbon atoms. R1 is H or an alkyl group having 1 to about 4 carbon atoms, (X3) and (X4) independently are a halide, and

<dl><dt>M1 is Zr or Hf. The first substituent of the disubstituted bridge group may be phenyl or methyl. Substituent of the disubstituted bridge group may be butenyl, pentenyl, or hexenyl. In accordance with this and other aspects of the present invention, the first metallocene may be:</dt><dd> The second </dd></dl>

<dl><dt>Ph </dt><dd>Cl Cl ; Ph Cl Cl ; </dd></dl>

<dl><dt>5 </dt><dd>Cl Cl ; Cl Cl ; </dd></dl>

<dl><dt>�� </dt><dd> �� �� �� �� �� �� �� </dd></dl>

<dl><dt>; </dt>&lt;dd /&gt;<dt>; </dt>&lt;dd /&gt;</dl>

<dl><dt>�� </dt><dd> �� �� �� �� �� �� �� </dd></dl>

<dl><dt>; </dt>&lt;dd /&gt;<dt>; </dt>&lt;dd /&gt;</dl>

<dl><dt>�� </dt><dd> �� �� �� �� �� �� �� </dd></dl>

<dl><dt>; </dt>&lt;dd /&gt;<dt>; </dt>&lt;dd /&gt;</dl>

<dl><dt>10 </dt><dd> �� � �� �� �� �� ; �� � �� �� �� �� ; </dd></dl>

or any combination thereof. The second metallocene compound has the formula:

where R2 is H or -CH3; R3 is CH2 = CHCH2-, CH2 = CH (CH2) 2-, Ph (CH2) 3-, CH3 (CH2) 3, or H; X5 and X6 independently 10 are a halide; and M2 is Zr or Hf.

In accordance with this and other aspects of the present invention, the ratio of the first metallocene compound and the second metallocene compound may be from about 1:10 to about 10: 1. In accordance with other aspects of the present invention, the ratio of the first metallocene compound and the second metallocene compound may be from about 1: 5 to about 5: 1. In compliance

With still other aspects of the present invention, the ratio of the first metallocene compound and the second metallocene compound may be from about 1: 2 to about 2: 1.

The organoaluminum compound used with the present invention may have the formula:

(R2) 3Al;

where (R2) is an aliphatic group that has 2 to about 6 carbon atoms. In some cases, (R2) is an ethyl group, a propyl group, a butyl group, a hexyl group, or an isobutyl group.

In accordance with another aspect of the present invention, a catalyst composition comprises an ansa-metallocene compound, a bridgeless metallocene compound, an activating support, and an organoaluminum compound. The ansa-metallocene compound is:

A combination of them.

The metallocene compound without bridge is:

; ; or

A combination of them.

fifteen In accordance with this and other aspects of the present invention, the activating support may be fluorinated aluminum oxide, chlorinated aluminum oxide, brominated aluminum oxide, sulfated aluminum oxide, silicon oxide and fluorinated aluminum, silicon oxide and chlorinated aluminum , silicon oxide and brominated aluminum, silicon oxide and sulfated aluminum, silicon oxide and fluorinated zirconium, silicon oxide and chlorinated zirconium, silicon oxide and brominated zirconium, silicon oxide and sulfated zirconium, a pilareada clay, or any combination thereof.

twenty The catalyst composition of the present invention can thus comprise a first metallocene compound, a second metallocene compound, an activating support, and at least one organoaluminum compound, wherein:

<dl><dt>(to) </dt><dd>The first metallocene compound is: </dd></dl>

<dl><dt>(b) </dt><dd>The second metallocene compound is: </dd></dl>

;

<dl><dt>(c) </dt><dd>the activating support is sulfated aluminum oxide; </dd></dl>

<dl><dt>(d) </dt><dd>The organoaluminum compound is tri-n-butylaluminum. </dd></dl>

The present invention also contemplates a process for polymerizing olefins in the presence of a composition

5 catalyst The process comprises contacting the catalyst composition with at least one type of olefinic monomer under polymerization conditions, where the catalyst composition comprises an ansametalocene compound, a metallocene compound without a bridge, an activating support, and an organoaluminum compound. The ansa-metallocene compound has the formula:

(X1) (X2R12) (X3) (X4) M1;

10 where (X1) is cyclopentadienyl, indenyl, or fluorenyl, (X2) is fluorenyl, and (X1) and (X2) are connected by a disubstituted bridge group comprising an atom attached to both (X1) and (X2), where the atom is carbon or silicon. A first substituent of the disubstituted bridge group is an aliphatic or aromatic group having 1 to about 20 carbon atoms. A second substituent of the disubstituted bridge group is a saturated or unsaturated aliphatic group having from 3 to about 10 carbon atoms. R1 is H or a group

fifteen alkyl having 1 to about 4 carbon atoms, (X3) and (X4) independently are a halide, and M1 is Zr or Hf.

The metallocene without bridge has the formula:

,

where R2 is H or -CH3; R3 is CH2 = CHCH2-, CH2 = CH (CH2) 2-, Ph (CH2) 3-, CH3 (CH2) 3, or H; X5 and X6 independently 20 are a halide; and M2 is Zr or Hf.

The present invention further contemplates a process for producing a catalyst composition comprising contacting a first metallocene compound, a second metallocene compound, an activating support, and at least one organoaluminum compound. The first metallocene compound has the formula:

(X1) (X2R12) (X3) (X4) M1;

25 where (X1) is cyclopentadienyl, indenyl, or fluorenyl, (X2) is fluorenyl, and (X1) and (X2) are connected by a disubstituted bridge group comprising an atom attached to both (X1) and (X2), where the atom is carbon or silicon. A first substituent of the disubstituted bridge group comprises an aliphatic or aromatic group having 1 to about 10 carbon atoms. A second substituent of the disubstituted bridge group is a saturated or unsaturated aliphatic group having from 3 to about 10 carbon atoms. R1 is H or a group

30 alkyl having 1 to about 4 carbon atoms, (X3) and (X4) independently are a halide, and M1 is Zr or Hf.

The second metallocene has the formula:

,

where R2 is H or -CH3; R3 is CH2 = CHCH2-, CH2 = CH (CH2) 2-, Ph (CH2) 3-, CH3 (CH2) 3, or H; X5 and X6 independently are a halide; and M2 is Zr or Hf.

Brief description of the figures

FIG. 1 represents the NMR spectrum for Zr [T-C5H4- (nBu)] Cl3 formed in accordance with Example 1.

FIG. 2 represents the NMR spectrum for Zr [T-C5H4- (nBu)] Cl3 formed in accordance with Example 2.

FIG. 3 represents a comparison of the level of monomer incorporation by using metallocene compounds of the present invention with that of bis-indenyl zirconium dichloride.

FIG. 4 represents the molecular weight distribution of an exemplary polymer prepared in accordance with the present invention.

Definitions

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

The term "polymer" is used herein to mean homopolymers comprising ethylene and copolymers of ethylene and another olefinic comonomer. "Polymer" is also used herein to mean homopolymers and copolymers of any other polymerizable monomer described herein.

The term "cocatalyst" is generally used herein to refer to the organoaluminum compound may constitute a component of the catalyst composition. Additionally, "cocatalyst" refers to the optional components of the catalyst composition that include, but are not limited to, aluminoxanes, organoboro compounds, organozinc compounds, or ionizing ionic compounds, as described herein. The term "cocatalyst" can be used regardless of the actual function of the compound or any chemical mechanism by which the compound can operate. In one aspect of the present invention, the term "cocatalyst" is used to distinguish that component of the catalyst composition from the metallocene compound.

The term "fluoron boron compound" is used herein with its common meaning to refer to neutral compounds of the form BY3. The term "fluoroorgano borate compound" also has its usual meaning to refer to the monoanionic salts of a boron fluoroorgano compound of the form [cation] + [BY4] -, where Y represents a fluorinated organic group. For convenience, the fluoroorgano boron and fluoroorgano borate compounds are typically collectively referred to as "organoboro compounds", or by name as the context requires.

The term "precontacted" mixture is used herein to describe a first mixture of catalyst components that come into contact for a first period of time prior to the first mixture being used to form a "postcontacted" mixture or second mixture of catalyst components that come into contact for a second period of time. Typically, the precontacted mixture describes a mixture of metallocene compound (or compounds), olefinic monomer, and organoaluminum compound (or compounds), before this mixture is contacted with the activating support and optional additional organoaluminum compound. Thus, precontacted describes components that are used to contact one another, but prior to contacting the components of the second postcontacted mixture. Accordingly, the present invention may occasionally distinguish between a component used to prepare the precontacted mixture and that component after the mixture has been prepared. For example, in accordance with this description, it is possible that the precontacted organoaluminum compound, once in contact with the metallocene and the olefinic monomer, has reacted to form at least one chemical compound, formulation, or structure other than the compound of different organoaluminum used to prepare the precontacted mixture. In this case, the precontacted organoaluminum compound or component is described as comprising an organoaluminum compound that was used to prepare the precontacted mixture.

Similarly, the term "postcontacted" mixture is used herein to describe a second mixture of catalyst components that come into contact for a second period of time, and a constituent of which is the "precontacted" or first mixture. of catalyst components that were contacted for a first period of time. Typically, the term "postcontacted" mixture is used herein to describe the mixture of the metallocene compound, olefinic monomer, organoaluminum compound, and chemically treated solid oxide, formed from the contact of the precontacted mixture of a portion thereof. components with any additional components added to manufacture the postcontacted mixture. In general, the additional component added to make the post-contacted mixture is the chemically treated solid oxide, and, optionally, may include an organoaluminum compound equal to or different from the organoaluminum compound used to prepare the precontacted mixture, as described in the present memory Accordingly, the present invention can also occasionally distinguish between a component used to prepare the post-contacted mixture and that component after the mixture has been prepared.

The term "metallocene," as used herein, describes a compound comprising two ligands of the T5-cycloalcadienyl type in the molecule. Thus, the metallocenes of the present invention give bis compounds (ligand of the T5-cyclopentadienyl type) as defined in the appended claims. In some contexts, the metallocene is simply referred to as the "catalyst", similarly the term "cocatalyst" is used herein to refer to the organoaluminum compound. Unless otherwise specified, the following abbreviations are used: Cp for cyclopentadienyl; Ind for indenyl; and Flu for fluorenyl.

The terms "catalyst composition", "catalyst mixture", and the like do not depend on the actual product resulting from the contact or reaction of the components of the mixtures, the nature of the active catalytic site, or the development of the aluminum cocatalyst, the compound of metallocene, any olefinic monomer used to prepare a precontacted mixture, or chemically treated solid oxide after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", and the like may include both heterogeneous compositions and homogeneous compositions.

The term "hydrocarbyl" is used herein to specify a hydrocarbon radical group that includes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalcadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like, and includes all derivatives thereof substituted with heteroatom, linear, branched, substituted, unsubstituted.

The terms "chemically treated solid oxide", "solid oxide activating support", "acid activating support", "activating support", "treated solid oxide compound", or simply "activator", and the like are used herein to indicate a solid inorganic oxide of relatively high porosity, which exhibits Lewis acid behavior or Brønsted acid, and which has been treated with an attractive electron component, typically an anion, and which is calcined. The electron attractant component is typically a source compound of attractant electron anion. Thus, the chemically treated solid oxide compound comprises the calcined contact product of at least one solid oxide compound with at least one attractant electron anion source compound. Typically, the chemically treated solid oxide comprises at least one acidic, ionizing solid oxide compound. The terms "support" and "activating support" are not used to imply that these components are inert, and such components should not be construed as an inert component of the catalyst composition.

Although any method, device, and material similar or equivalent to those described herein may be used in the practice or assay of the invention, typical methods, devices and materials are described herein.

All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructions and methodologies described in the publications, which may be used in connection with the invention now described. . The publications discussed above and throughout the text are provided only for disclosure prior to the date of submission of this application. Nothing herein should be construed as an admission that the inventors have no right to advance such disclosure by virtue of the previous invention.

For any particular compound described herein, any general structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents. The general structure also encompasses all enantiomers, diastereomers, and other typical isomers in either enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context requires.

Detailed Description of the Invention

The present invention is directed in general to new catalyst compositions, methods for preparing catalyst compositions, and methods for using catalyst compositions to polymerize olefins. The present invention is further directed to a method for preparing cyclopentadienyl complexes and a method for isolating said compounds as a solid.

In particular, the present invention relates to new catalyst compositions and methods for using said catalyst compositions to form polyolefins that possess an excellent balance of stiffness and resistance to

slow growth of cracks. The catalyst composition includes at least two metallocenes. The first metallocene compound is used to produce a high molecular weight component, and in general it is a narrow bridge metallocene containing a substituent that includes a terminal olefin. The second metallocene, used to produce the low molecular weight component, is generally bridgeless and is more sensitive to hydrogen than the first metallocene. The metallocenes are combined with a solid activator, an aluminum alkyl compound, and an olefinic monomer to produce the desired bimodal polyolefin. It has been found that the bi-metallocene catalyst system of the present invention provides a useful combination of polyolefin properties, such as stiffness and resistance to slow crack growth, whereby the resin is suitable for blowing film, forming a pipe, and so on. .

In accordance with one aspect of the present invention, a chemical composition is provided. The composition includes a first metallocene compound, a second metallocene compound, an activating support, and an organoaluminum compound. In accordance with other aspects, the present invention is directed to a catalyst composition, a catalyst composition for polymerizing olefins, a method for preparing a catalyst composition, a method for using a catalyst composition, and the like, where in each case encompasses a first compound of metallocene, a second metallocene compound, an activating support, and an organoaluminum compound. The present invention is further directed to a method for producing polyolefins and film, and polyolefins and film produced therefrom. In accordance with yet another aspect, the present invention is directed to a method for preparing monocyclopentadienyl compounds that can be used to form metallocene compounds.

A. Composition and catalyst components

The present invention is directed to a catalyst composition that includes a first metallocene compound, a second metallocene compound, an activating support, and an organoaluminum compound. The first metallocene produces a high molecular weight component, and in general it is a narrow bridge metallocene containing a substituent that includes a terminal olefin. The second metallocene, used to produce the low molecular weight component, is generally bridgeless and more sensitive to hydrogen than the first metallocene. The combination of metallocenes is used with an activating support and an organoaluminum compound to form polyolefins that have an excellent balance of stiffness and resistance to slow crack growth.

Catalyst compositions that include various combinations of these metallocenes include, but are not limited to, at least a first metallocene compound, at least a second metallocene compound, and any combination of more than a first metallocene compound, more than a second Metallocene compound is also contemplated by the present invention. In addition, the use of more than an activating support and more than an organoaluminum compound is also contemplated.

