Half-metallocene compounds and catalyst compositions.

(54) Title: COMPOUND WITH HALF METALLOCENE AND CATALYST COMPOSITIONS.

(54) Title: HALF-METALLOCENE COMPOUNDS AND CATALYST COMPOSITIONS.

(57) Summary

The present invention provides polymerization catalyst compositions employing half metallocene compounds with a ligand containing a heteroatom bound to the transition metal. Methods are also provided for making these hybrid metallocene compounds and for using such compounds in catalyst compositions for olefin polymerization.

(57) Abstract

The present invention provides polymerization catalyst compositions employing half-metallocene compounds with a heteroatom-containing ligand bound to the transition metal. Methods for making these hybrid metallocene compounds and for using such compounds in catalyst compositions for the polymerization of olefins also are provided.

PATENT TITLE No. 360528

Headlines):

Home:

Denomination:

<img file="MX360528B_D0001.tif" />

CHEVRON PHILLIPS CHEMICAL COMPANY LP

10001 Six Pines Drive, The Woodlands, Texas, 77380, USA

COMPOSED WITH HALF OF CATALYSTS.

METALLOCENE AND COMPOSITIONS OF

CIP: CPC:

C07F17 / f

C0ZF17 / F4 /&gt; 6; ' _tC08fe4 / 6 6; C08F210 / 16

ERRUfcj btflG; JOEL L. MA

<img file="MX360528B_D0002.tif" />

Classification!

Inventor (s):

<img file="MX360528B_D0003.tif" />

YANG; YOULU YU

International

Industrial.

/ 2012, non-extendable, counted to IOS.

C08F10 / 00; C08F4 / 65912;

Number:

MX / a / 2013/008582

US

Term years

Date of V¿ ^ cirwientÓF2¿ ~ of @ hero de '^ OjfeJ ^{* 1}

Who subscribes the present title with the function in (Official Gazette of the Federation 27/1

01/25/2006, 05/06/2009, 01/06/201® * W ^ / iftlO_M06/28/201 and 12th sections I and III of the Regíame »07/28/2004 and 09/07/2007); Articles 1 ', v, Industrial Property (DOF 12/27/1999, re »* Rad powers in the Deputy Directors General, Departmental Coordinators and other subordinates · 07/29/2004, 08/04/2004 and 09/13/2007) .

aey of Industrial Property / 1999, 01/26/2004, 06/16/2005, os 1 ·, 3rd fraction V subsection a), 4^ordo on 07/01/2002, 07/15/2004, the only one of the Mexican Institute of

ÍW °, 3 ° and 5 ° clause a) of the Agreement that delegates Regional Otas, Divisional Deputy Directors,. (DOF 12/15/1999, amended on 02/04/2000,

This letter is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 fraction III, 2 fraction V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

THE DIVISIONAL DIRECTOR OF PATENTS

<img file="MX360528B_D0004.tif" />

NAHANNY CANAL REYES

Original string:

NAHANNY MARISOL CANAL REYES | 00001000000403252793 | Administration Service

Tax | 1695 || MX / 2018/102714 | MX / a / 2013/008582 | PCT patent title | 1223 | GAGV | Page (s) | bOfb9np2AyptRACGURNAeqJDEXc =

Digital stamp:

U + 3TtekfORV7LHLiD96it45o9 / 7jHqzy7RRmnlSZPwust8bQZgm8bmPZFsrx2mTmFUkVQPe + u / E2YGGnyHY7l5lgRA ihRQVn5MpgwMbZRtqAyJY5sREbg4ygbbzBI2PsEHPhsb / HOII6ZoGPr5o4lb7r6YvXHz5QvifGjhd4r + HrFKW3876D V5iql0io5ObJFqpL67mXIRjs2ptFrs1r0OkLCxToy5gXMW3PjEoxadM + s1gsKzBHh6h4GjEEB65hhw43qn8w5gyTdG Z9nY8b6of \ / C3ssmmNFG9s7LGYHAsVOApxzjLklvyMp4ualtDlo32EGDgA9IH3T7C / == GE1tlbg

Arenal No. 550, Floor 1, Pueblo Santa María Tepepan, Xochimilco, 16020, Mexico City.

(55) 53340700 www.gob.mx/innpi

<img file="MX360528B_D0005.tif" />

MX / 2018/102714

MEXICAN INSTITUTE

OF THE MONEDAD

INDUSTRIAL

HALF METALOCENE COMPOUNDS AND COMPOSITIONS OF

36052$

CATALYSTS

BACKGROUND OF THE INVENTION

In general, the present invention relates to the field of olefin polymerization catalysis, with catalyst compositions, with methods for the polymerization of olefins and polyolefins. More specifically, this invention relates to metallocene half compounds with a ligand containing a transition metal-bound heteroatom, and to catalyst compositions employing these hybrid compounds.

Polyolefins such as high-density polyethylene homopolymer (HDPE) and linear low-density polyethylene copolymer (LLDPE) can be produced using various combinations of catalyst systems and polymerization processes. A method that can be used to produce such polyolefins employs a chromium based catalyst system. HDPE and LLDPE resins produced using a chromium based catalyst system generally have a wide molecular weight distribution. For example, resins that have a polydispersity index (PDI, or

Mw / Mn) greater than 6 are not unusual. Resins

IMPI

Mexican INSTITUTE or the N.c '&gt; ro «»' NOUSTSI »!

Polyolefin produced using a chromium catalyst can also have a low level of long chain branching. This combination of properties is difficult to duplicate with commercially viable catalyst systems. Metallocene catalysts, for example, can generally produce polyolefins with a much narrower molecular weight distribution and have too little or too much long chain branching. Also, Ziegler-type catalyst systems can produce polyolefin resins that are typically much narrower in molecular weight distribution and substantially have no long chain branching. Polyolefin resins produced using a Bailará-type catalyst, in general, may be too high in molecular weight, too wide in molecular weight distribution and contain too long a chain branching.

It would have been beneficial to have a catalyst system without

<img file="MX360528B_D0006.tif" />

chromium that could produce a define polymer having the desired combination of a relatively wide molecular weight distribution and a relatively low level of long chain branching. Therefore, it is for this purpose that the present invention is intended.

BRIEF DESCRIPTION OF THE INVENTION

IMPI

MEXICAN INSTITUTE OF LA MOHEDAL,, INDUSTRIAL

<img file="MX360528B_D0007.tif" />

This brief description provides a selection of concepts in a simplified introductory form which is described below in the detailed description of the invention. This brief description of the invention is not intended to identify the essential required features of the related subject matter claimed. Nor is this brief description of the invention intended to be used to limit the scope of the related subject matter claimed.

In general, the present invention relates to novel catalyst compositions, to methods of preparing catalyst compositions, to methods of using catalyst compositions to polymerize olefins, to polymeric resins produced using such catalyst compositions, and to articles produced using these polymeric resins. In particular, the present invention relates to half metallocene compounds with a ligand containing a heteroatom bound to the transition metal, and to catalyst compositions employing such hybrid metallocene compounds. The catalyst compositions of the present invention, which contain these hybrid metallocene compounds, can be used to produce, for example, ethylene-based homopolymers and copolymers.

Novel hybrid metallocene compounds are described herein having a metallocene radical and a ligand containing a heteroatom. In accordance with one aspect of the present invention, these hybrid unbridged metallocene compounds may have the formula:

<img file="MX360528B_D0008.tif" />

X * - M v3

TO·

<img file="MX360528B_D0009.tif" />

IMPI

<img file="MX360528B_D0010.tif" />

In formula (I), M can be Zr, Hf or Ti; XI and X2 independently may be a substituted or unsubstituted halide or aliphatic, aromatic or cyclic group, or a combination thereof; X3 may be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, wherein any of the substituents on X3 are independently a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; and X4 can be -O-RA, -NH - RA, -PH-RA, -S-RA, -O-YES-RB3 or -OC-RB3. RA may be an aryl group substituted with a first alkoxy group and a second substituent selected from an alkyl, cycloalkyl or a second alkoxy group, wherein any of the additional substituents on RA are independently a hydrogen atom or an alkyl, cycloalkyl or alkoxy.

IMPI MEXICAN INSTITUTE OF INDUSTRIAL FRONETY

<img file="MX360528B_D0011.tif" />

Each RB can independently be a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.

Catalyst compositions containing these hybrid metallocene compounds without spike are also provided by the present invention. In one aspect, a catalyst composition is described, which comprises a hybrid metallocene compound and an activator. This catalyst composition may further comprise an organoaluminum compound. In some aspects, the activator may comprise an activator support, while in other aspects, the activator may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.

In accordance with some aspects of the invention, novel hybrid metallocene compounds and catalyst compositions comprising these hybrid metallocene compounds and an activator are described and exemplified. For example, these hybrid metallocene compounds can have one of the following formulas:

<img file="MX360528B_D0012.tif" />

(IU); or

<img file="MX360528B_D0013.tif" />

"V).

IMPI

<img file="MX360528B_D0014.tif" />

WTITUTO MEXICANO PC THE INDUSTRIAL PROPERTY

In formula (III) and formula (IV), each M can be independently Zr, Hf or Ti; each XI and X2 can independently be a substituted or unsubstituted halide or aliphatic, aromatic or cyclic group, or a combination thereof; and each X3 can independently be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, wherein any of the substituents on X3 are independently a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.

Catalyst compositions containing a hybrid metallocene compound having formula (III) or formula (IV) may further comprise an organoaluminum compound, and the activator may comprise an activator support, an aluminoxane compound, an organoboron compound or organoborate, an ionizing ionic compound, or combinations thereof.

The present invention also contemplates olefin polymerization processes. Such processes may comprise contacting a catalyst composition with an olefin monomer and optionally, an olefin comonomer under polymerization conditions to produce an olefin polymer. In general, the catalyst composition employed can comprise any of the compounds of

IMPIOUS

MEXICAN INSTITUTE '

DE LA FRO.-UDAD INDUSTRIAL. metallocene hybrids described herein, and any

<img file="MX360528B_D0015.tif" />

of the activators described herein. Furthermore, organoaluminum compounds can also be used in polymerization processes.

Polymers produced from the polymerization of olefins, resulting in homopolymers, copolymers, terpolymers, etc., can be used to produce various articles of manufacture.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 presents the structures and abbreviations for some hybrid metallocene compounds or metallocene mita compounds described herein.

<td>The</td><td>Figure 2</td><td>presents</td><td>a</td><td>graph</td><td>of</td><td>1H-NMR</td><td>of the</td><td>product</td>

<td>from MET-H</td><td colspan="2">of Example 2.</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>The</td><td>Figure 3</td><td>presents</td><td>a</td><td>graph</td><td>of</td><td>1H-NMR</td><td>of the</td><td>product</td>

<td colspan="2">MET-J Example</td><td> 4 .</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>The</td><td>Figure 4</td><td>presents</td><td>a</td><td>graph</td><td>of</td><td>1H-NMR</td><td>of the</td><td>product</td>

<td>MET-K's</td><td>1 Example</td><td> 5.</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>The</td><td>Figure 5</td><td>presents</td><td>a</td><td>graph</td><td>of</td><td colspan="3">the distributions</td>

molecular weight of the polymer of Example 14 and of a comparative polymer produced using a standard metallocene catalyst system.

Figure 6 presents a graph of the distributions

<img file="MX360528B_D0016.tif" />

IMPI

MEXICAN INSTITUTE of molecular weight of polymers of

Figure 7 presents a graph of the di g.1-ri tnri ήη,. Of molecular weight of the polymer of Example 47.

Figure 8 presents a graph of the radius of gyration against the logarithm of the molecular weight for a linear standard and the polymers of Examples 34 and 56.

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 takes over.