1. Metallocene compounds

(a) The first metalloeeno compound

In accordance with one aspect of the present invention, the first metallocene compound is an ansa-metallocene compound having the formula:

(X1) (X2R12) (X3) (X4) M1 (I);

where (X1) is cyclopentadienyl, indenyl, or fluorenyl; (X2) is fluorenyl; (X1) and (X2) are connected by a disubstituted bridge group comprising an atom attached to both (X1) and (X2), where the atom is carbon or silicon; a first substituent of the disubstituted bridge group comprises an aliphatic or aromatic group having 1 to about 10 carbon atoms; a second substituent of the disubstituted bridge group is a saturated or unsaturated aliphatic group having from 3 to about 10 carbon atoms; R1 is H or an alkyl group having 1 to about 4 carbon atoms; (X3) and (X4) independently are a halide; and M1 is Zr or Hf.

In accordance with one aspect of the present invention, the first substituent of the disubstituted bridge group may be phenyl or methyl. The second substituent of the disubstituted bridge group may be butenyl, pentenyl, or hexenyl. In this and other aspects, (X3) and (X4) may be the same or different.

In accordance with yet another aspect of the present invention, the first metallocene compound is an ansa-metallocene compound having the formula:

(X1) (X2R12) (X3) (X4) M1;

where (X1) is cyclopentadienyl, indenyl, or fluorenyl; (X2) is fluorenyl; (X1) and (X2) are connected by a disubstituted bridge group comprising an atom attached to both (X1) and (X2), where the atom is carbon or silicon; a first substituent of the disubstituted bridge group comprises an aliphatic or aromatic group having 1 to about 6 carbon atoms; a second substituent of the disubstituted bridge group is a saturated or unsaturated aliphatic group having from 3 to about 6 carbon atoms; R1 is an alkyl group having 1 to about 4 carbon atoms; (X3) and (X4) independently are a halide; and M1 is Zr or Hf.

In accordance with one aspect of the present invention, the first substituent of the disubstituted bridge group may be phenyl or methyl. In accordance with another aspect of the present invention, the second substituent of the disubstituted bridge group may be butenyl, pentenyl, or hexenyl.

Some examples of metallocene compounds that may be suitable for use as the first metallocene compound according to the present invention include, but are not limited to:

Any combination thereof.

Additional examples of metallocene compounds that may be suitable for use as the first metallocene compound according to the present invention include, but are not limited to:

;

;

;

;

;

;

;

;

;

;

;

;

<dl>&lt;dt /&gt;<dd>or any combination thereof. </dd></dl>

<dl><dt>(b) </dt><dd>The second metalloeeno compound </dd></dl>

The second metallocene compound used in accordance with the present invention is characterized by the incorporation of comonomer poorer than Ind2ZrCl2. In addition, the second metallocene exhibits activity of

10 polymerization higher than Ind2ZrCl2. The catalysts are widely, and positively, sensitive to hydrogen, which produces a low molecular weight polymer that maintains high activity at the same time.

In accordance with the present invention, the second metallocene compound is a bridgeless metallocene compound having the formula:

(II);

where R2 is H or -CH3; and R3 is CH2 = CHCH2-, CH2 = CH (CH2) 2-, Ph (CH2) 3-, CH3 (CH2) 3, or H; X5 and X6 independently are a halide; and M2 is Zr or Hf. In this and other aspects, (X5) and (X6) may be the same or different. Examples of metallocene compounds that may be suitable for use as the second metallocene compound according to the present invention include, but are not limited to:

; ;

; ;

; ;

; ; or

Any combination thereof.

5 In this and other aspects of the present invention, the ratio of the first metallocene compound and the second metallocene compound may be from about 1:10 to about 10: 1. In still other aspects of the present invention, the ratio of the first metallocene compound and the second metallocene compound may be from about 1: 5 to about 5: 1. In still other aspects of the present invention, the ratio of the first metallocene compound and the second metallocene compound may be

10 about 1: 2 to about 2: 1.

(c) Synthesis of monoeielopentadienyl complexes

The present invention also provides a method for preparing monocyclopentadienyl compounds ("semi-metallocene compounds") that result in higher yield of the desired compound. The present invention further provides a method for isolating the desired compound as a solid. Yes I know

fifteen provide various exemplary compounds herein, it should be understood that the method of the present invention can be used to prepare numerous other semi-metallocene compounds. In one aspect, the semi-metallocene compounds formed in accordance with the present invention can be used to form metallocene compounds that are suitable for use in a dual catalyst system.

The currently known method of preparing a monocyclopentadienyl complex comprises adding solid ZrCl4

twenty in a stirring solution of ZrCp2Cl2 or a substituted Cp analogue in toluene at room temperature and stir for about 1 hour. The resulting mixture is filtered to produce the desired product as a dark oil. By using this method to manufacture said compounds, the resulting mixture basically consists of unreacted starting material zirconocene dichloride.

In accordance with the present invention, the reaction mixture is refluxed in toluene for

25 approximately 20 hours In doing this, the reaction is almost quantitative compared to the synthesis at room temperature currently known.

Toluene / Reflux

(1.3 R2R4Cp) 2MCl2 + MCl4

2 (1.3 R2R4Cp) MCl3

where M is Zr or Hf; R2 is H, an alkyl group, or an alkenyl group, and R4 is H, an alkyl group, or an alkenyl group. In one aspect, R2 is an alkyl group and R4 is H or an alkyl group. Thus, examples of semi-metallocene compounds that can be formed in accordance with the present invention include, but are not limited to Zr [T-C5H4- (nBu)] Cl3 and Zr [T-C5H3- (nBu, Me ) 1,3] Cl3.

In accordance with another aspect of the present invention, the semi-metallocene compound is optionally isolated as a solid. The solid is formed by contacting the reaction mixture with CH2Cl2 and pentane, hexane, heptane, or any combination thereof. In one aspect, the solid is formed by contacting the reaction mixture with a mixture of CH2Cl2 and pentane to produce the trichlorides as a solid. The ratio of CH2Cl2 and pentane can be 1: 2, 1: 3, 1: 4, 1: 5, or 1: 6, or any other appropriate ratio. Alternatively, a mixture of CH2Cl2 with hexane can be used. Alternatively still, a mixture of CH2Cl2 with heptane can be used. The amount of CH2Cl2 / pentane mixture used may vary for each reaction mixture, for example, for approximately 38g of (nBuCp) 2ZrCl2 approximately 150 ml of CH2Cl2 and 300 ml of pentane can be used.

The reaction mixture may be contacted several times with the CH2Cl2 / pentane mixture if necessary or desired. In one aspect, the reaction mixture can be contacted with the CH2Cl2 / pentane mixture once. In another aspect, the reaction mixture can be contacted with the CH2Cl2 / pentane mixture twice. In another aspect, the reaction mixture can be contacted with the CH2Cl2 / pentane mixture three times. In yet another aspect, the reaction mixture may be contacted with the CH2Cl2 / pentane mixture four or more times.

This method provides the semi-metallocene compound in at least about 50% yield. In one aspect, the method of the present invention provides the semi-metallocene compound in at least about 60% yield. In another aspect, the method of the present invention provides the semi-metallocene compound in at least about 70% yield. In yet another aspect, the method of the present invention provides the semi-metallocene compound in at least about 80% yield. In yet another aspect, the method of the present invention provides the semimetalocene compound in at least about 90% yield. In yet another aspect, the method of the present invention provides the semi-metallocene compound in at least about 95% yield.

two. The activator support

The present invention encompasses various catalyst compositions that include an activating support comprising a chemically treated solid oxide. Alternatively, the activating support may comprise a pilareada clay.

The chemically treated solid oxide exhibits enhanced acidity compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide also functions as an activating catalyst compared to the corresponding untreated solid oxide. While chemically treated solid oxide activates the metallocene in the absence of cocatalysts, it is not necessary to remove the cocatalysts from the catalyst composition. The activation function of the activating support is evident in the enhanced activity of the catalyst composition as a whole, as compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator, even in the absence of an organoaluminum compound, aluminoxanes, organoboro compounds, or ionizing ionic compounds.

The chemically treated solid oxide may comprise at least one solid oxide treated with at least one attractive electron anion. While we do not attempt to adhere to the following statement, it is believed that the treatment of solid oxide with an attractive electron component increases or enhances the acidity of the oxide. Thus, the activating support exhibits Lewis or Brønsted acidity that is typically greater than the acid strength of Lewis or Brønsted than the untreated solid oxide, or the activating support has a greater number of acid sites than the untreated solid oxide, or both. One method of quantifying the acidity of chemically treated and untreated solid oxide materials is to compare the polymerization activities of the treated and untreated oxides under acid catalyzed reactions.

The chemically treated solid oxide of the present invention is generally formed from an inorganic solid oxide having a relatively high porosity exhibiting Lewis acid or Brønsted acid behavior. The solid oxide is chemically treated with an attractive electron component, typically an attractive electron anion, to form an activating support.

In accordance with one aspect of the present invention, the solid oxide used to prepare the chemically treated solid oxide may have a pore volume greater than about 0.1 cc / g. In accordance with another aspect of the present invention, the solid oxide may have a pore volume greater than about 0.5 cc / g. In accordance with yet another aspect of the present invention, the solid oxide may have a pore volume greater than about 1.0 cc / g.

In accordance with another aspect of the present invention, the solid oxide may have a surface area of

approximately 100 to approximately 1000 m / g. In accordance with yet another aspect of this

invention, the solid oxide may have a surface area of ​​about 200 to about 800 m / g.

In accordance with yet another aspect of the present invention, the solid oxide may have a surface area of

about 250 to about 600 m / g.

The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and at least one element selected from group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 from the periodic table, or comprising oxygen and at least one element selected from the lanthanide or actinide elements. (See: Hawley's Condensed Chemical Dictionary, 11th Edition, John Wiley &amp; Sons; 1995; Cotton, FA; Wilkinson, G .; Murillo; CA; and Bochmann; M. Advanced Inorganic Chemistry, 6th Edition, Wiley-Interscience, 1999). For example, the inorganic oxide may comprise oxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn or Zr.

Suitable examples of solid oxide materials or compounds that can be used to form the chemically treated solid oxide include, but are not limited to, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including mixed oxides thereof, and combinations thereof. For example, the solid oxide may be silicon oxide, aluminum oxide, silicon and aluminum oxide, aluminum phosphate, heteropolitungstates, titanium oxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, or any combination thereof.

The solid oxide of the present invention encompasses oxide materials such as aluminum oxide, "mixed oxide" compounds thereof such as silicon oxide and aluminum, and combinations and mixtures thereof. Mixed oxide compounds such as silicon oxide and aluminum can be single or multiple chemical phases with more than a metal combined with oxygen to form a solid oxide compound. Examples of mixed oxide that can be used in the activating support of the present invention include, but are not limited to, silicon and aluminum oxide, silicon and titanium oxide, silicon and zirconium oxide, zeolites, various clay minerals, oxide of aluminum and titanium, aluminum oxide and zirconium, zinc aluminate and the like.

The electron attractant component used to treat the solid oxide can be any component that increases the Lewis or Brønsted acidity of the solid oxide with the treatment (as compared to the solid oxide that is not treated with at least one attractant electron anion). In accordance with one aspect of the present invention, the electron attracting component is an electron attracting anion obtained from a salt, an acid, or other compound, such as a volatile organic compound, which can serve as a source or precursor for that anion. Examples of attractive electron anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, trifluoroacetate, triflate, and the like, which It includes mixtures and combinations thereof. In addition, other ionic or non-ionic compounds that serve as sources for these attractant electron anions can also be employed in the present invention.

Thus, for example, the chemically treated solid oxide used with the present invention can be fluorinated aluminum oxide, chlorinated aluminum oxide, brominated aluminum oxide, sulfated aluminum oxide, silicon oxide and fluorinated aluminum, silicon oxide and chlorinated aluminum, silicon oxide and brominated aluminum, silicon oxide and sulfated aluminum, silicon oxide and fluorinated zirconium, silicon oxide and chlorinated zirconium, silicon oxide and brominated zirconium, silicon oxide and sulfated zirconium, or any combination thereof.

When the attracting electron component comprises a salt of an attracting electron anion, the counterion or cation of that salt can be selected from any cation that allows the salt to revert or decompose back to the acid during calcination. Factors that impose the adaptability of the particular salt to serve as a source for the attractive electron anion include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse reactivity of the cation, the effects of ionic mating between the cation and anion, the hygroscopic properties imparted to the salt by the cation, and the like, and the thermal stability of the anion. Examples of suitable cations in the electron-attractive anion salt include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H +, [H (OEt2) 2] +, and the like.

In addition, combinations of one or more different attractant electron anions, in varying proportions, can be used to adapt the specific acidity of the activating support to the desired level. Combinations of attractive electron components can be contacted with the oxide material simultaneously or individually, and in any order that produces the desired acidity of the chemically treated solid oxide. For example, one aspect of the present invention is to employ two or more source compounds of attractant electron anion in two or more separate contact steps.

Thus, an example of such a process by which a chemically treated solid oxide is prepared is as follows: a selected solid oxide compound, or a combination of oxide compounds, is contacted with a first attractant electron anion source compound to form a first mixture, this first mixture is then calcined and then contacted with a second compound source of attractive electron anion to form a second mixture, the second mixture is then calcined to form a treated solid oxide compound. In said process, the first and second source compounds of attractant electron anion can be different compounds or the same compound.

In accordance with another aspect of the present invention, the chemically treated solid oxide may comprise a material solid inorganic oxide, a material mixed oxide, or a combination of inorganic oxide materials, which is chemically treated with an electron attracting component, and optionally is dealt with a source of

metal, which includes metal salts, metal ions, or other compounds that contain metal. The metal or metal ion can be, for example, zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof. Examples of chemically treated solid oxides that include a metal or metal ion include, but are not limited to, chlorinated aluminum oxide impregnated with zinc, fluorinated aluminum oxide impregnated with titanium, fluorinated aluminum oxide impregnated with zinc, silicon oxide and chlorinated aluminum impregnated with zinc, silicon oxide and fluorinated aluminum impregnated with zinc, sulfated aluminum oxide impregnated with zinc, chlorinated zinc aluminate oxide, fluorinated zinc aluminate oxide, sulfated zinc aluminate oxide, or any combination thereof.

Any method can be used to impregnate the solid oxide material with a metal. The method by which the oxide is contacted with a metal source, typically a metal-containing salt or compound, may include, but is not limited to, gelation, co-gelation, impregnation of one compound in another, and the like. . If desired, the metal-containing compound can be added to or impregnated in the solid oxide in solution form, and subsequently converted into the metal supported with calcination. Accordingly, the solid inorganic oxide may further comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or a combination thereof. For example, zinc can be used to impregnate the solid oxide because it provides good catalytic activity and low cost.