The term polymer is used herein generically to include olefin homopolymer, copolymer, terpolymer, etc. A polymer is derived from one olefin monomer and one olefin comonomer, while a terpolymer is derived from one olefin monomer and two olefin comonomers. Therefore, the polymer encompasses copolymers, terpolymers, etc., derived from any olefin monomer and comonomer (s) described herein. Similarly, an ethylene polymer would include

<img file="MX360528B_D0017.tif" />

JL JLvjl 11

MEXií INSTITUTE

DS THE PROPL

INDUSTR copolymers dr

ethylene homopolymers, ethylene terpolymers, and the like. As an example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene a comonomer, such as 1-butene, 1-hexene

1-octene.

If the monomer and comonomer were ethylene

1-hexene, respectively, the resulting polymer would be categorized as an ethylene / 1-hexene copolymer.

Similarly, the scope of the term polymerization includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process would involve contacting a define monomer (eg, ethylene) and an olefin comonomer (eg, 1-hexene) to produce a copolymer.

The term co-catalyst is generally used herein to refer to organoaluminum compounds that may constitute a component of a catalyst composition. In addition, co-catalyst may refer to other compounds of a catalyst composition including, but not limited to, aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds, as described herein, when used in addition to an activating support. The term co-catalyst is used without regard to the actual function of the compound or any chemical mechanism by which the

IPI&gt; Lií; í; can &lt;j ¹ PROPItlíAÓ NDUSTÍUai

<img file="MX360528B_D0018.tif" />

In one aspect of the invention, the term co-catalyst can be used to distinguish the component of the catalyst composition from the hybrid metallocene compound (s).

The terms chemically treated solid oxide, activator support, treated solid oxide compound, and the like, are used herein to indicate a relatively high porosity solid, inorganic oxide which may exhibit Lewis acid or Bronsted acid behavior , and which has been treated with an electron extraction component, typically an anion, and which is calcined. The electron extraction component is typically a compound of an anionic electron extraction source.

Thus, the chemically treated solid oxide may comprise a calcined contact product of at least one solid oxide with at least one compound of an anionic electron extraction source. Typically, the chemically treated solid oxide comprises at least one acidic solid oxide compound. The terms support and activator 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. The activating support of the present invention can be a chemically treated solid oxide. The term

<img file="MX360528B_D0019.tif" />

activator, how to use

PI

INSTITUTO MEXICAW &lt;: DELA PROPIEDAD 'CV, INDUSTRIAL in the present, refers

<img file="MX360528B_D0020.tif" />

generally, to a substance that is capable of converting a metallocene component into a catalyst that can polymerize olefins, or convert a contact product of a metallocene component and a component that provides an activatable ligand (eg, an alkyl, a hydride ) to the metallocene, when the metallocene compound no longer comprises such a ligand, in a catalyst that can polymerize olefins. This term is used without considering the actual trigger mechanism. Illustrative activators include activator supports, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and the like.

Aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds in general are referred to as activators if used in a composition in which an activator support is not present. If the catalyst composition contains an activating support, then the aluminoxane, organoboron, or organoborate, and ionizing ionic materials are generally referred to as co-catalysts.

The term fluoroorganoboron compounds is used herein with its ordinary meaning to refer to neutral compounds of the form BY3. The term fluoroorgano borate compound also has its usual meaning for

<img file="MX360528B_D0021.tif" />

IΜ PI.

MEXICAN INSTITUTE refer to fluoroorganoboro monoanionic salts of the form [cati ó njÍ. 44 ^ .— where. Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as organoboron or organoborate compounds.

The term hybrid metallocene, as used herein, describes a metallocene half compound without a bridge, with a ligand containing a heteroatom bound to the transition metal. The hybrid metallocenes of this invention contain a radical of type η 3 η5cyclopentadienyl, wherein the radicals η3 η5cycloalcadienyl include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of these. Possible substituents on these ligands include hydrogen, therefore, the description substituted derivatives thereof in this invention encompasses partially saturated ligands, such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially substituted saturated indenyl, substituted partially saturated fluorenyl and the like.

In some contexts, the hybrid metallocene may simply be referred to as the catalyst,

<img file="MX360528B_D0022.tif" />

<img file="MX360528B_D0023.tif" />

that most of the time the

I

MF.XICANO INSTITUTE

Say THE PROrit'OA.O

INDUSTRIAL The term co-catalyst can be used to refer to, for example, an organoaluminum compound.

The terms catalyst composition, catalyst mixture, catalyst system and the like do not depend on the actual product or composition resulting from contact or reaction of the initial components of the claimed catalyst composition / mixture / system, the nature of the catalytic site active, or the nature of the co-catalyst, the metallocene compound (s), any olefin monomer used to prepare a precontacted mixture, or the activator (eg. activator support), after combining these components. Therefore, the terms catalyst composition, catalyst mixture, catalyst system, and the like, encompass the initial initiating components of the composition, as well as any product (s) that could result from contact with these initial initiating components, and that is inclusive of heterogeneous and homogeneous catalyst systems or compositions.

The term contact product is used herein to describe compositions, wherein the components are contacted with each other in any order, in any way, and for any length of time. For example,

IMPI

Mexican INSTITUTE

FROM industrial PROPERTY the components can be contacted by combination or

<img file="MX360528B_D0024.tif" />

mixed. Furthermore, contact of any component can occur in the presence or absence of any other component of the compositions described herein. The combination of additional materials or components can be done by any appropriate method. In addition, the term contact product includes mixtures, combinations, solutions, suspensions, reaction products and the like, or combinations thereof.

Although the contact product may include reaction products, the respective components are not required to react with each other. Similarly, the term contact is used herein to refer to materials that can be combined, mixed, suspended, dissolved, reacted, treated, or otherwise contacted in some other way.

The term "pre-contacted mixture" is used herein to describe a first mixture of catalyst components that are contacted for a first period of time before using the first mixture to form a post-contacted mixture or second mixture of the catalyst components they get in touch for a second period of time. Typically, the precontacted mixture can describe a mixture of a metallocene compound (one or more than one), monomer (or monomers) of

<img file="MX360528B_D0025.tif" />

olefin, and a compound (or before this activator mixture and an additional, optional. Of these components that are used to

PI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0026.tif" />

organoaluminum compounds), contacting an organoaluminum compound in a pre-contacted manner describes contacting each other, but before contacting the components in the second post-contacted mixture. Therefore, this invention may occasionally distinguish between a component used to prepare the pre-contacted mixture and such a component after the mixture has been prepared. For example, in accordance with this description, the pre-contacted organoaluminum compound, once contacted with the metallocene compound and the olefin monomer, may have to react to form at least one different chemical compound. , formulation or structure of the different organoaluminum compound used to prepare the pre-contacted mixture. In this case, the pre-contacted organoaluminum compound or component is described, which comprises an organoaluminum compound that was used to prepare the precontacted mixture.

Furthermore, the precontacted mixture may describe a mixture of metallocene compound (s) and organoaluminum compound (s), before contacting this mixture with an activator support (s). This precontacted mix can also describe a mix

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY of metallocene compound (s),

<img file="MX360528B_D0027.tif" />

olefin monomer (s) and in contact this mixture with an organoaluminum cocatalyst compound (s).

Similarly, the term post-contacted mixture is used herein to describe a second mixture of catalyst components that are contacted for a second period of time, and a constituent of which is the pre-contacted mixture or first mixture of catalyst components that were in contact for a first period of time. Typically, the term post-contacted mixture is used herein to describe the mixture of metallocene compound (s), olefin monomer (s), activating organoaluminum compound (s) formed from contact of the pre-contacted mixture of a portion of these components with any additional components added to make the postcontacted mixture.

Often the activating support can comprise a chemically treated solid oxide. For example, the additional component added to make the post-contacted mixture may be a chemically treated solid oxide (one or more than one), and optionally, may include an organoaluminum compound that is the same or different from the organoaluminum compound used to prepare mixture

IMPI,

V'XÍrasOS LA PRO MEXICAN INSTITUTE ?! INDUSTRIAL AGE pre-contacted, as defined herein. For 1

<img file="MX360528B_D0028.tif" />

This invention may occasionally distinguish between a component used to prepare the post-contacted mixture and the component after the mixture has been prepared.

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

All the publications and patents mentioned in 1 to present, are incorporated by reference for the purpose of describing and representing, for example, the constructions and methodologies described in the publications, which could be used in conjunction with the presently described invention. The publications described throughout the text are provided solely for your description prior to the date of publication of this application. I dont know

<td>will build</td><td>nothing in the</td><td colspan="2">present as</td><td>an admission that</td><td>the</td>

<td>inventors</td><td>they do not have</td><td>the</td><td>straight</td><td>to antedate</td><td>such</td>

<td>description</td><td colspan="2">according to the</td><td>invention</td><td>previous.</td><td></td>

For any particular compound described herein, any general or specific structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that could

<img file="MX360528B_D0029.tif" />

arise from a particular group of substituents, unless otherwise stated. Similarly, unless otherwise stated, the general or specific structure also encompasses all enantiomers, diastereomers, and other optical isomers, either in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a person experienced in the art.

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

Applicants describe various types of ranges in the present invention. These include, but are not limited to, an atom number range, an integer range, a weight ratio range, a molar ratio range, a molecular weight range, a temperature range, and so on. When applicants describe or claim an interval of any kind, the applicant's intention is to individually describe or claim each possible number that such interval could reasonably encompass, including the endpoints of each interval,

MEXICAN INSTITUTE

OF THE INDUSTRIAL MONEDAD as well as any sub-intervals and combinations of sub-intervals covered herein. For example, when applicants describe or claim a chemical radical having a certain number of carbon atoms, the applicant's intention is to individually describe or claim each possible number that such a range could encompass, consistent with the description herein. For example, the description of such a radical is a CI to C18 hydrocarbyl group, or in alternative language, a hydrocarbyl group having up to 18 carbon atoms, as used herein, refers to a radical that can be selected from a hydrocarbyl group independently selected from a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, '17 or 18 carbon atoms, as well as any interval between these two numbers (for example, a CI to C8 hydrocarbyl group), and which also includes any combination of ranges between these two numbers (eg, a C2 to C4 hydrocarbyl group and a C12 to C16 hydrocarbyl group).

Similarly, another representative example follows the Mw / Mn ratio provided in one aspect of this invention. By description, such Mw / Mn ratio can be in a range of about 3 to about 20, applicants intend to mention that Mw / Mn can be of

IMPI

ICυΤΟ MEXICAN OF FROFlITY

INBUSTR1AL

<img file="MX360528B_D0030.tif" />

<td>approximately</td><td> 3,</td><td>approximately</td><td> 4,</td><td>approximately</td><td> 5,</td>

<td>approximately</td><td> 6,</td><td>approximately</td><td> 7,</td><td>approximately</td><td> 8,</td>

<td>approximately</td><td> 9,</td><td>approximately</td><td> 10,</td><td>approximately</td><td> 11,</td>

<td>approximately</td><td> 12,</td><td>approximately</td><td> 13,</td><td>approximately</td><td> 14,</td>

<td>approximately</td><td> 15,</td><td>approximately</td><td> 16,</td><td>approximately</td><td> 17,</td>

<td>approximately</td><td> 18,</td><td>approximately</td><td>19th</td><td>approximately</td><td> 20.</td>

Furthermore, the Mw / Mn ratio can be within any range of from about 3 to about 20 (eg, from about 5 to about 15), and this also includes any combination of ranges from about 3 to about 20 (eg, Mw / Mn can be in the range of about 4 to about 6, or from about 8 to about 13). Likewise, all other ranges described herein should be interpreted in a similar way to these two examples.

Applicants reserve the right to qualify or exclude any individual numbers from any group, including any sub-ranges or combinations of sub-ranges within the group, that may be claimed according to a range or in any way, if for any reason the applicants they choose to claim less than the total measure of the description, for example, represent a reference that applicants may be unaware of at any time during the filing of any applicants

IMPI «τιτυτο Mexican

DELA INDUSTRIAL PROPERTY

<img file="MX360528B_D0031.tif" />

application. In addition, they reserve the right to qualify or exclude individual substituents, analogs, compounds, ligands, structures or groups thereof, or any members of a claimed group, if for any reason applicants choose to claim less than the full extent of the description, for example, represent a reference that the applicants might not know at that moment of the presentation of the application.

The terms un, una, el, la, etc., are intended to include plural alternatives, eg, at least one, unless otherwise specified. For example, the description of an activator support or a hybrid metallocene compound is understood to encompass one, or mixtures or combinations of more than one, activator support or hybrid metallocene compound, respectively.

While the compositions and methods are described in terms of comprising various components or steps, the compositions and methods may also consist essentially of or consist of the different components or steps. For example, a catalyst composition of the present invention may comprise; alternatively, it may consist essentially of; or alternatively, it may consist of; (i) a hybrid metallocene compound and (ii)

DETAILED DESCRIPTION OF THE INVENTION

<img file="MX360528B_D0032.tif" />

MEXICAN INSTITUTE

DS INDUSTRIAL PROPERTY

<img file="MX360528B_D0033.tif" />

an activator.

In general, the present invention relates to new catalyst compositions, to methods of preparing catalyst compositions, to methods of using catalyst compositions to polymerize olefins, using the polymeric resins produced such catalyst compositions, and articles produced using these polymeric resins. In particular, the present invention relates to metallocene half compounds with a ligand containing a transition metal-bound heteroatom, and to catalyst compositions employing such hybrid metallocene compounds.

HYBRID METALOCHENE COMPOUNDS

The present invention describes novel hybrid metallocene compounds having a metallocene radical and a ligand containing a heteroatom, and with methods for making such compounds. For convenience, these compounds will be referred to herein as hybrid metallocene compounds. In one aspect of this invention, the bridged hybrid metallocene compound may have the formula:

X¹—M ““ X³I x⁴ (11.

where:

M. can be Zr, Hf or Ti; ''

XI and X2 can independently be a substituted or unsubstituted halide or aliphatic, aromatic or cyclic group, or a combination thereof;

X3 can be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, wherein any one of the substituents on X3 can independently be a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;

X4 can be -O-RA, -NH-RA, -PH-RA, -S-RA, -O-S1-RB3, or

-OC-RB3; where:

RA may be an aryl group substituted with a first alkoxy group and a second substituent selected from an alkyl, cycloalkyl, or a second alkoxy group, wherein any of the additional substituents on RA can independently be a hydrogen atom or an alkyl group, cycloalkyl or alkoxy; and each RB can independently be a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic or cyclic group, or a combination thereof.

Unless otherwise specified, formula (I) above, any other formulas described herein, and any species of hybrid metallocene or

<img file="MX360528B_D0034.tif" />

IMPI „. MEXICAN INSTITUTE

4 Say THE ROMANCE

INDUSTRIAL compound described herein, are not designated to show stereochemistry or isomeric positioning of different radicals (eg, these formulas are not intended to exhibit cis or trans isomers, or R or S diastereoisomers), although these compounds are contemplated and encompassed by these formulas and / or structures.

In metal in formula (I), M, can be Zr, Hf, or Ti. In one aspect of the present invention, M can be either Zr or Ti, while in another aspect, M can be Ti.

In formula (I), XI and X2 can independently be a halide, such as a fluorine, chlorine, bromine or iodine atom. As used herein, an aliphatic group includes linear or branched alkyl or alkenyl groups. In general, the aliphatic group can contain from 1 to 20 carbon atoms. Unless otherwise specified, the alkyl and alkenyl groups described herein are intended to include all structural, linear or branched isomers of a given radical; for example, all enantiomers and all diastereomers are included within this definition. As an example, unless otherwise specified, the term propyl is understood to include n-propyl and isopropyl, while the term butyl is understood to include n-butyl, iso-butyl, t-butyl, sec-butyl, etc. For example, non-limiting examples of octyl isomers may include 2-ethyl hexyl, the appropriate alkyl groups which present invention may include,

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0035.tif" />

and neooctyl. Examples of may be used in, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or alkenyl, including, but not decyl, and the like. Examples of the groups of se pentenyl, hexenyl, and the like.

scope limited to, heptenyl,

Aliphatic aromatic groups include groups can include, substituted with alkyl, alkyl with naphthyl, and combinations of radical atoms include but are not present invention can be ethenyl, propenyl, butenyl, octenyl, nonenyl, decenyl and combinations with aryl and arylalkyl, they are limited to, phenyl, groups and these phenyl alkyl, naphthyl, naphthyl substituted with similar substituted.

carbon groups.

Here, those with phenyl, substituted alkyl

In general, these groups and may contain less than 20 non-limiting examples of such that can be used in the present invention may phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like.

Cyclic groups can include cycloalkyl and cycloalkenyl radicals and these radicals can include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. A

<img file="MX360528B_D0036.tif" />

MEXICAN INSTITUTE I heard THE PROf IFOAD INDUSTRIAL

<img file="MX360528B_D0037.tif" />

An example of a combination that includes a · cyclic group is a cyclohexylphenyl group. Unless otherwise specified, any substituted aromatic or cyclic radicals used herein are understood to include all regioisomers; for example, the term tolyl is understood to include any possible substituent position, that is, ortho, meta or para.

In one aspect of the present invention, XI and X2 can independently be a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms. In another aspect, XI and X2 can independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. In yet another aspect, either XI or X2, or both, can be trimethylsilyl methylthio. In yet another aspect, XI and X2 may independently be ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. XI and X2 can independently be a substituted or unsubstituted aromatic group, eg, having up to 20 carbon atoms, in another aspect of the present invention.

In a different aspect, XI and X2 can be chlorine atoms. XI and X2 can independently be phenyl, naphthyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl

<img file="MX360528B_D0038.tif" />

INSTITUTO MEX'CA D £ THE PROPERTY O ciff! ^ In other aspects of this invention. Even 'in another way',¹XI and X2 can independently be methyl, phenyl, benzyl, or halide. Furthermore, XI and X2 can independently be methyl, phenyl, benzyl, or a chlorine atom in another aspect of the present invention.

<td>In the</td><td>formula (I),</td><td>X3</td><td colspan="3">can be a group</td>

<td colspan="2">cyclopentadienyl, indenyl</td><td>or</td><td>fluorenyl</td><td>replaced</td><td>or</td>

<td>unsubstituted.</td><td>In one aspect</td><td>of</td><td>the present</td><td>invention,</td><td>X3</td>

<td>can be</td><td colspan="3">a cyclopentadienyl group</td><td>replaced</td><td>or</td>

<td>unsubstituted.</td><td>In another respect,</td><td>X3</td><td>It can be a</td><td colspan="2">indenyl group</td>

<td>substituted or</td><td>unsubstituted.</td><td></td><td></td><td></td><td></td>

X3 can be an unsubstituted cyclopentadienyl, indenyl, or fluorenyl group. Alternatively, X3 can have one or more substituents. Any one of the substituents on X3 can independently be a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic or cyclic group, or a combination thereof. Hydrogen is included, therefore, the notion of a substituted indenyl and substituted fluorenyl may include partially saturated indenyl and fluorenyl which include, but are not limited to tetrahydroindenyl, tetrahydrofluorenyl and octahydrofluorenyl. Examples of aliphatics that can be used in the present invention may include alkyls and

<img file="MX360528B_D0039.tif" />

MEXICAN INSTITUTE OF THE ΡΧΟΜΕΟλ;.! industrial

<img file="MX360528B_D0040.tif" />

alkenyls, examples of which may include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl or decenyl and the like. Illustrative aromatic groups and combinations with aliphatic groups, as described above, can include phenyl, tolyl, benzyl, and the like. Cyclic substituents are also contemplated herein, and non-limiting examples have also been provided above, including radicals, such as cyclopentyl and cyclohexyl.

In one aspect of this invention, each substituent on X3 can independently be a hydrogen atom, or a methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl group. In another aspect, the substituents on X3 can independently be ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, or a hydrogen atom.

X4 in formula (I) can be -O-RA, -NH-RA, -PH-RA, S-RA, -O-YES-RB3 or -OC-RB3. In accordance with one aspect of the present invention, X4 can be -O-RA. According to another aspect, X4 can be -NH-RA. According to yet another aspect, X4 can be -PH-RA or, alternatively, -S-RA. In the radicals -O-RA, -NH-RA, -PH-RA and -S-RA, RA can be a

MEXICAN INSTITUTE

DELAPKOhSOAD INDUSTRIAL aryl group substituted with a first alkoxy group and a second substituent selected from an alkyl, cycloalkyl or a second alkoxy group. RA can be an aryl group substituted with a first alkoxy group, and the first alkoxy group can have from 1 to 20 carbon atoms, from 1 to 12 carbon atoms, or from 1 to 8 carbon atoms. Representative alkoxy groups can include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and the like.

In this way, the first alkoxy group in RA can be, for example, a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

RA can be substituted with a second substituent selected from an alkyl, cycloalkyl group or a second alkoxy group. The alkyl group, cycloalkyl group, and the second alkoxy group can be any alkyl, cycloalkyl, and alkoxy group described herein.

group

In one aspect, the second substituent on RA may be a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group , a propoxy group or a butoxy group; alternatively, a methyl group, an ethyl group, a propyl group, an n-butyl group, or a t-butyl group; alternatively, a cyclopentyl group or a cyclohexyl group; or alternatively, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD

<img file="MX360528B_D0041.tif" />

In one aspect of this invention, RA can be a disubstituted aryl group, and in a further aspect, RA can be a 2,6-disubstituted aryl group. In other aspects, RA can be further substituted with additional substituents;

in general, such additional substituents can independently be a hydrogen atom or an alkyl, cycloalkyl or alkoxy group.

In some respects X4 can be -O-RA. Non-limiting examples of X4 in these aspects of the invention may include, but are not limited to, the following radicals:

<img file="MX360528B_D0042.tif" />

CH₃CH₂CH₂OX

<img file="MX360528B_D0043.tif" />

and the like.

In accordance with other aspects of the invention, X4 in

<img file="MX360528B_D0044.tif" />

<img file="MX360528B_D0045.tif" />

MEXICAN INSTITUTE

FROM INDUSTRIAL PROPERTY formula (I) can be -O-YES-RB3 or -OC-RB3; alternatively,

X4 can be -O-YES-RB3; or alternatively, X4 can be -OC-RB3. Each RB can independently be a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. Each RB, therefore, can be the same or different. Examples of the aliphatic, aromatic or cyclic groups, or combinations thereof, that can be used as RB, independently, can include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonllo , decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl, xylyl, methyl benzyl, l-ethenyl-2phenyl, l-ethynyl-2-phenyl, cyclopentyl, cyclohexyl and Similar.

In one aspect, X4 in formula (I) can be -O-YES-RB3

<td>or -OC-RB3, and each</td><td>RB can be</td><td>independently</td><td>a</td><td>atom</td>

<td>hydrogen, a</td><td>methyl group,</td><td>an ethyl group,</td><td>a</td><td>group</td>

<td>propyl, a group</td><td>n-butyl, a</td><td>t-butyl group,</td><td>a</td><td>group</td>

phenyl, a benzyl group, a tolyl group, a xylyl group, a methyl benzyl group, an l-ethenyl-2-phenyl group or an l-ethynyl-2-phenyl group. In another aspect, each RB can independently be a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a group

<img file="MX360528B_D0046.tif" />

phenyl, a benzyl group, a tolyl group, a lio group, a methyl benzyl group, an l-ethenyl-2-phenyl group or an l-ethinyl-2-phenyl group. Even, in another aspect, each RB can independently be a phenyl group, a benzyl group, a tolyl group, a xylyl group, a methyl benzyl group, an l-ethenyl-2-phenyl group or an l-ethynyl-2- group. phenyl. Furthermore, X4 in formula (I) can be -O-YES-RB3 or -OC-RB3, and each RB can independently be a phenyl group, a benzyl group, a methyl benzyl group, a l-ethenyl-2- group phenyl or a l-ethynyl-2-phenyl group, in a particular aspect of this invention.