The solid oxide can be treated with metal salts or metal-containing compounds before, after, or at the same time that the solid oxide is treated with the attractive electron anion. After any contact method, the contacted mixture of oxide compound, attractant electron anion, and the metal ion is typically calcined. Alternatively, a solid oxide material, an attractive electron anion source, and the metal salt or metal-containing compound are contacted and calcined simultaneously.

Various processes can be used to form the chemically treated solid oxide. The chemically treated solid oxide may comprise the contact product of at least one solid oxide compound and at least one source of attractive electron anion. The solid oxide compound is not required to be calcined prior to contact with the attractive electron anion source. The contact product may be calcined during or after the solid oxide compound comes into contact with the source of the attractive electron anion. The solid oxide compound can be calcined or uncalcined. Various processes for preparing solid oxide activating supports that can be used in the present invention have been reported. For example, such methods are described in US Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,391,816, 6,395,666, 6,524,987, and 6,548,441, each of which It is incorporated by reference herein, in its entirety.

In accordance with one aspect of the present invention, the solid material oxide can be chemically treated by contacting it with at least one attractant electron component, typically a source of attractant electron anion. In addition, the solid material oxide may optionally be chemically treated with a metal ion, and then calcined to form a chemically treated solid oxide containing metal or impregnated with metal. In accordance with another aspect of the present invention, the solid material oxide and source of attractant electron anion are contacted and calcined simultaneously.

The method by which the oxide is contacted with the electron attractant component, typically a salt or an acid of an attractant electron anion, may include, but is not limited to, gelation, co-gelation, impregnation of a compound in another , and the like. Thus, after any contact method, the contacted mixture of solid oxide, attractant electron anion, and optional metal ion is calcined.

The solid activator support oxide (chemically treated solid oxide) can thus be produced by a process comprising:

1) contacting a solid oxide compound with at least one attractant electron anion source compound to form a first mixture; and

2) calcine the first mixture to form the solid support activator oxide.

In accordance with another aspect of the present invention, the activator support solid oxide (chemically treated solid oxide) can be produced by a process comprising:

1) contact at least one solid oxide compound with a first attractant electron anion source compound to form a first mixture;

2) calcine the first mixture to produce a first calcined mixture;

3) contacting the first calcined mixture with a second attractant electron anion source compound to form a second mixture; and

4) calcine the second mixture to form the solid support activator oxide.

In accordance with yet another aspect of the present invention, the chemically treated solid oxide is produced or formed by contact of the solid oxide with the attracting electron anion source compound, where the solid oxide compound is calcined before, during, or after of contacting the attractive electron anion source, and where there is a substantial absence of aluminoxanes and organoborates.

The calcination of the treated solid oxide in general is conducted in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature of about 200 ° C to about 900 ° C, for about 1 minute to about 100 hours. The calcination can be conducted at a temperature of about 300 ° C to about 800 ° C, for example, at a temperature of about 400 ° C to about 700 ° C. The calcination can be conducted for about 1 hour to about 50 hours, for example, for about 3 hours to about 20 hours. Thus, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350 ° C to about 550 ° C. Any appropriate type of environment can be used during calcination. In general, calcination is conducted in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.

In accordance with one aspect of the present invention, the solid material oxide can be treated with a source of halide ion, sulfate ion, or a combination of anions, and optionally can be treated with a metal ion, and then can be calcined to provide the oxide chemically treated solid in the form of a particulate solid. For example, the solid oxide material can be treated with a sulfate source (called "sulfonating agent"), a source of chloride ion (called a "chlorinating agent"), a source of fluoride ion (called a fluorinating agent "), or a combination thereof, and calcined to provide the solid oxide activator. Acid activating supports include, but are not limited to: brominated aluminum oxide, chlorinated aluminum oxide, fluorinated aluminum oxide, sulfated aluminum oxide, silicon oxide and brominated aluminum, silicon oxide and chlorinated aluminum, silicon oxide and fluorinated aluminum, silicon oxide and sulfated aluminum, silicon oxide and brominated zirconium, silicon oxide and chlorinated zirconium, silicon oxide and fluorinated zirconium, silicon oxide and sulfated zirconium; a pilareada clay, such as a pilareated montmorillonite, optionally treated with fluoride, chloride, or sulfate; phosphate aluminum oxide or other aluminophosphates optionally treated with sulfate, fluoride, or chloride; or any combination of the above. In addition, any of the activating brackets can optionally be treated with a metal ion.

The chemically treated solid oxide may comprise a fluorinated solid oxide in the form of a particulate solid. The fluorinated solid oxide can be formed by contacting a solid oxide with a fluorinating agent. The fluoride ion can be added to the oxide by forming a suspension of the oxide in an appropriate solvent such as alcohol or water, which includes, but is not limited to, alcohols of one to three carbons due to their volatility and low surface tension. Examples of fluoridating agents that may be appropriate in the present invention include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), silicofluoride. ammonium (hexafluorosilicate) ((NH4) 2SiF6), ammonium hexafluorophosphate (NH4PF6), analogs thereof, and combinations thereof. For example, NH4HF2 ammonium bifluoride can be used as a fluoridating agent, due to its ease of use and rapid availability.

If desired, the solid oxide can be treated with a fluorinating agent during the calcination step. Any fluoridating agent capable of completely contacting the solid oxide can be used during the calcination step. For example, in addition to those previously described fluoridating agents, volatile organic fluorinating agents can be used. Examples of volatile organic fluoridating agents useful in this aspect of the invention include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and combinations thereof. The hydrogen fluoride gas or the fluorine itself can also be used with the solid oxide being fluorinated during calcination. A convenient method of contacting the solid oxide with the fluorinating agent is to evaporate a fluorinating agent in a gaseous stream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of the present invention, the chemically treated solid oxide may comprise a chlorinated solid oxide in the form of a particulate solid. The chlorinated solid oxide may be formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide by forming a suspension of the oxide in an appropriate solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a source of chloride and completely contacting the oxide can be used during the calcination stage . For example, volatile organic chlorinating agents can be used. Examples of useful volatile organic chlorinating agents that may be appropriate include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, or any combination thereof. Gaseous hydrogen chloride or the same chlorine with the solid oxide can also be used during calcination. A convenient method of contacting the oxide with the chlorinating agent is to evaporate a chlorinating agent in a gaseous stream used to fluidize the solid oxide during calcination.

The amount of fluoride or chloride ion present before the calcination of the solid oxide may be from about 2 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, for example, silicon oxide and aluminum, before calcination. In accordance with another aspect of the present invention, the amount of fluoride or chloride ion present before calcination of the solid oxide may be from about 3 to about 25% by weight, and in accordance with another aspect of the present invention, it may be from about 4 to about 20% by weight. Once impregnated with halide, the halide oxide can be dried by any method known in the art that includes, but is not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible to initiate the calcination step immediately without drying the impregnated solid oxide

The silicon and aluminum oxide used to prepare the treated silicon and aluminum oxide typically has a pore volume greater than about 0.5 cc / g. In accordance with one aspect of the present invention, the pore volume may be greater than about 0.8 cc / g, and in accordance with another aspect of the present invention, the pore volume may be greater than about 1.0 cc / g. In addition, silicon oxide and aluminum may have a surface area greater than about 100 m2 / g. In accordance with one aspect of the present invention, the surface area may be greater than about 250 m2 / g, and in accordance with another aspect of the present invention, the surface area may be greater than approximately 350 m2 / g.

The silicon and aluminum oxide used with the present invention typically has an aluminum oxide content of about 5 to about 95%. In accordance with one aspect of the present invention, the aluminum oxide content of the silicon and aluminum oxide may be from about 5 to about 50%, and in accordance with another aspect of the present invention, the aluminum oxide content of the Silicon and aluminum oxide can be from about 8% to about 30% aluminum oxide by weight. In accordance with yet another aspect of the present invention, the solid oxide component may comprise aluminum oxide without silicon oxide, and in accordance with another aspect of the present invention, the solid oxide component may comprise silicon oxide without oxide of aluminum.

The sulfated solid oxide comprises sulfate and a solid oxide component such as aluminum oxide or silicon oxide and aluminum, in the form of a particulate solid. Optionally, the sulfated oxide is further treated with a metal ion such that the calcined sulfated oxide comprises a metal. In accordance with one aspect of the present invention, the sulfated solid oxide comprises sulfate and aluminum oxide. In some cases, sulfated aluminum oxide is formed by a process where aluminum oxide is treated with a sulfate source, for example, but not limited to, sulfuric acid or a sulfate salt such as ammonium sulfate. This process can be carried out by forming an aluminum oxide suspension in an appropriate solvent such as alcohol or water, in which the desired concentration of sulphating agent has been added. Appropriate organic solvents include, but are not limited to, alcohols of one to three carbons due to their volatility and low surface tension.

In accordance with one aspect of the present invention, the amount of sulfate ion present before calcination can be from about 0.5 parts by weight to about 100 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. In accordance with another aspect of the present invention, the amount of sulfate ion present before calcination can be from about 1 part by weight to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and in accordance with yet another aspect of the present invention, from about 5 parts by weight to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of the solid oxide before calcination. Once impregnated with sulfate, the sulfated oxide can be dried by any method known in the art that includes, but is not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible to initiate the calcination stage immediately.

In accordance with another aspect of the present invention, the activating support comprises a pilareada clay. The term "pilareada clay" is used to refer to clay materials that have exchanged ions with large complex highly charged metal cations typically polynuclear. Examples of such ions include, but are not limited to, Keggin ions that may have charges such as 7+, various polyoxomethalates, and other large ions. Thus, the term pilarear refers to a simple exchange reaction in which the exchangeable cations of a clay material are replaced with large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the clay interlayers and when calcined they become "pillars" of metal oxide, effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded grid structure is maintained and the porosity is enhanced. The resulting pores may vary in shape and size as a function of the pillar material and the parent clay material used. Examples of pillarization and clay pilareadas are found in: TJ Pinnavaia, Seienee 220 (4595), 365-371 (1983); JM Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pages 55-99, Academic Press, Inc., (1972); US Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent No. 4,060,480; each of which is incorporated herein in its entirety.

The pillarization process uses clay minerals that have interchangeable cations and layers capable of expanding. Any pilareated clay that can enhance the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, clay minerals suitable for pillarization include, but are not limited to: allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; haloisites; vermiculites; micas; fluoromics; chlorites; mixed layer clays; fibrous clays that include but are not limited to sepiolites, attapulgites, and paligorsquitas; a serpentine clay; ilita; laponite; saponite; and any combination thereof. In one aspect, the pilareated clay activating support comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.

Pilareated clay can be pretreated if desired. For example, a pilareated bentonite can be pretreated by drying at about 300 ° C under an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although here it is

describes an exemplary pretreatment, it should be understood that preheating can be carried out at many other temperatures and times, which include any combination of temperature and time stages, where all are encompassed by the present invention.

The activating support used to prepare the catalyst compositions of the present invention may be combined with other inorganic support materials, which include, but are not limited to, zeolites, inorganic oxides, phosphate inorganic oxides, and the like. In one aspect, typical support materials that can be used include, but are not limited to, silicon oxide, silicon oxide and aluminum, aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, boron oxide, fluorinated aluminum oxide, silated aluminum oxide, thorium oxide, aluminophosphate, aluminum phosphate, phosphate silicon oxide, phosphate aluminum oxide, silicon and titanium oxide, coprecipitated silicon oxide and titanium oxide, fluorinated aluminum oxide / silage, and any combination or mixture thereof.

In accordance with yet another aspect of the present invention, one or more of the metallocene compounds may be precontacted with an olefinic monomer and an organoaluminum compound for a first period of time prior to the contact of this mixture with the activating support. Once the precontacted mixture of metallocene compounds / s, olefinic monomer, and organoaluminum compound is contacted with the activating support, the composition that further comprises the activating support is called a "postcontacted" mixture. The postcontacted mixture may be allowed to remain in additional contact for a second period of time prior to being loaded into the reactor in which the polymerization process will be carried out.

3. The organoaluminum compound

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

(R2) 3Al;

where (R2) is an aliphatic group that has 2 to about 6 carbon atoms. For example, (R2) can be an ethyl group, a propyl group, a butyl group, a hexyl group, or an isobutyl group.

Other organoaluminum compounds that can be used in accordance with the present invention include, but are not limited to, compounds having the formula:

Al (X9) n (X10) 3-n,

where (X9) is a hydrocarbyl having 1 to about 20 carbon atoms, (X10) is an alkoxide or an aryloxide, any one of which has 1 to about 20 carbon atoms, a halide, or a hydride, and n is a number from 1 to 3, inclusive. In accordance with one aspect of the present invention, (X9) is an alkyl having 1 to about 10 carbon atoms. Examples of moieties (X9) include, but are not limited to, ethyl, propyl, n-butyl, sec-butyl, isobutyl, hexyl, and the like. In accordance with another aspect of the present invention, (X10) can independently be selected from fluoro or chloro. In accordance with yet another aspect of the present invention, (X10) may be chlorine. In the formula Al (X9) n (X10) 3-n, n is a number from 1 to 3 inclusive, and typically, n is 3. The value of n is not limited to being an integer; Therefore, this formula includes sesquihalide compounds or other organoaluminum group compounds.

Examples of organoaluminum compounds that may be suitable for use with the present invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations of the same. Specific examples of organoaluminum compounds that may be appropriate include, but are not limited to: trimethylaluminum (TMA); triethylaluminum (ASD); tripropyl aluminum; diethylaluminum ethoxide; aluminum tributyl; disobutyl aluminum hydride; triisobutylaluminum (TIBA); and diethyl aluminum chloride.

The present invention contemplates precontacting the first metallocene compound, the second metallocene compound, or both, with at least one organoaluminum compound and an olefinic monomer to form a precontacted mixture, prior to contacting this precontacted mixture with the activating support to form the active catalyst When the catalyst composition is prepared in this manner, typically, although not necessarily, a portion of the organoaluminum compound is added to the precontacted mixture and another portion of the organoaluminum compound is added to the postcontacted mixture prepared when the precontacted mixture is contacted. with the solid oxide activator. However, the complete organoaluminum compound can be used to prepare the catalyst in the precontact or postcontact step. Alternatively, all catalyst components can be contacted in a single stage.

In addition, more than an organoaluminum compound can be used in the precontact or postcontact stage. When an organoaluminum compound is added in multiple stages, the amounts of organoaluminum compound described herein include the total amount of organoaluminum compound used in both precontacted and postcontacted mixtures, and any additional organoaluminum compounds added to the polymerization reactor. Therefore, the total amounts of organoaluminum compounds are described regardless of whether a single organoaluminum compound or more than an organoaluminum compound is used.