In formula (I), substituted aliphatic, aromatic or cyclic groups, and combinations thereof, are described. These groups described herein are intended to include substituted analogues with substitutions at any position in these groups that are in accordance with the normal rules of chemical valence. Thus, groups substituted with one or more than one substituent are contemplated.

These substituents, when present, can be independently selected from an oxygen group, a sulfur group, a nitrogen group, a phosphorous group, an arsenic group, a carbon group, a silicon group, a germanium group, a tin group, a lead group , a boron group, a

<img file="MX360528B_D0047.tif" />

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0048.tif" />

aluminum group, an inorganic group, a qruiao. organometallic, or a substituted derivative thereof, any one of which has from 1 to about 20 carbon atoms; a halide; or hydrogen; provided these groups do not terminate the activity of the catalyst composition. Examples of each of these substituent groups may include, but are not limited to, the following groups

Examples of halide substituents, at each occurrence, may include fluoride, chloride, bromide, and iodide.

At each occurrence, oxygen groups are oxygen-containing groups, examples of which may include, but are not limited to, alkoxy or aryloxy (-ORX) groups,

OSÍRX3, -OPRX2, -OA1RX2, and the like, including substituted derivatives thereof, wherein RX at each occurrence may be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to 20 atoms carbon. Examples of alkoxy groups or aryloxy groups (-ORX) can include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like.

In each occurrence, sulfur groups are sulfur-containing groups, examples of which may include, but are not limited to, -SRX and the like, including derivatives

IMPI

MUIVANC INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0049.tif" />

substituted thereof, wherein RX at each occurrence may be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to 20 carbon atoms.

At each occurrence, nitrogen groups are nitrogen-containing groups, which may include, but are not limited to, -NRX2 and the like, including substituted derivatives thereof, wherein RX at each occurrence may be alkyl, cycloalkyl, aryl , aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to 20 carbon atoms.

In each occurrence, phosphorous groups are phosphorous-containing groups, which may include, but are not limited to, -PRX2, -P (ORX) 2, and the like, including substituted derivatives thereof, wherein RX in each occurrence, may be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to 20 carbon atoms.

At each occurrence, arsenic groups are arsenic containing groups, which may include, but are not limited to, -AsRX2, -As (ORX) 2, and the like, including substituted derivatives thereof, wherein RX in each occurrence may be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl

MEXICAN INSTITUTE OF THE INDUSTRIAL PROPERTY

<img file="MX360528B_D0050.tif" />

It has 1 to 20 carbon atoms.

In each occurrence, carbon groups are carbon-containing groups, which may include, but are not limited to, alkyl halide groups comprising halide-substituted alkyl groups with 1 to 20 carbon atoms, aralkyl groups with 1 to 20 carbon atoms, -C (NRX) 'H, C (NRX) RX, -C (NRX) ORX and the like, including substituted derivatives thereof, wherein RX, at each occurrence, may be alkyl, cycloalkyl, aryl , aralkyl, substituted alkyl, substituted aryl or substituted aralkyl having 1 to 20 carbon atoms.

In each occurrence, silicon groups are silicon-containing groups, limited to, groups which may include, but are not silyl, such as alkylsilyl groups, arylsilyl groups, arylalkyl silyl groups, siloxy groups, and the like, which, at each occurrence, they can have 1 to 20 carbon atoms.

For example, substituents on the silicon group can include trimethylsilyl phenyloctylsilyl groups.

In each occurrence, germanium groups are germanium-containing groups, which may include, but are not limited to, germyl groups, such as alkylgermyl groups, arylgermyl groups, arylalkylgermyl groups, germiloxy groups, and the like, which in each occurrence may have 1 to 20 carbon atoms.

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0051.tif" />

At each occurrence, the groups contain tin-containing groups, which may include, but are not limited to, stanyl groups, such as alkyl stanyl groups, aryl stanyl groups, arylalkyl stanyl groups, stanoxy (or stanyloxy) groups, and similar, which, in each occurrence, can have from 1 to 20 carbon atoms. In this way, tin groups can include, but are not limited to, stanoxy groups.

In each occurrence, lead groups are lead-containing groups, which may include, but are not limited to, alkyl-lead groups, aryl-lead groups, arylalkyl-lead groups, and the like, which in each occurrence, may have from 1 to 20 carbon atoms .

In each occurrence, boron groups are boron-containing groups, which may include, but are not limited to, -BRX2, -BX2, -BRXX, and the like, where X may be a monoanionic group such as hydride, alkoxide, alkyl thiolate, and the like, and wherein RX at each occurrence, may be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to 20 carbon atoms.

In each occurrence, aluminum groups are aluminum-containing groups, which may include, but are not

IMPI

Mexican Institute of Industrial Property

<img file="MX360528B_D0052.tif" />

they are limited to, -A1RX, -A1X2, -A1RXX, where X 'can ..... be - tur monoanionic group, such as hydride, alkoxide, alkyl thiolate, and the like, and where RX at each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to 20 carbon atoms.

Examples of inorganic groups that can be used as substituents, in each occurrence, may include, but are not limited to, -OA1X2, -OSÍX3, -OPX2, -SX, -AsX2, -PX2 and the like, where X can be a monoanionic group such as hydride, amide, alkoxide, alkyl thiolate, and the like, and wherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted or substituent aralkyl group in these ligands can have from 1 to 20 carbon atoms.

Examples of the organometallic groups that can be used as substituents, in each occurrence, may include, but are not limited to, organoborium groups, organoaluminum groups, organogalium groups, organosilicon groups, organogermanium groups, organotin groups, organo-lead groups, organo-metal groups of transition, and the like, having 1 to 20 carbon atoms.

In accordance with one aspect of the present invention, M can be Zr or Ti in formula (I), and XI and X2 can be

<img file="MX360528B_D0053.tif" />

IMPI „MEXICAN INSTITUTE

OF THE PROPERTY

INDUSTRIAL independently a methyl group, a phenyl group, a benzyl group, or a halide. In this regard, X3 can be a substituted or unsubstituted cyclopentadienyl group, and X4 can be O-RA. In these and other respects, RA can be a disubstituted aryl group (eg, a 2,6-disubstituted aryl group), a substituent of which can be a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; and the other substituent of which may be a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

According to another aspect, M can be Zr or Ti in formula (I), and XI and X2 can independently be a methyl group, a phenyl group, a benzyl group or a halide. In this regard, X3 can be a substituted or unsubstituted cyclopentadienyl group, and X4 can be -O-YES-RB3 or -OC-RB3. In these and other aspects, each RB can independently be a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a phenyl group, a benzyl group, a tolyl group, a xylyl group , a methyl benzyl group, a l-ethenyl-2-phenyl group or a l-ethinyl-2-phenyl group; alternatively, each RB may independently be a phenyl group, a benzyl group, a tolyl group, a xylyl group, a methyl benzyl group, an l-ethenyl-2-phenyl group, or

IMPI

<img file="MX360528B_D0054.tif" />

an l-ethinyl-2-phenyl group.

In accordance with another aspect, the hybrid metallocene compounds described herein can have the

<img file="MX360528B_D0055.tif" />

gave);

formula:

where:

XI and X2 can independently be a methyl group, a phenyl group, a benzyl group, or a halide;

each RC can independently be a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group or a hexyl group;

n can be an integer from 0 to 5, inclusive;

X4 can be -O-RA, -O-YES-RB3 or -OC-RB3;

where:

RA can be a 2,6-disubstituted aryl group, where the substituent at position 2 can be a methoxy group, an ethoxy group, a propoxy group or a butoxy group, and the substituent at position 6 can be a methyl group , an ethyl group, a propyl group, an n-butyl group, a t40 group

IMPI

MEXICAN INSTITUTE OE THE PROPERTY

<img file="MX360528B_D0056.tif" />

butyl, a cyclopentyl group, a cycloKexi'io group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group; and each RB can independently be a phenyl group, a benzyl group, a tolyl group, a xylyl group, a methyl benzyl group, an l-ethenyl-2-phenyl group or a group

1ethynyl-2-phenyl.

Even, according to another aspect, the hybrid metallocene compounds described herein can have the formula:

where:

every every

<img file="MX360528B_D0057.tif" />

M can

XI and X2 are independently Zr,

Hf can independently be a substituted or unsubstituted halide or aliphatic, aromatic or cyclic group, or a combination thereof;

each X3 may independently be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, wherein any of the substituents on X3 ₄₁ IMPI

NJT1TVTO MEXICA NO

MONETY y * can independently be a substituted or unsubstituted hydrogen atom or uTi aliphatic, aromatic or cyclic group, or a combination thereof.

In the particular aspects contemplated herein p, M in formulas (III) and (IV) can be either Zr or Ti, or alternatively, M can be Ti. Each XI and X2 can independently be any halide or any substituted or unsubstituted aliphatic, aromatic or cyclic group, or a combination of the groups described herein. For example, each XI and X2 can independently be a methyl group, a phenyl group, a benzyl group, or a halide. Furthermore, each X3 can independently be a substituted or unsubstituted indenyl group or, alternatively, each X3 can independently be a substituted or unsubstituted cyclopentadienyl group. In some aspects, X3 may be unsubstituted (eg, an unsubstituted cyclopentadienyl group), while in other aspects, X3 may have one or more substituents. Any of the substituents on X3 can independently be a hydrogen atom or any substituted or unsubstituted aliphatic, aromatic or cyclic group, or a combination of the groups described herein. As an example, each substituent on each X3 can independently be a hydrogen atom or a methyl, ethyl, propyl, n-butyl, t-butyl or hexyl group.

IMPI MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0058.tif" />

Illustrative and non-limiting examples of the hybrid metallocene compounds of the present invention may include

<img file="MX360528B_D0059.tif" />

the following compounds:

and the like.

Other hybrid metallocene compounds are contemplated as appropriate for use in the present invention, therefore, the scope of the present invention is not limited to the hybrid metallocene species provided herein.

Methods for making the hybrid metallocene compounds of the present invention are also provided. In addition to the procedures employed in the following Examples, appropriate methods may include those described in Scholz et al., Journal of Organometallic Chemístry (1993), 443 (1), 93-9; Thorn et al., Journal of the Chemical Society, Dalton Transactions (2002), 17, 3398-3405; and US Patent Publication No. 2010-0010174; the descriptions of which are incorporated herein by reference in its

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0060.tif" />

whole.

ACTIVATOR SUPPORT

The present invention encompasses various catalyst compositions containing an activator, which may be an activator support. In one aspect, the activator support may comprise a chemically treated solid oxide. Alternatively, the activating support may comprise a clay mineral, a pillar clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a layered silicate mineral, an unlaminated silicate mineral, an aluminosilicate mineral layered, an unlaminated aluminosilicate mineral or combinations thereof.

In general, chemically treated solid oxides exhibit improved acidity compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide can also function as a catalyst activator, compared to the corresponding untreated solid oxide. While chemically treated solid oxide can activate hybrid metallocene in the absence of co-catalysts, it is not necessary to remove co-catalysts from the catalyst composition. The activation function of the activator support may be evident in the

IMPI

MEXICAN INSTITUTE

OF THE MONEDAD

INDUSTRIAL

<img file="MX360528B_D0061.tif" />

improved activity of the catalyst composition as a whole, 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, organoboron or organoborate compounds, ionizing ionic compounds and the like.