Four. The optional aluminoxane cocatalyst

The present invention further provides a catalyst composition comprising an optional aluminoxane cocatalyst. As used herein. The term "aluminoxane" refers to aluminoxane compounds, compositions, mixtures, or discrete species, regardless of how they are prepared, formed or otherwise.

5 such aluminoxanes are provided. For example, a catalyst composition comprising an optional aluminoxane cocatalyst can be prepared in which the aluminoxane is provided as a poly (aluminum hydrocarbyl oxide), or in which the aluminoxane is provided as the combination of an aluminum alkyl compound and a source of active protons such as water. Aluminoxanes are also called poly (aluminum hydrocarbyl oxides) or organoaluminoxanes.

The other catalyst components are typically contacted with the aluminoxane in a saturated hydrocarbon compound solvent, although any solvent that is substantially inert to the reagents, intermediates, and products of the activation step can be used. The catalyst composition formed in this manner can be collected by methods known to those skilled in the art that include, but are not limited to, filtration. Alternatively, the catalyst composition can be introduced into the reactor of

fifteen polymerization without being isolated.

The aluminoxane compound of the present invention may be an oligomeric aluminum compound comprising linear, cyclic structures, or cage structures, or mixtures of the three. Cyclic aluminoxane compounds that have the formula:

At o n

R;

where R is a linear or branched alkyl having 1 to 10 carbon atoms, and n is an integer from 3 to about 10, they are encompassed by the present invention. The remainder (AlRO) n shown here also constitutes the repeating unit in a linear aluminoxane. Thus, linear aluminoxanes that have the formula:

R

Ral OR To the n

R

R;

25 where R is a linear or branched alkyl having 1 to 10 carbon atoms, and n is an integer from 1 to about 50, they are also encompassed by the present invention.

In addition, aluminoxanes can also have cage structures of the formula Rt5m + aRbm-aAl4mO3m, where m is 3 or 4 is already = nAl (3) - nO (2) + nO (4), where nAl (3) e3s the number of three coordinated aluminum atoms, nO (2) is the number of two coordinated oxygen atoms, nO (4) is the number of 4 coordinated oxygen atoms, Rt is a terminal alkyl group, and Rb is a bridge alkyl group, and R is a linear or branched alkyl having 1 to 10 carbon atoms.

Thus, aluminoxanes that can serve as optional cocatalysts in the present invention in general are represented by formulas such as (R-Al-O) n, R (R-Al-O) nAlR2, and the like, where the group R is typically a linear or branched C1-C6 alkyl such as methyl, ethyl, propyl, butyl, pentyl, or hexyl where n

35 typically represents an integer from 1 to 50. Examples of aluminoxane compounds that can be used in accordance with the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propyl aluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane. , sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentyl aluminoxane, or any combination thereof. Methyl aluminoxane, ethyl aluminoxane, and isobutyl aluminoxane are prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively, and are sometimes referred to as poly (methyl aluminum oxide), poly (ethyl aluminum oxide), and poly ( isobutyl aluminum oxide), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminum, as described in US Patent No. 4,794,096, incorporated herein by reference in its entirety.

Four. Five The present invention contemplates many values ​​of n in the formulas of aluminoxane (R-Al-O) and R (R-Al-O) nAlR2, and n can typically be at least about 3. However, depending on how the organoaluminoxane is prepared , is stored, and used, the value of n can be variable within a single sample of aluminoxane, and said organoaluminoxane combinations are contemplated by the present invention.

In the preparation of the catalyst composition of the present invention comprising an optional aluminoxane, the molar ratio of aluminum in aluminoxane and metallocene in the composition may be approximately

1:10 to about 100,000: 1, for example, from about 5: 1 to about 15,000: 1. The amount of optional aluminoxane added to a polymerization zone may be approximately 0.01 mg / L

at about 1000 mg / L, from about 0.1 mg / L to about 100 mg / L, or from about 1 mg / L to about 50 mg / L.

Organoaluminoxanes can be prepared by various procedures that are well known in the art. Examples of organoaluminoxane preparations are described in US Patent Nos. 3,242,099 and 4,808,561, each of which is incorporated herein by reference in its entirety. For example, water in an inert organic solvent can be reacted with an aluminum alkyl compound such as AlR3 to form the desired organoaluminoxane compound. While we do not attempt to adhere to this statement, it is believed that this synthetic method can achieve a mixture of both cyclic and linear aluminoxane (R-Al-O) species, both of which are encompassed by the present invention. Alternatively, organoaluminoxanes can be prepared by reacting an aluminum alkyl compound such as AlR3 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.

5. The optional organoboro cocatalyst

The present invention further provides a catalyst composition comprising an optional organoboro cocatalyst. The organoboro compound may comprise neutral boron compounds, borate salts, or any combination thereof. For example, the organoboro compounds of the present invention may comprise a fluoroorgano boron compound, a fluoroorgano borate compound, or a combination thereof.

Any fluoroorganoboro or fluoroorganoborate compound known in the art can be used with the present invention. Examples of fluoroorgano borate compounds that can be used as cocatalysts in the present invention include, but are not limited to, fluorinated aryl borates such as, tetrakis (pentafluorophenyl) N borate, N -dimethylanilinium, tetrakis (pentafluorophenyl) triphenylcarbenium borate , tetrakis (pentafluorophenyl) lithium borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] N, N-dimethylanilinium borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] triphenylcarbenium borate, and the like, which include their mixtures. Examples of fluoroorgano boron compounds that can be used as cocatalysts in the present invention include, but are not limited to, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and the like, which include their mixtures Although we do not attempt to adhere to the following theory, these examples of fluoroorgano borate and fluoroorgano boron compounds, and related compounds, are thought to form "weak coordination" anions when combined with organometal compounds, as described in US Patent 5,919 .983, which is incorporated herein by reference in its entirety.

In general, any amount of organoboro compound can be used. In accordance with one aspect of the present invention, the molar ratio of the organoboro compound and the metallocene compound in the composition may be from about 0.1: 1 to about 10: 1. Typically, the amount of fluoroorgano boron or fluoroorgano borate compound used as a cocatalyst for metallocenes may be from about 0.5 mol to about 10 moles of boron compound per total moles of metallocene compounds. In accordance with another aspect of the present invention, the amount of fluoroorgano boron or fluoroorgano borate compound may be from about 0.8 moles to about 5 moles of boron compound per total moles of the metallocene compound.

6. The optional ionizing ionic compound cocatalyst

The present invention further provides a catalyst composition comprising an optional ionizing ionic compound cocatalyst. An ionizing ionic compound is an ionic compound that can function to enhance the activity of the catalyst composition. While we do not stick to the theory, it is believed that the ionizing ionic compound may be able to react with a metallocene compound and convert the metallocene into one or more cationic metallocene compounds, or incipient cationic metallocene compounds. Again, although we do not attempt to stick to the theory, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or partially extracting an anionic ligand, possibly a non-T5-alkadienyl ligand such as (X3) or (X4) of the metallocene. However, the ionizing ionic compound is an activator regardless of whether it ionizes the metallocenes, separates a ligand (X3) or (X4) in a way to form an ionic pair, weakens the metal- (X3) or metal- (X4) junction ) in the metallocene, simply coordinate the ligand (X3) or (X4), or activate the metallocene by some other mechanism.

In addition, it is not necessary for the ionizing ionic compound to activate the metallocenes only. The activation function of the ionizing ionic compound is evident in the enhanced activity of the catalyst composition as a whole, as compared to a catalyst composition containing catalyst composition which does not comprise any ionizing ionic compound. It is also not necessary for the ionizing ionic compound to activate each of the metallocene compounds present, nor is it necessary for it to activate any of the metallocene compounds to the same extent.

Examples of ionizing ionic compounds include, but are not limited to, the following compounds: tri (n-butyl) ammonium tetrakis (p-tolyl) borate, tri (n-butyl) ammonium tetrakis (m-tolyl), tri (n-butyl) ammonium tetrakis (2,4-dimethyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl], tri (n-) tetrakis (pentafluorophenyl) borate butyl) ammonium, N, N-dimethylanilinium tetrakis (p-tolyl) borate, N, N-dimethylanilinium tetrakis, N, N-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate, N, N-dimethylanilinium, tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium, tetrakis (p-) tetrakis [3,5-bis (trifluoromethyl) phenyl] borate tolyl) triphenylcarbenium borate, tetrakis (m-tolyl) triphenylcarbenium borate, tetrakis (2,4-dimethylphenyl) triphenylcarbenium borate, tetrakis (3,5

dimethylphenyl) triphenylcarbenium borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] triphenylcarbenium borate, tetrakis (pentafluorophenyl) triphenylcarbenium borate, tetrakis (p-tolyl) tropilio borate, tetrakis (m-tolyl) tropilio borate, Tropyllium tetrakis (2,4-dimethylphenyl) borate, tetrakis (3,5-dimethylphenyl) tropyl borate, tetrakis [3,5bis (trifluoromethyl) phenyl] tropyl borate, tetrakis (pentafluorophenyl) tropyl borate, tetrakis (pentafluorophenyl) lithium borate, lithium tetrakis (phenyl) borate, lithium tetrakis (p-tolyl) borate, lithium tetrakis (m-tolyl), tetrakis (2,4-dimethylphenyl) lithium borate, tetrakis (3,5-dimethylphenyl) lithium borate, lithium tetrafluoroborate, sodium tetrakis (pentafluorophenyl) borate, sodium tetrakis (phenyl) borate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, tetrakis (2,4-dimethylphenyl) borate sodium, sodium tetrakis (3,5-dimethylphenyl) borate, sodium tetrafluoroborate, tetrakis (pentafluorophenyl) potassium borate, tetrakis (phenyl) potassium borate, tetrakis (p-tolyl) potassium borate, tetrakis (m-tolyl) potassium borate, tetrakis (2,4-dimethylphenyl) potassium borate, tetrakis ( Potassium 3,5-dimethylphenyl) borate, potassium tetrafluoroborate, tri (n-butyl) ammonium tetrakis (p-tolyl) aluminate, tri (n-butyl) ammonium tetrakis (m-tolyl) aluminate, tetrakis (2, Tri (n-butyl) ammonium 4-dimethyl) aluminate, tri (nbutyl) ammonium tetrakis (3,5-dimethylphenyl) aluminate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) aluminate, N-N-dimethylanilinium tetrakis (p-tolyl) aluminate, N-N-dimethylanilinium tetrakis (m-tolyl) aluminate, tetrakis (2,4-dimethylphenyl) aluminate N, N-dimethylanilinium, tetrakis (3,5-dimethylphenyl) aluminate of N, N-dimethylanilinium, tetrakis (pentafluorophenyl) aluminate of N, N-dimethylanilinium, tetrakis (p-tolyl) triphenylcarbenium tetrakis, tetrakis (m-tolyl) alumina of triphenylcarbenium triphenylcarbenium tetrakis (2,4-dimethylphenyl) aluminate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) aluminate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, tropilium tetrakis (p-tolyl) aluminate, tetrakyl tetrakis (mtolyl) aluminate, tetrakis (2,4-dimethylphenyl) tropilium aluminate, tropyl tetrakis (3,5-dimethylphenyl) aluminate, tropyl tetrakis (pentafluorophenyl) aluminate, lithium tetrakis (pentafluorophenyl) aluminate, lithium tetrakis (phenyl) aluminate, lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate, lithium tetrakis (2,4-dimethylphenyl) lithium, lithium tetrakis (3,5-dimethylphenyl) aluminate, lithium tetrafluoroaluminate, sodium tetrakis (pentafluorophenyl) aluminate, tetrakis (phenyl) sodium aluminate, sodium tetrakis (p-tolyl) aluminate, sodium tetrakis (m-tolyl) aluminate, sodium tetrakis (2,4-dimethylphenyl) aluminate, sodium tetrakis (3,5-dimethylphenyl) aluminate, tetrafluoroaluminate sodium, tetrakis (pentafluorophenyl) potassium aluminate, potassium tetrakis (phenyl) aluminate, potassium tetrakis (p-tolyl) aluminate, potassium tetrakis (m-tolyl) aluminate, potassium tetrakis (2,4-dimethylphenyl) aluminate, tetrakis (3,5-dimethylphenyl) potassium aluminate, potassium tetrafluoroaluminate and the like. However, ionizing ionic compounds that are useful in the present invention are not limited thereto. Other examples of ionizing ionic compounds are described in US Pat. Nos. 5,576,259 and 5,807,938, each of which is incorporated herein by reference in its entirety.

B. Oleanic mon6me ro

Unsaturated reagents that may be useful with the catalyst compositions and polymerization processes of the present invention include olefinic compounds having from about 2 to about 30 carbon atoms per molecule and at least one olefinic double bond. The present invention encompasses homopolymerization processes by using a single olefin such as ethylene or propylene, as well as copolymerization reactions with at least one different olefinic compound. The resulting copolymer can comprise a significant amount of ethylene (&gt; 50 percent by mol) and a smaller amount of comonomer &lt;50 percent by mole), although this is not a requirement. Comonomers that can be copolymerized with ethylene can typically have three to about 20 carbon atoms in their molecular chain.

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

When a copolymer is desired, the ethylene monomer can be polymerized with a comonomer. Examples of the comonomer include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1heptene, 2-heptene, 3-heptene, the normal four octenes, the four normal nonenos, or the five normal deans. In accordance with one aspect of the present invention, the comonomer may be selected from 1butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or styrene.

The amount of comonomer introduced into a reactor zone to produce the copolymer in general may be from about 0.01 to about 50 percent by weight of comonomer based on the total weight of the monomer and comonomer. In accordance with another aspect of the present invention, the amount of comonomer introduced into a reactor zone may be from about 0.01 to about 40 percent by weight of comonomer based on the total weight of the monomer and comonomer. In accordance with yet another aspect of the present invention, the amount of comonomer introduced into a reactor zone may be from about 0.1 to about 35 percent by weight of comonomer based on the total weight of monomer and comonomer. Alternatively, the amount of comonomer introduced into a reactor zone may be any amount sufficient to provide the above weight concentrations.

While we do not attempt to adhere to this theory, where branched, substituted, or functionalized olefins are used as reagents, it is believed that steric blockage can prevent and / or reduce the speed of the polymerization process. Thus, the portion (s) is branched / s and / or cyclic / s of the olefin somewhat removed from the double bond

Carbon-carbon would not be expected to prevent the reaction in the way that the same olefinic substituents closest to the carbon-carbon double bond could do them. In accordance with one aspect of the present invention, at least one reagent for the catalyst compositions of the present invention may be ethylene, so the polymerizations are homopolymerizations or copolymerizations with a different acyclic, cyclic, terminal, internal, linear, branched olefin. substituted, or unsubstituted. In addition, the catalyst compositions of the present invention can be used in the polymerization of diolefin compounds, including but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

C. Preparation of the catalyst composition

The present invention encompasses a catalyst composition comprising the contact product of a first metallocene compound, a second metallocene compound, an activating support, and an organoaluminum compound. The present invention further encompasses methods for manufacturing the catalyst composition that includes contacting a first metallocene compound, a second metallocene compound, an activating support, and an organoaluminum compound, in any order. In accordance with said methods, a catalyst composition is obtained when the catalyst components are contacted in any sequence or order.

One or more of the metallocene compounds may be precontacted with an olefinic monomer if desired, not necessarily the olefinic monomer should be polymerized, and an organoaluminum cocatalyst for a first period of time prior to contacting this precontacted mixture with the activating support. The first period of time for contact, the precontact time, between the metallocene compound or compounds, the olefinic monomer, and the organoaluminum compound can typically vary in time from about 0.1 hour to about 24 hours, for example, from about 0.1 to about 1 hour. Precontact times of about 10 minutes to about 30 minutes are also typical.

Once the precontacted mixture of the metallocene compound or compounds, olefinic monomer, and organoaluminum cocatalyst is contacted with activating support, this composition (which further comprises the activating support) is called "postcontacted mixture". The postcontacted mixture may optionally be allowed to remain in contact for a second period of time, the postcontact time, prior to starting the polymerization process. Postcontact times between the precontacted mixture and the activating support can vary in time from about 0.1 hour to about 24 hours, for example, from about 0.1 hour to about 1 hour. In the precontact or postcontact stage, or both can increase the productivity of the polymer compared to the same catalyst composition that is prepared without the precontact or postcontact. However, neither a precontact stage nor a postcontact stage is required.

The postcontacted mixture may be heated to a temperature and for a duration sufficient to allow adsorption, impregnation, or interaction of the precontacted mixture and the activating support, such that a portion of the components of the precontacted mixture is immobilized, absorbed, or deposited therein. When heating is used, the postcontacted mixture can be heated from about 0 ° F to about 150 ° F, for example, from about 40 ° F to about 95 ° F.

In accordance with one aspect of the present invention, the molar ratio of the total moles of the metallocene compounds and the organoaluminum compound may be from about 1: 1 to about 1: 10,000. In accordance with another aspect of the present invention, the molar ratio of the total moles of the combined metallocene compounds and the organoaluminum compound may be from about 1: 1 to about 1: 1,000. In accordance with yet another aspect of the present invention, the molar ratio of the total moles of the combined metallocene compounds and the organoaluminum compound may be from about 1: 1 to about 1: 100. The molar ratios reflect the ratio of the metallocene compounds and the total amount of the organoaluminum compound in both the precontacted mixture and the postcontacted mixture combined.

When a precontact step is used, the molar ratio of olefinic monomer and total moles of the metallocene compound combined in the precontacted mixture may be from about 1:10 to about 100,000: 1, for example, from about 10: 1 to about 1,000 :1.

The weight ratio of the activating support and the organoaluminum compound may be from about 1: 5 to about 1,000: 1. The weight ratio of the activating support and the organoaluminum compound may be from about 1: 3 to about 100: 1, for example, from about 1: 1 to about

50:1.

In accordance with another aspect of the present invention, the weight ratio of the total moles of the combined metallocene compound and the activating support may be from about 1: 1 to about

1: 1,000,000. In accordance with yet another aspect of the present invention, the weight ratio of the total moles of the combined metallocene compound and the activating support may be from about 1:10 to about 1: 10,000. In accordance with yet another aspect of the present invention, the weight ratio of the total moles of the combined metallocene compound and the activating support may be approximately

1:20 to about 1: 1000.

Aluminoxane compounds are not required to form the catalyst composition of the present invention. Thus, polymerization advances in the absence of aluminoxanes. Accordingly, the present invention

You can use organoaluminum compounds of the AlR3 type and an activating support in the absence of aluminoxanes. While we do not attempt to stick to the theory, it is believed that the organoaluminum compound may not activate the metallocene catalyst in the same way as an organoaluminoxane. As a result, the present invention results in lower polymer production costs.

Additionally, no expensive borate compound or MgCl2 is required to form the catalyst composition of the present invention. However, aluminoxanes, organoboro compounds, ionizing ionic compounds, organozinc compounds, MgCl2, or any combination thereof may optionally be used in the catalyst composition of the present invention. In addition, cocatalysts such as aluminoxanes, organoboro compounds, ionizing ionic compounds, organozinc compounds, or any combination thereof can be used as cocatalysts with the metallocene compound, in the presence

or in the absence of the activating support, and in the presence or absence of the organoaluminum compound.

In accordance with one aspect of the present invention, the catalyst activity of the catalyst of the present invention may be greater than or equal to approximately 100 grams of polyethylene per gram of chemically treated solid oxide per hour (abbreviated gP / (gCTSO · hr)) . In accordance with another aspect of the present invention, the catalyst of the present invention can be characterized by an activity greater than or equal to about 250 gP / (gCTSO · hr). In accordance with yet another aspect of the present invention, the catalyst of the present invention can be characterized by an activity greater than or equal to approximately 500 gP / (gCTSO · hr). In accordance with yet another aspect of the present invention, the catalyst of the present invention can be characterized by an activity greater than or equal to approximately 1000 gP / (gCTSO · hr). In accordance with another aspect of the present invention, the catalyst of the present invention can be characterized by an activity greater than or equal to about 2000 gP / (gCTSO · hr). This activity is measured under suspension polymerization conditions by using isobutane as the diluent, at a polymerization temperature of approximately 90 ° C and an ethylene pressure of approximately 550 psig. The reactor must have substantially no indication of any scale of wall, coating or other form of coating when making these measurements.

Any combination of the metallocene compounds, the activating support, the organoaluminum compound, and the olefinic monomer, can be precontacted. When any precontact with an olefinic monomer is produced, it is necessary that the olefinic monomer used in the precontact step be the same as the olefin that must be polymerized. In addition, when a precontact stage is used between any combination of the catalyst components for a first period of time, this precontacted mixture can be used at a subsequent postcontact stage between any combination of catalyst components for a second period of time. For example, all catalyst and 1-hexene components can be used in a precontact stage for a first period of time, and this precontacted mixture can then be contacted with the activating support to form a postcontacted mixture that is in contact during a second period of time before starting the polymerization reaction. For example, the first period of time for contact, the precontact time, between any combination of the metallocene compounds, the olefinic monomer, the activating support, and the organoaluminum compound can be from about 0.1 hour to about 24 hours, for example, from about 0.1 to about 1 hour. Precontact times of about 10 minutes to about 30 minutes are also typical. The postcontacted mixture may optionally be allowed to remain in contact for a second period of time, the precontact time, prior to starting the polymerization process. In accordance with one aspect of the present invention, the postcontact times between the precontacted mixture and any remaining catalyst component may be from about 0.1 hour to about 24 hours, for example, from about 0.1 hour to about 1 hour.

D. Use of the catalyst composition in polymerization processes

After catalyst activation, the catalyst composition is used to homopolymerize ethylene or copolymerize ethylene with a comonomer.

The polymerization temperature may be from about 60 ° C to about 280 ° C, for example, from about 70 ° C to about 110 ° C. The polymerization reaction typically begins in an inert atmosphere substantially free of oxygen and under substantially anhydrous conditions. For example, an inert, dry atmosphere such as dry nitrogen or dry argon can be used.

The polymerization reaction pressure can be any pressure that does not interrupt the polymerization reaction, and is typically a pressure higher than the pretreatment pressures. In accordance with one aspect of the present invention, the polymerization pressures may be from approximately atmospheric pressure to 1000 psig. In accordance with another aspect of the present invention, the polymerization pressure may be from about 50 psig to about 800 psig. In addition, hydrogen can be used in the polymerization process of the present invention to control the polymer molecular weight.

The polymerizations by utilizing the catalysts of the present invention can be carried out in any manner known in the art. Such processes that may be appropriate for use with the present invention include, but are not limited to suspension polymerizations, gas phase polymerizations, solution polymerizations, and combinations of multiple reactors thereof. Thus, any polymerization zone known in the art can be used to produce olefin-containing polymers.

For example, a stirred reactor can be used for a batch process, or a loop reactor or a continuous stirred reactor can be used for a continuous process.

A typical polymerization method is a suspension polymerization process (also known as a particle formation process), which is well known in the art and is described, for example, in US Patent No. 3,248,179, which is incorporated by reference herein, in its entirety. Other polymerization methods of the present invention for suspension processes are those that employ a loop reactor of the type described in US Patent No. 3,248,179, which is incorporated by reference herein, in its entirety and those used in a plurality of agitated reactors in series, parallel,

or combinations thereof, where the reaction conditions are different in the different reactors.

Appropriate diluents used in suspension polymerization are well known in the art and include hydrocarbons that are liquid under reaction conditions. The term "diluent" as used in this disclosure does not necessarily mean an inert material, since this term is intended to include compounds and compositions that may contribute to the polymerization process. Examples of hydrocarbons that can be used as diluents include, but are not limited to, cyclohexane, isobutane, nbutane, propane, n-pentane, isopentane, neopentane, and n-hexane. Typically, isobutane can be used as a diluent in a suspension polymerization, as provided by US Pat. Nos. 4,424,341; 4,501,885; 4,613,484; 4,737,280; and 5,597,892; each of which is incorporated by reference herein, in its entirety.

Various polymerization reactors are contemplated by the present invention. As used herein, "polymerization reactor" includes any polymerization reactor or polymerization reactor system capable of polymerizing olefinic monomers to produce homopolymers or copolymers of the present invention. Said reactors may comprise suspended reactors, gas phase reactors, solution reactors, or any combination thereof. The gas phase reactors may comprise fluidized bed reactors or tubular reactors. Suspended reactors may comprise vertical loops or horizontal loops. The reactors in solution may comprise stirred tank or autoclave reactors.

The polymerization reactors suitable for the present invention may comprise at least one raw material feed system, at least one feed system for catalyst or catalyst components, at least one reactor system, at least one polymer recovery system or any appropriate combination thereof. The reactors suitable for the present invention may further comprise any one, or combination of, a catalyst storage system, an extrusion system, a cooling system, a diluent recycling system, or a control system. Such reactors may comprise continuous extraction and direct recycling of the catalyst, diluent, and polymer. In general, the continuous processes may comprise the continuous introduction of a monomer, a catalyst, and a diluent in a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent.

The polymerization reactor systems of the present invention may comprise one type of reactor system per system or multiple reactor systems comprising two or more types of reactors operated in parallel or in series. Multiple reactor systems may comprise reactors connected together to carry out the polymerization, or reactors that are not connected. The polymer can be polymerized in a reactor under a set of conditions, and then the polymer can be transferred to a second reactor for polymerization under a different set of conditions.

In accordance with one aspect of the invention, the polymerization reactor system may comprise at least one loop suspended reactor. Such reactors are known in the art and can comprise vertical or horizontal loops. Said loops may comprise a single loop or a series of loops. Multiple loop reactors can comprise both vertical and horizontal loops. The suspension polymerization can be carried out in an organic solvent that can disperse the catalyst and polymer. Examples of suitable solvents include butane, hexane, cyclohexane, octane, and isobutane. The monomer, solvent, catalyst and any comonomer can be fed continuously to a loop reactor where polymerization occurs. Polymerization can occur at low temperatures and pressures. The reactor effluent can be evaporated instantly to remove the solid resin.

In accordance with yet another aspect of the present invention, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recycle stream containing one or more continuously cycled monomers through the fluidized bed in the presence of the catalyst under polymerization conditions. The recycle stream can be extracted from the fluidized bed and recycled back into the reactor. Simultaneously, the polymer product can be extracted from the reactor and the new or fresh monomer can be added to replace the polymerized monomer. Said gas phase reactors may comprise a process for the multistage gas phase polymerization of the olefins, wherein the olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone.

In accordance with yet another aspect of the invention, the polymerization reactor may comprise a tubular reactor. Tubular reactors can make polymers by initiating free radicals, or by

use of catalysts typically used for coordination polymerization. Tubular reactors can have several zones where fresh monomer, initiators, or catalysts are added. The monomer can be entrained in an inert gas stream and a reactor zone introduced. The initiators, catalysts, and / or catalyst components may be entrained in a gas stream and introduced into another area of ​​the reactor. Gaseous streams can be intermingled for polymerization. Heat and pressure can be used appropriately to obtain optimal polymerization reaction conditions.

In accordance with yet another aspect of the invention, the polymerization reactor may comprise a solution polymerization reactor. During solution polymerization, the monomer is contacted with the catalyst composition by appropriate stirring or other means. A vehicle comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer can be contacted in the vapor phase with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Stirring may be employed during polymerization to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization. The polymerization can be carried out in a batch form, or in a continuous form. The reactor may comprise a series of at least one separator that employs high pressure and low pressure to separate the desired polymer.

In accordance with another aspect of the invention, the polymerization reactor system may comprise the combination of two or more reactors. The production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device which makes it possible to transfer the polymers resulting from the polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization. Such reactors may include any combination that includes, but is not limited to, multiple loop reactors, multiple gas reactors, a combination of loop and gas reactors, a combination of autoclave reactors or reactors in solution with gas or loop reactors, multiple reactors in solution, or multiple autoclave reactors.

After the polymer is produced, they can be formed into various items, including but not limited to household containers, utensils, film products, drums, fuel tanks, pipes, geomembranes, and coatings. Various processes can be used to form these articles. Usually, additives and modifiers are added to the polymer to provide the desired effects. By using the invention described herein, the articles can possibly be produced at a lower cost, while maintaining most or all of the unique properties of polymers produced with metallocene catalysts.

E. Pipe Extrusion

In accordance with one aspect, the present invention includes a method for manufacturing a PE-100 pipe, the method comprising extruding the polymer or copolymer in a molten state through a die to form the PE-100 pipe and cooling the pipe.

In accordance with still other aspects, a PE-100 pipe comprising the polymer or copolymer of the present invention is contemplated.

Pipe extrusion in the simplest terms is carried out by melting, transporting polyethylene pellets to a particular shape (generally an annular shape), and solidifying that way during a cooling process. There are numerous stages for pipe extrusion as provided below.

The polymer feed can be a prepreg polyethylene resin or it can be a mixture of natural and concentrated color polyethylene (called "salt and pepper mixtures"). In North America, the most common feed load for pipe extrusion is "salt and pepper mixtures." In Europe and other areas of the world, the most common feed load for pipe extrusion is prepreg polyethylene resin. The feed load is rigidly controlled to obtain the appropriate finished product (pipe) and final consumer specifications.