The chemically treated solid oxide may comprise a solid oxide treated with an electron extraction anion. While not intended to be related by the following statement, treatment of the solid oxide with an electron extraction component is believed to increase or improve the acidity of the oxide. Thus, the activator support exhibits a Lewis or Bransted acidity that is typically greater than the Lewis or Bronsted acid concentration of the untreated solid oxide, or the activator support has a higher number of acidic sites than the untreated solid oxide. , or both. One method of quantifying the acidity of the chemically treated and untreated solid oxide materials can be by comparing the polymerization activities of the treated and untreated oxides under acid catalyzed reactions.

In general, the chemically treated solid oxides of this invention can be formed from an oxide, colide-i'iiejriyáir ± TO that exhibits a Lewis acid or

Bronsted and has a relatively high porosity. Rust

MEXICAN INSTITUTE

INDUSTRIAL PROPERTY SOLID can be chemically treated with an electron extraction component, typically an electron extraction 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 of greater than about 0.1 cc / g. In accordance with another aspect of the present invention, the solid oxide may have a pore volume of greater than about 0.5 cc / g.

another aspect of the present invention, the

According to even solid oxide it can have a pore volume greater than about 1.0 cc / g.

In another aspect, the solid oxide can have a surface area of ​​about 100 to about 1000 m2 / g. In yet another aspect, the solid oxide can have a surface area of ​​from about 200 to about 800 m2 / g. In yet another aspect of the present invention, the solid oxide can have a surface area of ​​from about 250 to about 600 m2 / g.

The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10

<img file="MX360528B_D0062.tif" />

<img file="MX360528B_D0063.tif" />

11, 12, 13, 14 or 15 of the periodic table, or comprising oxygen and one or more elements of the elements lanthanides or actinides (See: Hawley's Condensed Chemical Dictionary, llth Ed., John Wiley &amp; Sons, 1995; Cotton, FA, Wilkinson, G., Murillo, CA, and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, the inorganic oxide may comprise oxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.

Appropriate examples of the solid oxide or compound materials that can be used to form the chemically treated solid oxide may include, but are not limited to, A12O3, B2O3, BeO, BÍ2O3, CdO, Co304, Cr2O3, CuO,

Fe2O3, Ga2O3, La2O3, Mn2O3, Mo03, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, and the like, including mixed oxides thereof and combinations thereof. For example, the solid oxide can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof.

The solid oxide of this invention encompasses materials of

IMPI MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD

<img file="MX360528B_D0064.tif" />

Oxides, such as alumina, encompass solid oxide materials, such as alumina, mixed oxide compounds thereof, such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds, such as silica-alumina, can be single or multiple chemical phases with oxygen to form a solid oxide compound. Examples of the mixed oxides that can be used in the activating support of the present invention, either alone or in combination, may include, but are not limited to, silica alumina, silica titania, silica zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silicon-boria, aluminophosphate, silica, titania-zirconia and the like. The solid oxide of this invention also encompasses oxide materials, such as silica-coated alumina, as described in US Patent Publication No. 2010-0076167, the disclosure of which is incorporated herein by reference in its entirety.

The electron extraction component used to treat the solid oxide can be any component that increases the Lewis or Bronsted acidity of the solid oxide with treatment (compared to solid oxide that is not treated with at least one electron extraction anion. ).

In accordance with one aspect of the present invention, the

<img file="MX360528B_D0065.tif" />

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INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL electron extraction component can be an electron extraction anion derived from a salt, an acid or another compound, such as a volatile organic compound, that serves as a source or precursor for such anion. Examples of the electron extracting anions can include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, and the like, including mixtures and combinations thereof. Furthermore, other ionic or nonionic compounds that serve as sources for these electron extracting anions can also be employed in the present invention. It is contemplated that the electron extracting anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate or sulfate, and the like, or any combination thereof, in some aspects of this invention. In other aspects, the electron extracting anion may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and the like or combinations thereof.

Thus, for example, the activating support (eg, chemically treated solid oxide) used in catalyst compositions of the

IMPI MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0067.tif" />

present invention, may be, or may comprise, fluorinated alumina, chlorinated alumina, brominated alumina, sulfate alumina, fluorinated silica-alumina, chlorinated silica-alumina, sulfate silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia , brominated silica-zirconia, sulphated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulphated silica-coated alumina, phosphate-coated silica-alumina and the like, or combinations thereof. In one aspect, the activating support may be, or may comprise, fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulphated silica-alumina, fluorinated silica-coated alumina, sulphated silica-coated alumina, phosphate-coated silica alumina, and the like, or any combination thereof. In another aspect, the activating support may comprise fluorinated alumina; alternatively, chlorinated alumina; alternatively sulfated alumina;

alternatively, fluorinated silica-alumina;

alternatively, sulfated silica-alumina; alternatively, fluorinated silica-zirconia; alternatively, chlorinated silica-zirconia or alternatively, fluorinated silica-coated alumina.

When the electron extraction component comprises a salt of an electron extraction anion, the counterion or cation of such salt

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0068.tif" />

it can be selected from any cation that allows the salt to revert or decompose to acid again during calcination. Factors that dictate the suitability of the particular salt to serve as a source for the electron extracting anion may include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse cation reactivity, the effects of the ion pair between the cation and the anion, the hygroscopic properties imparted to the salt by the cation, and the like, and the thermal stability of the anion.

Examples of the appropriate cations in the electron extraction anion salt may include, but are not limited to, ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H +, and the like.

Furthermore, combinations of one or more different electron extraction anions, in varying proportions, can be used to size the specific acidity of the activator support to the desired level. The combinations of the electron extraction components can be contacted with the oxide material simultaneously or individually, and in any order that provides the desired acidity of the chemically treated solid oxide. For example, one aspect of this invention may employ two or more. ₅₁ IMPI

MEXICAN INSTITUTE £ ζ * · ββ5Ρ * ^ Ο

PROPERTY composed of anion extraction sources' electrons * in two or more separate contact stages.

Thus, a process by which a chemically treated solid oxide can be prepared is as follows: a selected solid oxide, or a combination of solid oxides, can be contacted with a first compound from an electron extraction anion source, to form a first mixture; This first mixture can be calcined and then contacted with a second compound from an electron extraction anion source to form a second mixture; The second mixture can then be calcined to form a treated solid oxide. In such a process, the first and second compounds of the electron extraction anion source may be the same or different compounds.

In accordance with another aspect of the present invention, the chemically treated solid oxide may comprise a solid inorganic oxide material, a mixed oxide material, or a combination of inorganic oxide materials, which is chemically treated with an electron extraction component. , and optionally, is treated with a metal source, which includes metal salts, metal ions, or other metal-containing compounds. Non-limiting examples of the metal or metal ion may include zinc, nickel, vanadium, titanium, silver,, INDUSTRIAL copper, gallium,

IMPI

MEXICAN INSTITUTE OF LA MONEDAD

<img file="MX360528B_D0069.tif" />

anus, tungsten, molybdenum, zirconium and the like, or combinations thereof.

Examples of chemically treated solid oxides containing a metal or metal ion may include, but are not chlorinated, alumina limited to fluorinated zinc impregnated zinc impregnated alumina, chlorinated zinc, silica-alumina chlorinated impregnated alumina, sulfated aluminate, alumina hexafluorotitanic, with zinc zinc coated with fluorinated titanium, silica-alumina alumina impregnated with sulfated impregnated, fluorinated, with fluorinated zinc, aluminate aluminate de with silica treated with alumina coated with silica zinc and then fluorinated, and the like, or any acid zinc zinc treated with combination thereof.

Any method can be used to impregnate solid oxide. Oxide is typically placed, one may include, with salt the material a metal. The method by contact with or a compound one that but is not limited to, source contains which the metallic, a metal, gelation, cogelification, impregnation of one compound in another, and the like. If desired, the metal-containing compound can be added to, or impregnated into the solid oxide in the form of a solution, and subsequently converted to the supported metal upon calcination. Therefore, the solid inorganic oxide can also

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0070.tif" />

comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals. For example, zinc can often be used to impregnate solid oxide because it can provide improved catalyst activity at low cost.

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

Various processes can be used to form the chemically treated solid oxide useful in the present invention. The chemically treated solid oxide can comprise the contact product of one or more solids with one or more electron extraction anion sources. The solid oxide is not required to be calcined prior to contact of the electron extraction anion source. Typically the

<img file="MX360528B_D0071.tif" />

₅₄ IMPI

INSTITUTO MEXICANO DE LA MONEDAD INDUSTRIAL contact product can be calcined either during or after the solid oxide comes into contact with the electron extraction anion source. Solid oxide may or may not be calcined. Different processes have been reported to prepare the solid oxide activator supports that can be used in this invention. For example, such methods are described in US Patent Nos.

<td> 6,107,230,</td><td> 6,165,929,</td><td> 6,294,494,</td><td colspan="2"> 6,300,271, 6,316,553,</td>

<td> 6,355,594,</td><td> 6,376,415,</td><td> 6,388,017,</td><td colspan="2"> 6,391,816, 6,395,666,</td>

<td> 6,524,987,</td><td> 6,548,441,</td><td> 6,548,442,</td><td> 6,576,583, 6,613,7</td><td> 12,</td>

<td> 6,632,894,</td><td>6,667,274 and</td><td colspan="2">6,750,302, the descriptions of</td><td>the</td>

<td>which ones</td><td colspan="2">incorporate herein</td><td>by reference in</td><td>its</td>

<td>whole.</td><td></td><td></td><td></td><td></td>

<td colspan="2">According to a</td><td>aspect of the</td><td>present invention,</td><td>the</td>

<td>material</td><td colspan="2">solid oxide can</td><td colspan="2">chemically treated</td>

<td>putting it on</td><td>in contact</td><td colspan="2">with an extraction component</td><td>of</td>

<td>electrons</td><td>, typically</td><td>a source of</td><td>extraction anion</td><td>of</td>

<td>electrons</td><td>. Furthermore, the</td><td>material of</td><td colspan="2">solid oxide can,</td>

optionally, chemically treated with a metal ion, and then calcined to form a solid oxide containing a metal or chemically treated impregnated with a metal. In accordance with another aspect of the present invention, the solid oxide material and the electron extraction anion source can be contacted and calcined.

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0072.tif" />

simultaneously. _____________

The method by which the oxide is contacted with the electron extraction component, typically a salt or an acid of an electron extraction anion, may include, but is not limited to, gelation, cogelification, impregnation of a compound in another, and the like. In this way, after any contact method, the contact mixture of the solid oxide, the electron extraction anion and the optional metal ion can be calcined.

In this way, the solid oxide activating support (i.e., the chemically treated solid oxide) can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with a compound (or compounds) of an electron extraction anion source to form a first mixture; and

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

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

1) contacting a solid oxide (or solid oxides) with a first compound of an electron extraction anion to form a first mixture;

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0073.tif" />

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

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

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

<td>In accordance with</td><td>yet another aspect of this</td>

<td>invention oxide</td><td>chemically treated solid can</td>

<td>occur or form</td><td>contacting the solid oxide</td>

with a compound of an electron extraction anion source, wherein the solid oxide compound is calcined before, after or after contacting the electron extraction anion source, and where there is a substantial absence of aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds.

In general, calcination of the treated solid oxide can be carried out in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature of from about 200 ° C to about 900 ° C, and for a time of from about 1 minute to about 100 hours. The calcination can be carried out at a temperature of about 300 ° C to about 800 ° C,

<img file="MX360528B_D0074.tif" />

IMPI

MEXICAN INSTITUTE

OF EA PROPERTY

INDUSTRIAL alternatively, at a temperature of about 400 ° C to about 700 ° C. The calcination can be carried out for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. In this way, 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 ambient temperature can be used during calcination. In general, the calcination can be carried out in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reduced atmosphere, such as hydrogen or carbon monoxide, can be used.