The feed load is then fed into an extruder. The most common extruder system for pipe production is a single screw extruder. The purpose of the extruder is to melt, transport and homogenize the polyethylene pellets. Extrusion temperatures typically vary from 178 ° C to 232 ° C depending on the extruder screw design and flow properties of polyethylene.

The molten polymer is then passed through a matrix. The matrix distributes the molten homogeneous polyethylene polymer around the solid mandrel, which takes the form of an annular shape.

Adjustments can be made to the exit of the matrix to try to compensate for the sinking of the polymer throughout the rest of the process.

In order for the pipe to meet the appropriate dimension parameters, the pipe is then given the appropriate dimensions. There are two methods to provide adequate dimensions: vacuum or pressure. Both employ different techniques and different equipment.

Then, the pipe is cooled and solidified to the desired dimensions. The cooling is carried out by using several water tanks where the external pipe is submerged or water is sprayed on the outside of the pipe. The pipe is cooled from the outer surface to the inner surface. The inner wall and the internal surfaces of the pipe can be very hot for a long period of time, since polyethylene is a poor conductor of heat.

Finally, the pipe is printed and rolled or cut to length.

The present invention is further illustrated by the following examples, which should not be construed in any way as imposition limitations within the scope thereof. On the contrary, it should be clearly understood that various other aspects, embodiments, modifications, and equivalent thereof may have to be resorted to which, after reading the description herein, may be suggested to one with common experience in the art without depart from the spirit of the present invention or the scope of the appended claims.

Examples

For each of the following examples, the test procedures were as follows.

The flow rate (MI, g / 10 min) was determined according to the conditions F of ASTM D1238 at 190 ° C with a weight of 2,160 grams.

The high load melt index (HLMI, g / 10 min) was determined according to condition E of ASTM D1238 at 190 ° C with a weight of 21,600 grams.

The density of the polymer was determined in grams per cubic centimeter (g / cc) in a compression molded sample, cooled to approximately 15 ° C per hour, and conditioned for approximately 40 hours at room temperature according to ASTM D1505 and ASTM D1928, procedure C.

The rheological characterizations of melt were carried out as follows. Small tension oscillatory shear measurements (10%) were performed on a Rheometrics Scientific, Inc. ARES rheometer using parallel plate geometry. All rheological tests were carried out at 190 ° C Complex viscosity data | T * | versus frequency (m) were then adjusted to the curve by using the three-parameter modified Carreau-Yasuda (CY) empirical model to obtain zero shear viscosity - To, characteristic viscous relaxation time - T and amplitude parameter -a . The simplified Carreau-Yasuda (CY) empirical model is as follows.

T0

1T * m 1,

Tm

where: | T * (m) | = magnitude of complex shear viscosity;

To = zero shear viscosity;

T = viscous relaxation time;

a = "amplitude" parameter;

n = sets the slope of the final power law, set to 2/11; and

m = angular frequency of oscillatory shear deformation

Details of the meaning and interpretation of the CY model and parameters obtained can be found in: CA Hieber and HH Chiang, Rheol. Aeta, 28, 321 (1989); CA Hieber and HH Chiang, Polym. Eng. Sei., 32, 931 (1992); Oh

RB Bird, RC Armstrong and O. Hasseger, Dynamies of Polymerie Liquids, Volume 1, Fluid Meehanies, 2nd Edition, John Wiley &amp; Sons (1987); each of which is incorporated herein by reference in its entirety. Parameter "a" of CY is reported in the tables for the resins described herein.

A "Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument" was used to determine the specific surface area ("surface area") and the specific pore volume ("pore volume"). This instrument was purchased from Quantachrome Corporation, Syosset, NY

Molecular weights and molecular weight distributions were obtained by using a PL 220 SEC high temperature chromatographic unit (Polymer Laboratories) with trichlorobenzene (TCB) as a solvent, with a flow rate of 1 ml / minute at a temperature of 145 ° C BHT (2,6-di-tert-butyl-4-methylphenol) was used in a concentration of 0.5 g / l as a stabilizer in the TCB. An injection volume of 200 µl with a nominal polymer concentration of 1.5 mg / ml was used. Dissolution of the sample in stabilized TCB was carried out by heating at 150 ° C for 5 hours with gentle, occasional stirring. The columns used were three columns of PLgel Mixed A LS (7.8x300mm) and were calibrated with a wide linear polyethylene standard (Phillips Marlex® BHB 5003) for which the molecular weight had been determined.

Molecular weight distributions and branching profiles were collected through size exclusion chromatography using an FTIR detector. The chromatographic conditions are those described above. However, the injection volume of the sample was 500 1l. Samples were introduced to the FTIR detector through a transfer line and flow cell (KBr windows, 1 mm optical pitch, and approximately 70 1l cell volume). The temperatures of the transfer line and flow cell were maintained at 143 + 1oC and 140 + 1oC, respectively. In these studies, the Perkin Elmer FTIR spectrophotometer (PE 2000) equipped with a narrow-band cadmium telluride telluride detector (MCT) was used.

All spectra were acquired through the use of Perkin Elmer Timebase software. Background spectra of the TCB solvent were obtained prior to each run. All IR spectra were measured at 8 cm-1 resolution (16 scans). Chromatograms were generated by using the quadratic root mean absorbance over the spectral region of 3000-2700 cm-1 (ie, FTIR serves as a concentration detector). Molecular weight calculations were performed according to what was previously described by using a wide molecular weight polyethylene (PE) standard [see Jordens K, Wilkes GL, Janzen J, Rohlfing DC, Welch MB. Polymer 2000; 41: 7175]. The spectra of the individual time sheets of the chromatogram are subsequently analyzed for comonomer branching levels through the use of chemometric techniques. All calibration spectra were taken at sample concentrations that exceeded that necessary for the good signal to noise (ie,&gt; 0.08 mg / ml in the detector).

Branching determination was performed as follows. Narrow molecular weight (Mw / Mn ~ 1.1 to 1.3), solvent gradient fractions of ethylene 1-butene, ethylene 1-hexene, polyethylene homopolymers, and low molecular weight alkanes were used in the calibration and Verification studies The total methyl content of these samples varied from 1.4 to 82.7 methyl per 1000 total carbons. The methyl content of the samples was calculated from Mn or measured by the use of C-13 NMR spectroscopy. The C-13 NMR spectra were obtained in samples of 15% by weight on TCB by using a 500 MHz Varian Unit Spectrometer run as previously described [see Randall JC, Hsieh ET, NMR and Macromolecules; Sequence, Dynamic, and Domain Structure, ACS Symposium Series 247, JC Randall, Ed., American Chemical Society, Washington DC, 1984.]. The methyl content per 1000 carbons by NMR was obtained by multiplying (X 1000) the ratio of total methyl signals by the total signal intensity.

A partial least squares (PLS) calibration cure was generated by using Pirouette chemometric software (Infometrix) to correlate the changes in the FTIR absorption spectra with the values ​​calculated or measured by NMR for methyl / 1000 total carbons for the 25 samples. The FTIR absorption spectra used in the calibration model were made from the co-added spectra collected throughout the entire sample. Only a portion of the spectral region (2996 and 2836 cm1) was used in the calibration stage to minimize the effects of residual solvent absorption. The preprocessing of the spectral data included the normalization of the area, taking the first derivative of the spectra and focusing all the data on the average.

A four component calibration model was calculated and optimized by using the cross-validation process (RSQ = 0.999, SEV = 0.7). The calibration model was verified by using 23 additional samples. Actual values ​​versus predicted values ​​for validation data showed excellent correlation (RSQ = 0.987) and exhibited a mean square prediction error equal to +/- 0.4 methyl groups per 1000 total carbon molecules.

Short chain branching levels were calculated by subtracting contributions from methyl chain ends. The amount of methyl chain ends were calculated using the equation Mece = C (2-Vce) / M, where Mece is the number of methyl chain ends per 1000 total carbon molecules, C is an equal constant at 14000, Vce is the number of the vinyl terminal chain ends (1 for chromium catalyzed resins), and M is the calculated molecular weight for a particular sheet of the molecular weight distribution.

Slow growth resistance values ​​of PENT cracks were obtained at 80 ° C (176 ° F) in accordance with ASTM F1473 (2001), with the exception that the initial load was 3.8 MPa, to accelerate the test. This 3.8 MPa PENT test may be referred to herein as a "high voltage" PENT test.

The Charpy test was the Charpy Energy test with notch at room temperature carried out in accordance with ASTM F2231.

Preparation of eielopentadienyl complexes and metallocene compounds

The cyclopentadienyl and metallocene complexes used in the various examples or described herein were purchased or prepared as follows. All manipulations that include reagents and air-sensitive materials were carried out under nitrogen using Schlenk's standard line.

or dry box techniques. The THF solvent was distilled from potassium, while anhydrous diethyl ether, methylene chloride, pentane, and toluene (Fisher Scientific Company) were stored on activated aluminum oxide. All solvents were degassed and stored under nitrogen. Zirconium (IV) chloride (99.5%) and n-butyllithium were purchased from Aldrich Chemical Company and used as received. Products were analyzed by 1 H NMR (300 MHz, CDCl3, referenced against residual CHCl3 peak at 7.24 ppm) or 13 C NMR (75 MHz, CDCl3, referenced against CDCl3 centerline at 77.00 ppm).

Preparation of sulfated aluminum oxide aetivating support

Aluminum oxide A, from WR Grace Company, was impregnated to incipient moisture with an aqueous solution of ammonium sulfate. Typically, the aluminum oxide had a surface area of ​​approximately 330 m2 / grams and a pore volume of approximately 1.3 cc / grams. The amount of ammonium sulfate used was equal to 20% of the aluminum oxide partitioned. The volume of water used to dissolve and ammonium sulfate was calculated from the total pore volume of the starting sample (ie 2.6 ml of water for each gram of aluminum oxide to be treated). Thus, a solution of approximately 0.08 grams of ammonium sulfate per ml of water was used. The resulting wet sand was dried in a vacuum oven overnight at 120 ° C, and then selected through a 35 mesh screen. Finally, the material was activated in a dry air fluidization stream at 550 ° C for 3 hours, in the case of laboratory scale samples, or 6 hours,

10 for larger pilot plant samples. The samples were then stored under nitrogen.

Example 1

Synthesis at room temperature of Zr [T-CsH4- (nBu)] Cl3

Zr [T-C5H4- (nBu)] Cl3 was prepared as described in Example 2, except that the reflux step was omitted. Instead, the mixture of (n-BuCp) 2ZrCl2 and ZrCl4 was stirred at room temperature for 20 hours. FIG. 1 presents

fifteen the NMR spectrum for Zr [T-C5H4- (nBu)] Cl3 formed in accordance with Example 1. The molar ratio obtained for the product Zr [T-C5H4- (nBu)] Cl3 and the starting material (n- BuCp) 2ZrCl2 was 1.4: 1.

Example 2

Inventive preparation of Zr [T-CsH4- (nBu)] Cl3

twenty A 500 ml Schlenk bottle was charged with (n-BuCp) 2ZrCl2 (20.0g, 49.4 mmol), ZrCl4 (12.7g, 54.4 mmol), 300 ml of toluene and a stir bar. The resulting yellow suspension was refluxed under N2 for approximately 20 hours. The dark brown-black reaction mixture was centrifuged to remove excess ZrCl4 and toluene was removed from the filtrate under reduced pressure to obtain a thick brown-black oil. The product was precipitated a couple of times with a mixture of CH2Cl2 / pentane and dried in vacuo (0.1 mm, 1 hour) to

25 produce the desired product as a brown solid. (27 g, 87%). FIG. 2 presents the NMR spectrum for Zr [T-C5H4- (nBu)] Cl3 formed in accordance with Example 2. The molar ratio obtained for the product Zr [TC5H4- (nBu)] Cl3 and the starting material (n- BuCp) 2ZrCl2 was 52: 1. Thus, the method of manufacturing Zr [T-C5H4 (nBu)] Cl3 in accordance with the present invention significantly improves the yield and selectivity of the reaction.

30 Example 3

Preparation of Zr [T-CsH3- (nBu, Me) 1,3] Cl3

A 500 ml Schlenk bottle was charged with (1.3 Me, nBuCp) 2ZrCl2 (20.0g, 46.2 mmol), ZrCl4 (11.9g, 50.7 mmol), 200 ml of toluene and a stir bar . A resulting yellow suspension was refluxed under N2 for approximately 20 hours. The dark brown-black reaction mixture was centrifuged to remove ZrCl4 in

35 excess and toluene was removed from the filtrate under reduced pressure to obtain a thick brown-black oil. The product was precipitated a couple of times with a mixture of CH2Cl2 / pentane and dried in vacuo (0.1 mm, 1 hour) to yield the desired product as a brown solid. (23 g, 76%). 1H NMR (CDCl3, 8) 0.94 (t, J = 7.5Hz, CH3), 1.62-1.31 (m, CH2 (CH2) 2CH3), 2.44 (s, CH3), 2, 81-2.75 (m, CH2 (CH2) 2CH3), 6.24 (broad s, 1, C5H4), 6.45 (broad s, 2, C5H4).

40 Example 4

Preparation of Zr {Ts-CsH4 - [(CH2) 3CH3]} {Ts-C9H6-1- (CH2CH = CH2)} Cl2

(G)

A 500 ml Schlenk bottle was charged with nBuCpZrCl3 (20.0g, 62.7mmol) and approximately 400 ml of diethyl ether. The resulting suspension was cooled to 0 ° C, after that time (10.7g, 66.0mmol) of Li [(C9H6) 45 1 (allyl)] were cannulated as an ethereal solution. The reaction mixture was stirred overnight at room temperature and the solvent was removed in vacuo. The resulting solid was dissolved in toluene and centrifuged to remove LiCl. Removal of the solvent in vacuo yielded a yellow-brown solid that was dissolved in a dichloromethane / pentane mixture and cooled to -35 ° C for a couple of hours. The resulting suspension was filtered, and the precipitate was dried under reduced pressure (0.1 mm, 1 hour) to produce the product as a yellow solid.

(17.0g, 62%). 1 H NMR (CDCl3, 8) 0.87 (t, J = 7.2Hz, CH3), 1.50-1.22 (m, CH2 (CH2) 2CH3), 2.58-2.42 (m, CH2 (CH2) 2CH3), 3.77-3.62 (m, CH2 = CHCH2), 5.10-5.02 (m, CH2 = CHCH2), 5.78-5.76 (m, 1, C5H4) , 5.87-5.83 (m, 2, C5H4), 5.99-5.91 (m, CH2 = CHCH2), 6.04-6.00 (m, 1, C5H4), 6.39- 6.37 (m, 1, C9H6), 6.63 (d, J = 3.0Hz, 1, C9H6), 7.287.18 (m, 2, C9H6), 7.60-7.56 (m, 2 , C9H6).

Example 5

Preparation of Zr {Ts-CsH4 - [(CH2) 3CH3]} {Ts-C9H6-1 - [(CH2) 2CH = CH2]} Cl2

(H)

A 500 ml Schlenk bottle was charged with nBuCpZrCl3 (5.4g, 17.0mmol) and approximately 150 ml of diethyl ether. The resulting suspension was cooled to 0 ° C, after that time (3.0g, 17.0mmol) of Li [(C9H6) -1- (butenyl)] 10 were cannulated as an ethereal solution. The reaction mixture was stirred overnight at room temperature and the solvent was removed in vacuo. The resulting solid was dissolved in toluene and centrifuged to remove LiCl. Solvent removal in vacuo produced a yellow-brown solid that was dissolved in a dichloromethane / pentane mixture and cooled to -35 ° C for a couple of hours. The resulting suspension was filtered, and the precipitate was dried under reduced pressure (0.1 mm, 1 hour) to produce the product as a yellow solid (7.2g, 93%).

fifteen 1H NMR (CDCl3, 8) 0.79 (t, J = 7.2Hz, CH3), 1.41-1.14 (m, CH2 (CH2) 2CH3), 2.49-2.19 (m, 4 , CH2), 3.07-2.84 (m, CH2), 4.97-4.84 (m, CH2 = CHCH2), 5.65-5.62 (m, 1, C5H4), 5.81 -5.68 (m, 3, CH2 = CHCH2, C5H4), 5.95-5.91 (m, 1, C5H4), 6.30-6.29 (m, 1, C9H6), 6.56 ( d, J = 3.3Hz, 1, C9H6), 7.20-7.11 (m, 2, C9H6), 7.53-7.49 (m, 2, C9H6).

Example 6

Preparation of Zr {Ts-CsH4 - [(CH2) 3CH3]} {Ts-C9H6-1 - [(CH2) 3Ph]} Cl2

A 500 ml Schlenk bottle was charged with nBuCpZrCl3 (19.9g, 62.4mmol) and approximately 400 ml of ether

diethyl The resulting suspension was cooled to 0 ° C, after that time (15.0g, 62.4mmol) of Li [(C9H6) -1

(3-phenylpropyl)] were cannulated as an ethereal solution. The reaction mixture was stirred overnight to

room temperature and the solvent was removed in vacuo. The resulting solid was dissolved in toluene and centrifuged to remove LiCl. Removal of the solvent in vacuo produced a yellow-brown solid that dissolved in a

dichloromethane / pentane mixture and cooled to -35 ° C for a couple of hours. The suspension was filtered

resulting, and the precipitate was dried under reduced pressure (0.1 mm, 1 hour) to produce the product as a solid

yellow (23.6g, 73%). 1H NMR (CDCl3, 8) 0.80 (t, J = 7.2Hz, CH3), 1.42-1.15 (m, CH2 (CH2) 2CH3), 1.96-1.84 (m, 2 ,

CH2), 2.49-2.34 (m, CH2 (CH2) 2CH3), 2.69-2.53 (m, 2, CH2), 3.03-2.80 (m, 2, CH2), 5.64-5.62 (m, 1, C5H4), 5.7530 5.71 (m, 2, C5H4), 5.93-5.91 (m, 1, C5H4), 6.31-6, 30 (m, 1, C9H6), 6.56 (d, J = 3.3Hz, 1, C9H6), 7.20-7.05 (m, 7, C9H6,

C6H5), 7.53-7.46 (m, 2, C9H6).

Example 7

Preparation of Zr {Ts-CsH4 - [(CH2) 3CH3]} {Ts-C9H6-1 - [(CH2) 3CH3]} Cl2

A 500 ml Schlenk bottle was charged with nBuCpZrCl3 (5.4g, 16.8mmol) and approximately 150 ml of diethyl ether. The resulting suspension was cooled to 0 ° C, after that time (3.0g, 16.8mmol) of Li [(C9H6) -1- (butyl)] were cannulated as an ethereal solution. The reaction mixture was stirred overnight at room temperature and the solvent was removed in vacuo. The resulting solid was dissolved in toluene and centrifuged to remove LiCl. Removal of the solvent in vacuo produced a yellow-brown solid that was dissolved in a dichloromethane / pentane mixture and cooled to -35 ° C for a couple of hours. The resulting suspension was filtered, and the precipitate was dried under reduced pressure (0.1 mm, 1 hour) to yield the product as a yellow solid (3.7g, 48%) .1 H NMR (CDCl3.8) 0.88 -0.78 (m, 6, CH3), 1.58-1.15 (m, 8, CH2), 2.50-2.35 (m, CH2 (CH2) 2CH3), 2.99-2, 73 (m, 2, CH2), 5.67-5.64 (m, 1, C5H4), 5.77-5.73 (m, 2, C5H4), 5.96-5.92 (m, 1 , C5H4), 6.31-6.30 (m, 1, C9H6), 6.56 (d, J =

10 3.3Hz, 1, C9H7), 7.21-7.09 (m, 2, C9H7), 7.54-7.49 (m, 2, C9H7).

Example 8

Preparation of Zr {Ts-CsH4 - [(CH2) 3CH3]} {Ts-C9H}} Cl2

A 500 ml Schlenk bottle was charged with nBuCpZrCl3 (1.0g, 3.1mmol) and approximately 150 ml of diethyl ether.

fifteen The resulting suspension was cooled to 0 ° C, after that time (0.4g, 3.1mmol) of indenyl lithium were cannulated as an ethereal solution. The reaction mixture was stirred overnight at room temperature and the solvent was removed in vacuo. The resulting solid was dissolved in toluene and centrifuged to remove LiCl. Solvent removal in vacuo produced a yellow-brown solid that was dissolved in a dichloromethane / pentane mixture and cooled to -35 ° C for a couple of hours. The resulting suspension was filtered, and dried

twenty the precipitate under reduced pressure (0.1 mm, 1 hour) to produce the product as a yellow solid (0.8g, 64%). 1H NMR (CDCl3, 8) 0.81 (t, J = 5.0Hz, CH3), 1.43-1.16 (m, CH2 (CH2) 2CH3), 2.47-2.42 (m, CH2 (CH2) 2CH3), 5.76 (t, J = 2.4Hz, 2, C5H4), 5.87 (t, J = 2.4Hz, 2, C5H4), 6.42 (d, J = 3, 0Hz, 2, C9H7), 6.82 (t, J = 3.3Hz, 1, C9H7), 7.22-7.16 (m, 2, C9H7), 7.60-7.56 (m, 2 , C9H7).

Example 9

25 Preparation of Zr [Ts-CsH3- (nBu, Me) 1,3]]} {Ts-C9H6-1- (CH2CH = CH2)} Cl2

(P)

A 500 ml Schlenk bottle was charged with (1,3-MeBuCp) ZrCl3 (5.0g, 15.0 mmol) and approximately 150 ml of diethyl ether. The resulting suspension was cooled to 0 ° C, after that time (2.5g, 15.0 mmol) of Li [(C9H6) 1 (allyl)] were cannulated as an ethereal solution. The reaction mixture was stirred overnight at room temperature and the solvent was removed in vacuo. The resulting solid was dissolved in toluene and centrifuged to remove LiCl. Removal of the solvent in vacuo produced a yellow-brown oily solid that was dissolved in pentane, filtered, and the filtrate was cooled to -35 ° C. The resulting suspension was filtered, and the precipitate was dried under reduced pressure (0.1 mm, 1 hour) to produce the product as a yellow oily solid (3.9g, 57%). 1 H NMR (CDCl3, 8) 0.85-0.77 (m, 6, CH3), 1.46-1.12 (m, 8, CH2 (CH2) 2CH3), 1.96 (s, CH3), 2.04 (s, CH3), 2.49-2.11 (m,

35 4, CH2 (CH2) 2CH3), 3.72-3.53 (m, 4, CH2 = CHCH2), 5.02-4.92 (m, 4, CH2 = CHCH2), 5.16 (t, J = 2.7Hz, 1, C5H4), 5.26 (t, J = 2.7Hz, 1, C5H4), 5.74-5.70 (m, 2, C5H4), 5.87-5.82 ( m, 2, C5H4), 5.80-5.88 (m, CH2 = CHCH2), 6.27-6.25 (m, 2, C9H6), 6.47-6.46 (m, 2, C9H6 ), 7.19-7.09 (m, 4, C9H6), 7.51-7.44 (m, 4, C9H6).

Example 10

1- (methyl) -1- (3-butenyl) -1- (eielopentadienyl) -1- (2,} - di-tere-butylfluorenyl) methane zireonium chloride preparation

40 1- (methyl) -1- (3-butenyl) -1- (cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) methane zirconiodichloride can be prepared by using numerous techniques. Several techniques are described in US 2005/0285284 for "IMPROVED SYNTHESIS OF ANSA-METALLOCENES AND THEIR PARENT LIGANDS IN HIGH YIELD", incorporated by reference herein in its entirety.

Several techniques are provided for preparing the ligand herein by way of example and not by way of limitation. The corresponding ansa-metallocenes comprising the ligands described herein are prepared in the usual manner, in accordance with any one of the procedures known in the art, as understood by one with common experience. For example, a process for preparing the corresponding zirconium dichloride ansa-metallocene from these ligands uses 2 equivalents of n-butyllithium (in hexanes) to treat a stirred diethyl ether solution of the parent ligand, typically at about 0 ° C. Once the n-butyllithium has been added, the ether solution is typically allowed to cool to room temperature overnight. The diluted parent ligand solution is then added slowly to a suspension of ZrCl4 in pentane, usually at about 0 ° C. The solvent is removed in vaefo to produce a solid that can be washed with pentane and extracted with dichloromethane or similar solvents.

to. Prepare aeion of 1- (methyl) -1- (3-butenyl) -1-eielopentadienyl) -1- (2,} - di-tere-butylfluorenyl) methane from 2,} di-tere-butylfluorenyl lithium and 6 -butenyl-6-methylfulvene

A one-liter bottle is loaded with 2,7-di-tert-butylfluorene (50 g, 179.6 mmol) and a stir bar, covered with a rubber septum, and placed under a nitrogen atmosphere. Diethyl ether (approximately 200 ml) is added through a cannula, and the resulting mixture is cooled to -78 ° C in a dry ice bath. The mixture is stirred at this temperature as n-butyllithium (19.0 ml of 10 M in hexanes, 190 mmol) is added slowly through a syringe. After the addition of n-butyllithium is finished, the reddish solution is slowly warmed to room temperature and stirred overnight (at least about 12 hours). After this time, the reaction mixture is cooled to -78 ° C, and 6-butenyl-6-methylfulvene (40 ml) (in less than 1 minute) is added quickly at this temperature with stirring. Upon completion of the addition of fulvene, the mixture is removed from the dry ice bath and warmed to room temperature, and an aliquot of GC is taken after approximately 15 minutes after removal of the dry ice bath.

Stirring is continued for 7 hours, after that time the reaction mixture is quenched with a saturated NH4Cl / H2O solution (300 ml). The organic layer is extracted with diethyl ether, washed twice with H2O (500 ml), dried over anhydrous Na2SO4, filtered, and the filtrate is evaporated to dryness to yield a solid. Methanol (approximately 500 ml) is added to the solid and the mixture is stirred overnight to form the product as a finely divided white solid. After filtration, washing with MeOH, and drying overnight, the desired parent ligand 1- (methyl) -1- (3-butenyl) -1- (cyclopentadienyl) -1- (2,7-di -tercbutylfluorenyl) methane is isolated and can be used without further purification.

b. Preparation of 1- (methyl) -1- (3-butenyl) -1- (eielopentadienyl) -1- (2,} - di-tere-butylfluorenyl) methane - Method A1

A one-liter bottle is loaded with 2,7-di-tert-butylfluorene (50 g, 179.6 mmol) and a stir bar, covered with a rubber septum, and placed under a nitrogen atmosphere. Diethyl ether (approximately 300 ml) is added through a cannula, and the resulting mixture is cooled to -78 ° C in a dry ice bath. The mixture is stirred at this temperature as n-butyllithium (21.5 ml of 10 M in hexanes, 215 mmol) is slowly added through a syringe. After the addition of n-butyllithium is completed, the reddish solution is slowly warmed to room temperature and stirred overnight (at least about 12 hours), to provide an ether solution of 2,7-di-tere -butylfluorenyl lithium.

Another one-liter bottle equipped with an addition funnel is loaded with 6-butenyl-6-methylfulvene (37 g, 253 mmol) and a stir bar, and cooled to 0 ° C under a nitrogen atmosphere. The, 7-di-terebutilfluorenyl lithium ether solution prepared as above is added dropwise to the fulvene at 0 ° C through the addition funnel over the course of about an hour. The resulting dark reaction mixture is warmed to room temperature and stirred overnight (at least about 12 hours) under a nitrogen atmosphere. The reaction mixture is then quenched with the slow addition of a saturated NH4Cl / H2O solution (300 ml), the organic layer is extracted with ether, washed twice with H2O (500 ml), dried over anhydrous Na2SO4, filter, and the filtrate evaporates to dryness. The crude product obtained by this method is then dissolved in pentane and kept at about 0 ° C in a freezer, thereby producing the product as a white solid that is washed with cold pentane, dried under vacuum, and isolated and It is used without further purification. The additional product could be isolated in small quantities through the concentration of the mother liquors and the combined washes and the placement of them again in the freezer.

and. Preparation of 1- (methyl) -1- (3-butenyl) -1- (eielopentadienyl) -1- (2,} - di-tere-butylfluorenyl) methane - Method A2

A solution of 2,7-di-tere-butylfluorenyl lithium ether is prepared and added dropwise over approximately one hour to pure 6-butenyl-6-methylfulvene (at 0 ° C) in the same manner as in Method A1. The resulting reaction mixture is then warmed to room temperature and stirred for 2 days under a nitrogen atmosphere. After this time, an additional 5 ml of 6-butenyl-6-methylfulvene and an additional 30 ml of the n-butyllithium solution are added to the reaction mixture at room temperature. The mixture is stirred overnight at room temperature.