In accordance with one aspect of the present invention, the solid oxide material may be treated with a source of halide ion, sulfate ion, or a combination of anions, optionally treated with a metal ion, and then calcined to provide the chemically treated solid oxide. the form of a particulate solid. For example, the solid oxide material can be treated with a source of sulfate (called a sulfating 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. Activator mounts include, but are not limited to, chlorinated, brominated,

IMPI

MEXICAN INSTITUTE OF INDUSTRY PROPERTY!

<img file="MX360528B_D0075.tif" />

Useful acids can include brominated alumina, fluorinated alumina alumina, sulfated alumina, silica-alumina, silica-chlorinated alumina, silica-fluorinated alumina, silica-brominated alumina, silica-brominated zirconia, silica-fluorinated zirconia, silica-zirconia, zirconia fluorinated silica-titania, hexafluorotitanic acid-treated alumina, hexafluorotitanic acid-treated silica-coated alumina, hexafluorozirconic acid-treated silica-alumina, silica-alumina treated with trifluoroacetic acid, fluorinated boria-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillar clay, such as pillar montmorillonite, optionally treated with fluoride sulfate; phosphate alumina or other aluminophosphates optionally treated with sulfate, fluoride or chloride; or any combination of the above. Furthermore, any of these activating supports can be optionally treated or impregnated with a metal ion.

The chemically treated solid oxide may comprise a fluorinated oxide in the form of a particulate solid. Fluorinated solid oxide can be formed by contacting a solid oxide with a fluorinating agent. Fluoride ion can

IMPI

9 MEXICAN INSTITUTE

FROM INDUSTRIAL PROPERTY add 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

<img file="MX360528B_D0076.tif" />

to its volatility and low surface tension. Examples of appropriate fluorinating agents may include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) ( (NH4) 2SÍF6), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TÍF6), hexafluorotitanic ammonium hexafluorozirconic acid (H2ZrF6), the same, and combinations of using triflic acid ((NH4) 2TF6)

<td>A1F3,</td><td>NH4A1F4,</td><td>analogues</td><td>of the</td>

<td>the</td><td>themselves.</td><td>Too</td><td>they can</td>

<td>and the</td><td>triflate</td><td colspan="2">ammonium. By</td>

For example, ammonium bifluoride (NH4HF2) can be used as the fluorinating agent, due to its ease of use and availability.

If desired, the solid oxide can be treated with a fluorinating agent during the calcination step. Any fluorinating agent capable of fully contacting the solid oxide can be used during the calcination step. For example, in addition to the fluorination agents previously described, volatile organic fluorination agents can be used. Examples of the agents of «or IMPI ^^ k

MEXICAN INSTITUTE&gt;

Say THE PROPERTY useful volatile organic fluoridation in eS⁴IS^Twétepeftter^?The invention may include, but is not limited to, S6llMltáh 57 TfyófWs, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. The calcination temperatures in general must be high enough to decompose the compound and release the fluoride. Gaseous hydrogen fluoride (HF) or molecular fluorine (F2) itself can also be used as the solid oxide if it is fluorinated while calcining. Silicon tetrafluoride (SiF4) and tetrafluoroborate containing compounds (BF4-) can also be used. A convenient method of contacting the solid oxide with the fluorinating agent may be to vaporize a fluorinating agent in a gas stream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically treated solid oxide may comprise a chlorinated solid oxide in the form of a particulate solid. Chlorinated solid oxide can be formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide, forming a suspension of the oxide in an appropriate solvent. The solid oxide can be treated with a chlorination agent during the calcination step. Any chlorination agent capable of serving as a

INSTITUTO MEXICANO DS LA TUOf'ÍEDAD INDUSTRIAL source of chloride and completely contact the oxide during the calcination stage, such as SÍC14, SiMe2C12,

TIC14, BC13 and the like, including mixtures thereof

Volatile chlorination agents can be used. Examples of the appropriate volatile organics can include, but are not limited to, some freons, perchlorobenzene, chloromethane tetrachloride, dichloromethane, chloroform, carbon, trichloroethanol, and the like, or any combination thereof. Gaseous hydrogen chloride, or chlorine itself, can also be used as the solid oxide during calcination. A convenient method of contacting the oxide with the chlorination agent may be to vaporize a chlorination agent in a gas stream to fluidize the solid oxide during calcination.

The amount of fluoride or chloride ion present before the calcination of the solid oxide, in general, can be from about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, for example silica -alumina, before calcination. According to another aspect of this invention, the amount of the fluoride or chloride ion present before the calcination of the solid oxide can be from about 1 to about 25% by weight, and according to another aspect of the invention, from about 2 to about 20% by weight. Agree

IMPI with yet another aspect of

MEXICAN INSTITUTE

OF THE PROPERTY the present invention,

<img file="MX360528B_D0077.tif" />

fluoride or chloride ion present before calcination of the solid oxide, can be from about 4 to about

10% by weight. Once impregnated with halide, the halide oxide can, including, but not suction followed by evaporation, be dried by any method limited to drying, vacuum filtration, spray drying and the like, but also immediately calcining step without impregnation.

it is possible to start drying the solid oxide

The silica-alumina used to prepare treated may have about 0.5 present invention, about 0.8 the silica-alumina typically has a volume cc / g. According to a larger aspect pore the pore volume may be greater cc / g, and according to another aspect present invention,

In addition, in general, surface greater than of than of greater than approximately

1.0 cc / g.

the silica-alumina can have an area of ​​approximately 100 m2 / g. In accordance with another aspect of this invention, the surface area may be greater than about 250 m2 / g.

even, in another aspect, the surface area may be greater than about

350 m2 / g.

The silica-alumina used in the present invention can typically have an alumina content of approximately

IMPI

<img file="MX360528B_D0078.tif" />

at about 95% by weight.

In accordance with one aspect of this invention, the alumina content of the silica-alumina can be from about 5 to about 50%, or from about 8% to about 30%, alumina by weight. In another aspect, high alumina silica-alumina compounds can be employed, where the alumina content of these silica-alumina compounds typically ranges from about 60% to about 90%, or from about 65% to about 80 % of alumina by weight. In accordance with yet another aspect of this invention, the solid oxide component can comprise alumina without silica, and according to another aspect of this invention, the solid oxide component can comprise silica without alumina.

The sulfated solid oxide can comprise sulfate and the solid oxide component, such as alumina or silica alumina, in the form of a particulate solid. Optionally, the sulfate oxide may be further treated with a metal ion so that the calcined sulfate oxide comprises a metal. In accordance with one aspect of the present invention, the sulfated solid oxide can comprise sulfate and alumina. In some cases, sulfated alumina can be formed by a process where the alumina is treated with a source of sulfate, for example, sulfuric acid or a salt of ₆4 IMPIAS

MEXICAN INSTITUTE OF PROPERTY sulfate, such as ammonium sulfate. In generalT^L This process can be accomplished by forming a suspension of alumina 5Π an appropriate solvent, such as alcohol or water, to which the desired concentration of the sulfating agent has been added. Appropriate organic solvents can include, but are not limited to, one to three carbon alcohols due to their volatility and low surface tension.

In accordance with one aspect of this invention, the amount of sulfate ion present prior to calcination can be from about 0.5 to about 100 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. In accordance with another aspect of this invention, the amount of sulfate ion present prior to calcination can be from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and according to another aspect of this invention, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of 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 appropriate method including, but not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible

<img file="MX360528B_D0079.tif" />

start the stage of

IMPI

INSTITUTO MEXICANO DE LA PROFIF.OAD INDUSTRIAL calcination immediately.

In accordance with another aspect of the present invention, the activating support used in the preparation of the catalyst compositions of this invention may comprise an ion exchange activating support including, but not limited to, silicate and aluminosilicate compounds or minerals, either with layered or non-layered structures and combinations thereof. In another aspect of the layered aluminosilicates of the present invention, ion exchange, such as abutment clays, can be used as activator supports. When the acid activating support comprises an ion exchange activating support, it can optionally be treated with at least one electron extraction anion, such as those described herein, although typically the ion exchange activating support is not treated with a electron extraction.

In accordance with another aspect of the present invention, the activating support of this invention may comprise clay minerals having interchangeable cations and layers capable of expansion. Typical clay mineral activator supports may include, but are not limited to, ion exchange layered aluminosilicates, such as abutment clays. Although the

IMPI MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0080.tif" />

By the term "support", it is not understood that it is constructed as an inert component of the catalyst composition, but can be considered an active part of the catalyst composition, due to its close association with the hybrid metallocene component.

In accordance with another aspect of the present invention, the clay materials of this invention may encompass materials in their natural state or that have been treated with various ions by wetting, ion exchange, or pillar formation. Typically, the activating support for the clay material of this invention may comprise clays that have been ion-exchanged with large cations, including highly charged, polynuclear, metal complex cations. However, the supports of the clay material of this invention may also encompass clays that have been ion-exchanged with simple salts, including, but not limited to, Al (III), Fe (II), Fe ( III) and Zn (II) with ligands such as halide, acetate, sulfate, nitrate or nitrite.

In accordance with another aspect of the present invention, the activating support may comprise a pillar clay. The term pillar clay is used to refer to clay materials that have been ion-exchanged with highly charged metal complex cations,

IMPI

<img file="MX360528B_D0081.tif" />

typically polynuclear. Examples of such ions can include, but are not limited to, Keggin ions that can have fillers, such as 7+, various polyoxometalates, and other large ions. In this way, the term pillar can refer 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 can then be immobilized within the clay interlayers and when calcined they are converted to metal oxide pillars, which effectively support the clay layers as column-like structures. In this way, once the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded network structure can be maintained and the porosity can be improved. The resulting pores can vary in shape and size as a function of the abutment material and the parent clay material used. Examples of pillar and pillar composite clays are found in: TJ Pinnavaia, Science 220 (4595), 365-371 (1983); JM Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Chapter 3, pp. 55-99, Academic Press, Inc., (1972); US Patent No. 4,452,910; US Patent No. 5,376,611; and US Patent No. 4,060,480; the descriptions of which are incorporated herein by reference in its

<img file="MX360528B_D0082.tif" />

₆₈ IMPI

MEXICAN INSTITUTE OF MONEDAD entirely. industrial

The abutment formation process can use a myriad of clay that has interchangeable cations and layers capable of expansion. An abutment clay that can enhance the polymerization of olefins can be used in the catalyst composition of the present invention. Therefore, appropriate clay minerals for pillar formation may include, but are not limited to, allophanes; smectites, dioctahedral (Al) and tri-octahedral (Mg) and their derivatives, such as: montmorillonites (bentonites), nontronites, hectorites or laponites; halloisites; vermiculites; micas; fluoromics; chlorites; mixed layer clays; fibrous layers that include, but are not limited to sepiolites, attapulgites, and paligorschites; a serpentine clay; illite; laponite; saponite and any combination thereof. In one aspect, the pillar clay activating support may comprise bentonite or montmorillonite. The main component of bentonite is montmorillonite.

If desired, the pillar clay can be pretreated. For example, a column 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 exemplary pretreatment is described herein, it should

<img file="MX360528B_D0083.tif" />

IMPI

INSTITUTO MEXICANO M LA MONEDA D INDUSTRIAL it is understood that preheating can be carried out at many other temperatures and times, including any combination of temperature and time stages, all of which are encompassed by this invention.

The support catalyst used activator compositions to be combined with other materials for the present support to prepare the invention may be inorganic, including, but 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, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminum phosphate, silica-titania, silica / co-precipitated titania, mixtures thereof, or any combination thereof.