The reaction mixture is then quenched with the slow addition of a saturated NH4Cl / H2O solution (300 ml), the organic layer is extracted with ether, washed twice with H2O (500 ml), dried over anhydrous Na2SO4, filter, and the filtrate evaporates to dryness. The crude product obtained by this method is dissolved in and crystallized from a solution of pentane: Et2O (mixture of 4: 1 by volume) at about 0 ° C, thereby producing the product as a white solid.

d. Preparation of 1- (methyl) -1- (3-butenyl) -1- (eielopentadienyl) -1- (2,} - di-tere-butylfluorenyl) methane - Method A3

A THF solution of 2,7-di-tere-butylfluorenyl lithium is prepared and added dropwise over the course of about an hour to the 6-butenyl-6-methylfulvene solution (at 0 ° C) in the same way than what is described in Method A1. The resulting dark reaction mixture is warmed to room temperature 5 and stirred overnight (at least about 12 hours) under a nitrogen atmosphere. This THF reaction mixture is then quenched with the slow addition of a saturated NH4Cl / H2O solution (300 ml), the organic layer is extracted with diethyl ether, washed twice with H2O (500 ml), dried over anhydrous Na2SO4 is filtered, and the filtrate is evaporated to dryness. The crude product obtained by this method is then dissolved in and crystallized from pentane at about 0 ° C, thereby producing a

10 product as white solid.

Example 11

1- (phenyl) -1- (butenyl) -1- (eielopentadienyl) -1- (2,} - di-tere-butylfluorenyl) methane zireonium chloride preparation

A 1 L round bottom flask is loaded with fluorene (23.2 g, 139.6 mmol), THF (400 ml), and a stir bar, and cooled to –78 ° C as it is slowly added n-butyllithium (165 mmol). The mixture is warmed at room temperature, stirred overnight, cooled to 0 ° C, and added through a 6-phenyl-6- (5-butenyl) fulvene cannula (38 g, 171 mmol) , dissolved in THF. After stirring for two days at room temperature the reaction is quenched with saturated NH4Cl solution, the organic material is extracted with diethyl ether, and the extracts are dried over anhydrous Na2SO4. With the removal of the solvent, a yellow oil is isolated. Chromatography of this oil through silicon oxide using heptane produces the ligand

twenty desired that can be used without further purification.

Example 12

Comparison of eatalizers eon Ind2ZrCl2

Several polymerization runs were conducted to demonstrate the support activity of various metallocenes that can be used in the present invention compared to the bis zirconio dichloride support activity.

25 indenyl (obtained from Witco under the trade name Eurecen 5032).

All polymerization runs in the laboratory were conducted in a gallon stainless steel reactor (3,785 liters). The reactor employed an air-operated agitator with a three-blade impeller and was set to run at 1180 rpm for the duration of a run. The reactor was also housed in the steel jacket with supply lines leading to a heat exchange unit, which in turn was connected to the power line.

30 cooling water and steam line, which allowed temperature control.

The initiation of the loading sequence to the reactor was through an open loading port while ventilating with isobutane vapor. Alkylaluminum was injected, quickly followed by the addition of the activating solid and the catalyst solution. The loading port was closed and 20 psi of isobutane vapor was added. A side vessel was used to hold a measured amount of hexene and this was pushed into the reactor with two liters of isobutane liquid supported by nitrogen pressure. The reactor contents were stirred and heated to 2 degrees Celsius below the desired run temperature, and then ethylene was introduced. A mass flow unit allowed the pressure to rapidly climb up to 5 psi below the required run pressure, and the smooth transition of ethylene flow to the specified temperature (90 ° C) was allowed and the pressure levels of the reactor (450 psi). The reactor pressure was maintained by adding ethylene on demand. These

40 temperature and pressure levels were maintained for the duration of the run (30 min). At the end of the run time the ethylene flow was interrupted and the reactor pressure was slowly released. When the pressure and temperature were sufficiently and calmly low the reactor was opened and the granular polymer powder was collected. The activity was specified as grams of polymer produced per gram of solid activator charged per hour. A summary of the various runs is presented in Table 1.

Four. Five Table 1.

<dl><dt>Run</dt><dd>Catalyst Catalyst Weight (mg) R3Al (ml) Time (min) 1-Hexene (g) Support Support (mg) Solid PE (g) Support activity (g / g / h) MI (g / 10 min) HLMI g / 10 min </dd></dl>

<dl><dt>12-1 </dt><dd>G 1.5 TNBAL 1 30 10 Sulfated Al2O3 fifty 227 9080 0.09 2.36 </dd></dl>

<dl><dt>12-2 </dt><dd>G 1.5 TIBA 1 30 10 Sulfated Al2O3 fifty 136 5440 0.05 1.5 </dd></dl>

<dl><dt>12-3 </dt><dd>H 1.5 TIBA 1 30 10 Sulfated Al2O3 fifty 177 7080 0 0.87 </dd></dl>

<dl><dt>Run</dt><dd>Catalyst Catalyst Weight (mg) R3Al (ml) Time (min) 1-Hexene (g) Support Support (mg) Solid PE (g) Support activity (g / g / h) MI (g / 10 min) HLMI g / 10 min </dd></dl>

<dl><dt>12-4 </dt><dd>J 1.5 TNBAL 1 30 10 Sulfated Al2O3 fifty 90 3600 0.03 1.18 </dd></dl>

<dl><dt>12-5 </dt><dd>J 1.5 TIBA 1 30 10 Sulfated Al2O3 fifty 87 3480 0.01 0.78 </dd></dl>

<dl><dt>12-6 </dt><dd>K 1.5 TNBAL 1 60 10 Sulfated Al2O3 fifty 210 4200 0.09 2.02 </dd></dl>

<dl><dt>12-7</dt><dd> L 3 TIBA 1 30 10 Sulfated Al2O3 100 177 3540 0 1.76 </dd></dl>

<dl><dt>12-8 </dt><dd>P 3 TIBA 1 30 10 Sulfated Al2O3 100 130 2600 0.01 0.56 </dd></dl>

<dl><dt>12-9 12-10 </dt><dd>Ind2ZrCl2Ind2ZrCl2 3 2 TIBA 1 TNBAL 1 3030 10 10 Sulfated Al2O3 Sulfated Al2O3 100100 219 175 4380 3500 0 0.37 1 6.76 </dd></dl>

As shown in Table 1, the catalysts G (Runs 12-1 and 12-2) and H (Run 12-3), each possesses an indenyl with a substituent in position 1 which incorporates a terminal olefin, and a monosubstituted cyclopentadienyl, show about 25 to about 60% more polymerization activities

5 high (support activity) than Ind2ZrCl2 under similar conditions (Runs 12-9 and 12-10).

Additionally, the polymers produced by the metallocene compounds G and J, and Ind2ZrCl2 were evaluated by using 13 C NMR to determine the level of 1-hexene incorporation (Runs 12-11 to 12-15). Ind2ZrCl2 in general is considered to be a poor comonomer that incorporates catalyst. The results of the evaluation are presented in Table 2 and are illustrated in FIG. 3. As is evident from the data

10 presented, there is a drop of almost 50% in the incorporation of 1-hexene in the polymers formed by the use of metallocene compounds G and J compared to the polymer formed by the use of Ind2ZrCl2.

Table 2.

<dl><dt>Run </dt><dd>Catalyst Catalyst Weight (mg) 1-Hexene (g) R3Al (ml) Support Support (mg) Solid PE (g) MI (g / 10 min) HLMI (g / 10 min) 1-Hexene (mol% butyl </dd></dl>

<dl><dt>12-11</dt><dd> Ind2ZrCl2 1.5 10 TIBA Sulfated Al2O3 fifty 101 0.04 3.32 0.13 </dd></dl>

<dl><dt>12-12 </dt><dd>G 1.5 10 TIBA Sulfated Al2O3 fifty 117 0.09 2.24 0.08 </dd></dl>

<dl><dt>12-13 </dt><dd>J 3.0 10 TIBA Sulfated Al2O3 100 340 0 0.88 0.066 </dd></dl>

<dl><dt>12-14</dt><dd> Ind2ZrCl2 2.0 25 TIBA Sulfated Al2O3 100 246 0.43 11.02 0.37 </dd></dl>

<dl><dt>12-15 </dt><dd>J 3.0 25 TIBA Sulfated Al2O3 100 258 0.20 5.47 0.19 </dd></dl>

Example 13

Pilot plant polymerizations were conducted to demonstrate the ability to use dual metallocene catalyst systems in accordance with the present invention to form a bimodal polymer. The metallocene compound C was used to form the high molecular weight component and the metallocene compound G was used to form the low molecular weight component.

To prepare a solution of metallocene C, 2.00 g of solid metallocene C, zirconium dichloride 1- (phenyl) -1- (3butenyl) -1- (cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) ) methane, suspended in approximately 200 ml of

10 hexene-1, followed by the addition of 25 grams of (93%) pure triethylaluminum, under nitrogen. This solution was diluted with 100 to 240 grams of n-heptane and transferred to a steel container. Isobutane was added to obtain a total of 18.12 kg of solution.

To prepare a solution of metallocene G, 2.00 g of solid metallocene G was dissolved in 420 ml of toluene under nitrogen. The solution was transferred to a steel container. Isobutane was added to obtain a total of 18.12 kg

fifteen from solution.

Tri-n-butylaluminum (TNBAL) (obtained from Akzo Corporation) was used as a co-catalyst. TNBAL was obtained as a pure solution and diluted to 10 percent by weight with heptane. Cocatalyst was added in a concentration in a range of about 8 to about 26 parts per million of the diluent in the polymerization reactor (s). To avoid static accumulation in the reactor, usually a

twenty small amount (less than 5 ppm by weight of diluent) of a commercial antistatic agent sold as "Stadis 450".

The pilot plant polymerizations were conducted in a 87-liter suspension loop reactor at a production rate of approximately 11.32 kg of polymer per hour. The polymerization runs were carried out under continuous conditions of particle formation process in a loop reactor (also

25 known as a suspension process) by contacting a solution of metallocene, tri-n-butylaluminum, and a solid activator in a 300 ml stirred autoclave with continuous exit to the loop reactor.

The precontact was carried out as follows. The tri-n-butylaluminum solution and metallocene solution were fed as separate streams in an upstream in T of the autoclave where they are brought into contact with each other. The solid activator (sulfated aluminum oxide) was rinsed with isobutane in a T between the T before

30 mentioned and the autoclave, contacting the tri-n-butylaluminum / metallocene mixture just before entering the autoclave. The isobutane circulation used to transport the solid activator in the autoclave was set at a rate that would result in a residence time of approximately 25 minutes in the autoclave. Total autoclave flow then entered the loop reactor.

The ethylene used was ethylene suitable for polymerization (obtained from Union Carbide Corporation) which was purified to

35 through an aluminum oxide column and activated at 250 ° C (482 ° F) under nitrogen. The 1-hexene, when used, was 1-hexene suitable for polymerization (obtained from Chevron Phillips Chemical Company LP) which was purified by purging with nitrogen and storage on activated 13x molecular sieve at 250 ° C (482 ° F) in nitrogen . The loop reactor was a loop reactor of 15.2 cm in diameter, of complete liquid, which had a volume of 87 liters (23 gallons). Liquid isobutane was used as diluent. Some hydrogen was added to

40 regulate the molecular weight of the low molecular weight component of the polymer product. The isobutane was isobutane suitable for polymerization (obtained from Chevron Phillips Chemical, Borger, Tex.) Which was further purified by distillation and subsequently passed through an aluminum oxide column (activated at 250 ° C (482 ° F)). nitrogen).

The reactor conditions included a pressure of approximately 580 psi (4 MPa), and a temperature that was

Four. Five ranged from approximately 90 ° C (194 ° F) to approximately 99 ° C (210 ° F). Also, the reactor was operated to have a residence time of approximately 1 hour. The solid activator was added through a 0.35cc circulation ball control feeder and fed into a 300ml autoclave as described above. The catalyst system concentrations in the reactor were within a range of about 1 to 2 parts per million (ppm) of the diluent in the polymerization reactor. The polymer was removed from the reactor at a

fifty speed of approximately 11.32 kg per hour and recovered in an instant evaporation chamber. A Vulcan dryer was used to dry the polymer under nitrogen at about 60 to about 80 ° C (about 40 to about 176 ° F).

Various resins were prepared in accordance with the above procedure. The results of the evaluation are presented in Table 3.

Table 3.

<dl><dt>Run </dt><dd>Metallocene (Relaeion) H2 (mLb / hr) HLMI pellet (dg / 10 min) Pellet MI (dg / 10 min) Density (pellets) (g / ee) Mw (x103) Mw / Mn Charpy (J @ 23 C) eon notch </dd></dl>

<dl><dt>13-1 </dt><dd>C + G (2,3) 4 3.96 0.08 0.9497 243 9.9 1.55 </dd></dl>

<dl><dt>13-2 </dt><dd>C + G (2) 4 7.2 0.12 0.9522 210 16.9 1.56 </dd></dl>

<dl><dt>13-3 </dt><dd>C + G (1,9) 4 4.24 0.08 0.9497 239 9.9 1.94 </dd></dl>

<dl><dt>13-4 </dt><dd>C + G (2) 6 5.2 0.12 0.9486 200 15.3 1.64 </dd></dl>

5 As is evident, the resins produced in accordance with the present invention exhibit excellent high impact resistance, illustrated by the impact of Charpy with notch at 23 ° C.

FIG. 4 presents the GPC curves for the resins produced in Run 13-1, 13-2, 13-3 and 13-4, which demonstrate that a true bimodal molecular weight distribution polymer is obtained from the catalyst compositions herein. invention.

10 In summary, the present invention provides various catalyst compositions, methods for forming a catalyst composition, and resins and pipes formed by utilizing the catalyst compositions. The catalyst composition in general includes two metallocene compounds, an activator, and a cocatalyst. The compounds of two metallocenes are selected so that the two metallocenes produce polymers that have two clearly different molecular weights. The metallocenes are combined with an activating support,

fifteen an organoaluminum compound, and an olefinic monomer to produce a polyolefin having a bimodal molecular weight distribution. The resulting polymers possess excellent impact resistance. The present invention also provides new metallocene compounds and an improved method of synthesis of semi-metallocene compounds.

While expensive aluminoxanes and organoborates are not required by the present invention, they can be used

twenty as desired. As demonstrated by the examples above, the use of a system of three catalysts, such as those described herein, produces polyolefin films that possess desirably low turbidity while maintaining other physical attributes, such as dart impact.

The above description has been presented for the purpose of illustration and description. It is not intended to be exhaustive or limit the invention to the precise examples or embodiments described. Modifications or variations

25 Obvious are possible in light of the above teachings. The embodiment or debated embodiments were chosen and described to provide the best illustration of the principles of the invention and their practical application to allow one with common experience in the art to use the invention in various embodiments and with various modifications as conforming to the particular use contemplated. All such modifications and variations are within the scope and the invention as determined by the appended claims.