In accordance with another aspect of the present invention, one or more of the hybrid metallocene compounds may be pre-contacted with an olefin monomer and an organoaluminum compound for a first period of time before contacting this mixture with the activator support. . Once the pre-contacted mixture of the metallocene compound (s), olefin monomer, and organoaluminum compound is contacted with the activator support, the composition further comprising the activator support is

<img file="MX360528B_D0084.tif" />

IMPI

INSTITUTO MEXICANO DE LA MONEDAD INDUSTRIAL calls it a post-contacted mix. The postcontacted mixture can be allowed to remain in additional contact for a second period of time before being charged to the reactor where the polymerization process will take place.

In accordance with yet another aspect of the present invention, one or more of the hybrid metallocene compounds may be pre-contacted with an olefin monomer and an activator support for a first period of time before this mixture is contacted with the compound of organoaluminum. Once the pre-contacted mixture of the metallocene compound (s), olefin monomer and activator support is contacted with the organoaluminum compound, the composition that further comprises the organoaluminum is called a post-contacted mixture. The postcontacted mixture can be allowed to remain in additional contact for a second period of time before being introduced into the polymerization reactor.

ORGANOALUMINUM COMPOUNDS

In some aspects, the catalyst compositions of the present invention may comprise one or more organoaluminum compounds. These compounds may include, but are not limited to, compounds having the formula:

IMPI MEXICAN INSTITUTE BE LA MONEDAD INDUSTRIAL

<img file="MX360528B_D0085.tif" />

(R1) 3A1;

where R1 can be an aliphatic group having 1 to 10 carbon atoms. For example, R1 can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds that can be used in the catalyst compositions described herein can include, but are not limited to, compounds having the formula:

Al (X5) m (X6) 3-m, where X5 may be a hydrocarbyl; X6 can be an alkoxide or an aryloxide, a halide, or a hydride; and m can be from 1 to 3, inclusive. Hydrocarbyl is used herein to specify a group of hydrocarbon radical and includes, but is not limited to, aryl, alkenyl, cycloalkyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralquinyl, and the like, and includes all substituted, unsubstituted derivatives. , branched, linear and / or substituted heteroatoms thereof.

In one aspect, X5 can be a hydrocarbyl having from about 18 carbon atoms. In another aspect of the present invention, X5 can be an alkyl having 1 to 10 carbon atoms. For example, X5 can be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet another aspect of the present invention.

<img file="MX360528B_D0086.tif" />

In accordance with one aspect of the present invention, X6 can be an alkoxide or an aryloxide, either of which has 1 to 18 carbon atoms, a halide, or a hydride. In another aspect of the present invention, X6 can be independently selected from fluorine or chlorine. Even in another respect, X6 can be chlorine.

In the formula, Al (X5) m (X6) 3-m, m can be a number from 1 to 3, inclusive, and typically, m can be 3. The value of m is not restricted to being an integer; therefore, this formula may include sesquihalide compounds or other organoaluminum compounds as a group.

Examples of the appropriate organoaluminum compounds for use in accordance with the present invention may include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. . Specific non-limiting examples of appropriate organoaluminum compounds may include trimethylaluminum (ΤΜΆ), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA) triisobutylaluminum (TIBA) trin-hexylaluminum, tri-n -octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride and the like or combinations thereof.

<img file="MX360528B_D0087.tif" />

IMPI

The present invention contemplates

INDUSTRIAL a method of pre-contacting a hybrid metallocene compound with an organoaluminum compound and an olefin monomer to form a pre-contacted mixture, prior to contacting this pre-contacted mixture with an activator support to form a catalyst composition. When the catalyst composition is prepared in this manner, typically, but not necessarily, a portion of the organoaluminum compound may be added to the pre-contacted mixture and another portion of the organoaluminum compound may be added to the post-contacted mixture prepared when the mixture Pre-contacted contacts the solid oxide activator support. However, the total organoaluminum compound can be used to prepare the catalyst composition in the pre-contact or post-contact stage. Alternatively, all of the catalyst components can be contacted in one step.

Furthermore, more than one organoaluminum compound can be used in either the pre-contact or post-contact stages. When adding an organoaluminum compound in multiple steps, the amounts of organoaluminum compound described herein include the total amount of organoaluminum compound used in the pre-contacted and post-contacted mixtures, and any

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INDUSTRIAL additional organoaluminum compound added to the polymerization reactor. Therefore, the total amounts of the organoaluminum compounds are described without considering whether an organoaluminum compound or more than one organoaluminum compound is used.

<img file="MX360528B_D0088.tif" />

ALUMINOXANE COMPOUNDS

The present invention further provides a catalyst composition which may comprise an aluminoxane compound. As used herein, the term "aluminoxane" refers to discrete aluminoxane compounds, compositions, mixtures, or species, regardless of how such aluminoxanes are prepared, formed, or otherwise provided. For example, a catalyst composition can be prepared comprising an aluminoxane compound in which the aluminoxane is provided as the poly (hydrocarbyl aluminum 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 may also be referred to as poly (hydrocarbyl aluminum) organoaluminoxane oxides.

contact typically with aluminoxane in a solvent

The other catalyst components can be put into

IMPI • MEXICAN WTITUTO DE LA FROFIEDAD industrial

<img file="MX360528B_D0089.tif" />

saturated hydrocarbon compound, although any solvent that is substantially inert to the reagents, intermediates and products of the activation step can be used. The catalyst composition thus formed can be collected, by any appropriate method, for example, by filtration. Alternatively, the catalyst composition can be introduced into the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminum compound comprising linear structures, cyclic structures or box structures or mixtures of these three. Cyclic aluminoxane compounds having the formula are encompassed by this invention:

wherein R in this formula can be a linear or branched alkyl having 1 to 10 carbon atoms, and p in this formula can be an integer from 3 to 20. The AIRO radical shown herein can also constitute the repeating unit in a linear aluminoxane. Thus, linear aluminoxanes having the formula are also encompassed by this invention:

<img file="MX360528B_D0090.tif" />

A | -o4AI l R

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MEXICAN INSTITUTE M LA MOHEDAL · INDUSTRIAL

<img file="MX360528B_D0091.tif" />

where R in this formula can be a linear or branched alkyl having 1 to 10 carbon atoms, and q in this formula can be an integer from 1 to 50.

Furthermore, the aluminoxanes can have box structures of the formula Rt5r + aRbr-aA14rO3r, where Rt can be a terminal linear or branched alkyl group having 1 to 10 carbon atoms; Rb can be a bridged linear or branched alkyl group having 1 to 10 carbon atoms;

<td>r can</td><td>be 3 or 4; and</td><td>to</td><td colspan="2">can be the same</td><td>a nAl (3)</td><td>- nO (2)</td><td> +</td>

<td>nO (4),</td><td>where nAl</td><td> (3)</td><td colspan="2">It's the number</td><td>of three</td><td>atoms</td><td>of</td>

<td>aluminum</td><td>coordinated,</td><td colspan="4">n0 (2) is the number of two</td><td>atoms</td><td>of</td>

<td>carbon</td><td>coordinated,</td><td>and</td><td>nO (4) is the</td><td colspan="2">number 4</td><td>atoms</td><td>of</td>

<td>oxygen</td><td>coordinated.</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Of</td><td colspan="2">this way, the</td><td>aluminoxanes</td><td>than</td><td colspan="2">can be used</td><td>in</td>

<td colspan="2">the compositions of</td><td colspan="2">catalyst of</td><td>the</td><td>Present</td><td colspan="2">invention</td>

they can be represented, in general, by formulas, such as (R-Al-O) p, R (R-Al-O) qAlR2, and the like. In these formulas, the group R can typically be a linear or branched C1-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of the aluminoxane compounds that can be used in accordance with the present invention may include, but are not limited to

<img file="MX360528B_D0092.tif" />

<img file="MX360528B_D0093.tif" />

INSTITUTO MEXICANO DE LA FRCHEDAD INDUSTRIAL

<img file="MX360528B_D0094.tif" />

methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,

1-pentilaluminoxane,

2pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane and isobutylaluminoxane can be prepared from trimethylaluminum, triethylaluminum, triisobutylaluminum, respectively, and are often referred to as poly (methyl aluminum oxide), ethyl aluminum), and poly (isobutyl aluminum oxide), respectively. It is also within the scope of the invention to use an aluminoxane in trialkylaluminum, as described in combination with one in US Pat.

No. 4,794,096, incorporated herein by reference in its entirety.

The present invention contemplates many values ​​of pyq in the formulas of aluminoxane (R-Al-O) p and R (R-Al-O) qAlR2, respectively. In some respects, p and q may be at least 3. However, depending on how the organoaluminoxane compound is prepared, stored, and used, the value of p and q may vary within a single sample of aluminoxane, and are discussed in present such combinations of organoaluminoxanes.

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<img file="MX360528B_D0095.tif" />

In preparing an aluminoxane-containing catalyst composition, the molar ratio of the total moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of metallocene compound (s) in the composition, in general, can be between approximately 1:10 and approximately 100,000: 1. In another aspect, the molar ratio can be in a range from about 5: 1 to about 15,000: 1. Optionally, the aluminoxane can be added to a polymerization zone in the ranges of from about 0.01 mg / L to about 1000 mg / L, from about 0.1 mg / L to about 100 mg / L, or from about 1 mg / L to about 50 mg / L.

Organoaluminoxanes can be prepared by various procedures. Examples of the preparations are described in US Patent Nos. 3,242,099 and 4,808,561, the disclosures of which are incorporated herein by reference in their entirety. For example, water in an inert organic solvent can be reacted with aluminum alkyl compound, such as (R1) 3A1, to form the desired organoaluminoxane compound. While not intended to be related by this statement, it is believed that this synthesis method can provide a mixture of linear and cyclic R-A1-0 aluminoxane species, which are encompassed by the present invention.

Alternatively, by reacting a like (R1) 3A1, with a

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY organoaluminoxanes can be prepared

<img file="MX360528B_D0096.tif" />

aluminum alkyl compound, such a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.

ORGANOBORO / ORGANOBORATE COMPOUNDS

In accordance with another aspect of the present invention, the catalyst composition may comprise an organoboron or organoborate compound. Such compounds can include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, the fluoroorgano boron and fluoroorgano borate compounds are contemplated.

Any fluoroorgano boron fluoroorgano borate compound can be used with the present invention.

Examples of the fluoroorgano borate compounds that can be used in the present invention may include, but are not limited to, fluorinated aryl borates, such as tetracis (pentafluorophenyl) borate of

N, N-dimethylanilinium ,.

tri-phenylcarbenium, tetracis (pentafluorophenyl) lithium borate, tetracis [3,5de

Triphenylcarbenium N, N-dimethylanilinium, triphecyl [3,5-bis (trifluoromethyl) phenyl] borate, and the like, or mixtures thereof.

Examples of the fluoroorgano boron compounds which can be used as co-catalysts or

IMPI

MEXICAN INSTITUTE OF PROPERTY. ,, INDUSTRIAL activators in the

<img file="MX360528B_D0097.tif" />

Invention may include, but are not limited to, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and the like, or mixtures thereof. Although not intended to be related by theory, these examples of fluoroorgano borate and fluoroorgano boron compounds, and related compounds, are thought to form weakly coordinating anions when combined with hybrid metallocene compounds, as described in US Patent 5, 919, 983, the disclosure of which is incorporated herein by reference in its entirety. Applicants also contemplate the use of diboro, or bisboro, compounds, or other bifunctional compounds containing two or more boron atoms in the chemical structure, as described in J. Am. Chem. Soc., 2005, 127, pp. . 14756-14768, the content of which is incorporated herein by reference in its entirety.

In general, any amount of organoboro compound can be used. In accordance with one aspect of this invention, the molar ratio of the total moles of organoboron or organoborate compound (or compounds) to the total moles of hybrid metallocene compound (or compounds) in the catalyst composition may be in the range from about 0.1: 1 to about 15: 1. Typically the

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY amount of fluoroorgano boron compound ο._Ί Fluorooraan borate used can be from about 0.5 mole to about 10 mole of boron / borate compound per mole of approximately hybrid compound (s). In accordance with another aspect of this invention, the amount of fluoroorgano boron compound or fluoroorgano borate can be from about 0.8 mole to about 5 mole of boron / borate compound per mole of hybrid metallocene compound (s).

IONIZING IONIC COMPOUNDS

The present invention further provides a catalyst composition which may comprise an ionizing ionic compound. An ionizing ionic compound is an ionic compound that can function as an activator or co-catalyst to enhance the activity of the catalyst composition. While not wishing to be related by theory, the ionizing ionic compound is believed to be capable of reacting with a hybrid metallocene compound and converting the metallocene to one or more cationic metallocene compounds, or incipient cationic metallocene compounds. Again, while not wishing to be related by theory, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or partially extracting an anionic ligand,

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MEXICAN INSTITUTE Say THE INDUSTRIAL PROPERTY

<img file="MX360528B_D0098.tif" />

possibly a non-alkadienyl ligand, such as XI or X2, of the hybrid metallocene. However, the ionizing ionic compound can be an activator or co-catalyst regardless of whether it ionizes the hybrid metallocene, subtracts an XI or X2 ligand in a way to form an ion pair, weakens the metal-Xl or metal-X2 bond in the Hybrid metallocene, simply coordinates an XI or X2 ligand or activates the hybrid metallocene compound by some other mechanism.

Furthermore, the ionizing ionic compound need not activate only the hybrid metallocene compound. The activation function of the ionizing ionic compound may be evident in the improved activity of the catalyst composition as a whole, compared to the catalyst composition which does not contain an ionizing ionic compound.

Examples of ionizing ionic compounds may include, but are not limited to, the following compounds:

tri (n-butyl) ammonium dimethylphenyl) borate, tri (n-butyl) ammonium dimethylphenyl) borate, tri (n-butyl) ammonium tetracis [3,5-tri (n-butyl) ammonium, tri (n- butyl) ammonium,

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<img file="MX360528B_D0099.tif" />

N, N-dimethylanilinium tetracis (p-tolyl) borate, tetracis (mde

N, N-dimethylanilinium, N, N-dimethylanilinium, dimethyl.ylphenyl) borate N, N-dimethylanilinium, tetracis [3,5 - de

N, N-dimethylanilinium, tetracis (pentafluorophenyl) borate of

N, N-dimethylanilinium, triphenylcarbenium, tolyl) triphenylcarbenium, dimethylphenyl) triphenylcarbenium borate, dimethylphenyl) triphenylcarbenium, triphenylcarbenium, tetracis (pentafluorophenyl) borate, triphenylcarbenium, tetraphenyl) tropic borate, tetracis [3,5bis (trifluoromethyl) phenyl] tropic borate, tetracis (pentafluorophenyl) tropic borate, lithium tetracis (pentafluorophenyl) borate, lithium tetraphenylborate, tetracis (p-tolyl) lithium borate, tetracis (mlithium, lithium tetracis (3,5-dimethylphenyl) borate, lithium tetrafluoroborate, sodium tetracis (pentafluorophenyl) borate, sodium tetracis (m-tolyl) borate, sodium tetracis (2,484 dimethylphenyl) borate),

<img file="MX360528B_D0100.tif" />

IMPI

ΤΟυΤΟ MEXICANO »1 LA MOHEDAO INDUSTRIAL Tetracis (3,5dimethylphenyl) sodium borate, sodium tetrafluoroborate, potassium tetracis (pentafluorophenyl) potassium borate, potassium tetracis (2,4-dimethylphenyl) potassium borate, potassium , potassium tetrafluoroborate, lithium tetracis (pentafluorophenyl) aluminate, lithium tetraphenylaluminate, lithium tetracis (p-tolyl) aluminate, lithium tetracis (m-tolyl) aluminate, lithium tetracis (2,4dimethylphenyl) aluminate, lithium dimethylphenyl) aluminate, lithium tetrafluoroaluminate, sodium tetracis (pentafluorophenyl) aluminate, sodium tetraphenylaluminate, sodium tetracis (p-tolyl) aluminate, sodium tetracis (m-tolyl) aluminate, tetracis (2,4-dimethylphenyl) sodium aluminate, sodium tetracis (3,5dimethylphenyl) aluminate, sodium tetrafluoroaluminate, potassium tetracis (pentafluorophenyl) aluminate, potassium tetraphenylaluminate, potassium tetracis (p-tolyl) aluminate, tetracis (m-tolyl) potassium aluminate, potassium tetracis (2,4-dimethylphenyl) aluminate, potassium tetracis (3,5-dimethylphenyl) aluminate, potassium tetrafluoroaluminate and the like, or combinations thereof. The ionizing ionic compounds useful in this invention are not limited to these:

other examples of ionizers

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MEXICAN INFO

BE LA MOHEBAB

INDUSTRIAL

<img file="MX360528B_D0101.tif" />

ionic compounds are described in US Patent

Nos. 5,576,259 and

5,807,938, the disclosures of which are hereby incorporated by reference in their entirety.

OLEFINE MONOMERS

Unsaturated reagents that can be used with the catalyst compositions and polymerization processes of this invention can typically include olefin compounds that have from 2 to 30 carbon atoms per molecule, and that have at least one olefinic double bond. This invention encompasses homopolymerization processes using a simple olefin, such as ethylene or propylene, as well as copolymerization, terpolymerization, etc., reactions using an olefin monomer with at least one different olefinic compound. For example, the resulting ethylene copolymers, terpolymers, etc. may generally contain a larger amount of ethylene (&gt; 50 mole percent) and a smaller amount of comonomer (&lt;50 mole percent), although this does not it is a requirement. Comonomers that can be copolymerized with ethylene can often have 3 to 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, internal (a), linear, olefins

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MEXICAN INSTITUTE Dt LA MONEDAD INDUSTRIAL

<img file="MX360528B_D0102.tif" />

Branched, substituted, unsubstituted, functionalized, and non-functionalized can be employed in this invention. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention may include, but are not limited to, ethylene, propylene, 1-butene,

2-butene, 3-methyl-l-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-l-pentene, 4-methyl-l-pentene, 1-hexene, 2hexene, 3-hexene, 3-ethyl- l-hexene, 1-heptene, 2-heptene, 3heptene, the four normal octenes (eg, 1-octene), the four normal nonanes, the five normal decene and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including, but not limited to, cyclopentene, cyclohexene, norbornylene, norborne Canadian, and the like, can also be polymerized as described above. Styrene can also be used as a monomer in the present invention. In one aspect, the olefin monomer can be a C2-C10 olefin; alternatively, the olefin monomer can be ethylene; or alternatively, the olefin monomer can be propylene.

When a copolymer (or alternatively a terpolymer) is desired, the olefin monomer may comprise, for example, ethylene or propylene, which is copolymerized with at least one comonomer. In accordance with one aspect of this invention, the olefin monomer

IMPI

MEXICAN INSTITUTE

OF THE PROPERTY

INDUSTRIAL

<img file="MX360528B_D0103.tif" />

in the polymerization process it may comprise ethylene. In this aspect,

<td>ex emplos</td><td>of the comonomers</td><td>olefin</td><td>appropriate can</td>

<td>include,</td><td>but they are not limited to,</td><td>propylene,</td><td>1-butene, 2-butene,</td>

<td>3-methyl-l</td><td>-butene, isobutylene,</td><td>1-pentene,</td><td>2-pentene, 3-methyl-</td>

<td>1-pentene</td><td>, 4-methyl-l-pentene,</td><td>1-hexene,</td><td>2-hexene, 3-ethyl-l-</td>

<td>hexene 1</td><td>-heptene, 2-heptene,</td><td>3-heptene,</td><td>1-octene, 1-decene,</td>

<td>styrene,</td><td colspan="2">and the like, or combinations</td><td>thereof. Of</td>

In accordance with one aspect of the present invention, the comonomer can comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof.

In general ·, the amount of comonomer introduced into a reactor zone to produce a copolymer can be from about 0.01 to about 50 weight percent of the 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 zone of the reactor can be from about 0.01 to about 40 weight percent, based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into a zone of the reactor can be from about 0.1 to about 35 weight percent of comonomer, based on the total weight of the monomer and comonomer.

Even,

<img file="MX360528B_D0104.tif" />

MEXICAN INSTITUTE OF PROPERTY

INDUSTRIAL

<img file="MX360528B_D0105.tif" />

in another aspect, the amount of comonomer introduced into a reactor zone can be from about 0.5 to about 20 weight percent comonomer, based on total weight of the monomer and comonomer.

While not intended to be related by this theory, when branched, substituted or functionalized olefins are used as reagents, it is believed that a hysterical impedance can impede and / or decrease the polymerization process. Thus, the branched and / or cyclic portion (s) of the olefin removed from the carbon-carbon double bond would not be expected to prevent the reaction in the same way as the same olefin substituents closest to the carbon double bond would. -carbon. In accordance with one aspect of the present invention, at least one monomer / reagent can be ethylene, so that the polymerizations are only a homopolymerization involving ethylene, or copolymerizations with an acyclic, cyclic, internal terminal, linear, branched, substituted or unsubstituted different. Furthermore, the catalyst compositions of this invention can be used in the polymerization of diolefin compounds including, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

<img file="MX360528B_D0106.tif" />

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MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD

<img file="MX360528B_D0107.tif" />

CATALYST COMPOSITIONS

In some aspects, the present invention employs catalyst compositions containing a hybrid metallocene having a ligand containing a heteroatom and an activator, while in other aspects, the present invention employs catalyst compositions containing a hybrid metallocene having a ligand containing a heteroatom and an activator support. These catalyst compositions can be used to produce homopolymer, copolymer and the like polyolefins - for a variety of end use applications.

Hybrid metallocene compounds having formulas (I), (II), (III) and (IV) were described above. In aspects of the present invention, it is contemplated that the catalyst composition may contain more than one hybrid metallocene compound. Furthermore, additional metallocene compounds - different from those with formulas (I), (II), (III) and / or (IV) - can be used in the catalyst composition and / or the polymerization process, with the provided that the additional metallocene compound (s) does not diminish the advantages described herein. Furthermore, more than one activator and / or more than one activator support may also be used.

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MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD

In general, catalyst compositions

<img file="MX360528B_D0108.tif" />

The present invention may comprise a hybrid metallocene compound having the formula (I), (II), (III) and / or activator. In aspects of the invention, the activator may comprise an activator support.

Activator supports useful in the present invention were described above. These catalyst compositions may further comprise an organoaluminum compound or compounds (organoaluminum compounds have also been described above in this manner, a catalyst composition of this invention may comprise a hybrid metallocene compound having the formula (I), (II) , (III) and / or (IV), and an organoaluminum compound. For example, the activating support may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, silica-fluorinated alumina, silica-brominated alumina, silica-brominated alumina, silica-sulphated alumina, Fluorinated Silica-Zirconia, Chlorinated Zirconia Silica, Brominated Silica-Zirconia, Sulfated Silica-Zirconia, Fluorinated Silica-Titania, Fluorinated Silica Coated Alumina, Sulfated Silica Coated Alumina, phosphate silica-coated alumina, the like, or combinations thereof.

Furthermore, the organoaluminum compound can essentially comprise

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MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD

<img file="MX360528B_D0109.tif" />

of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octi1aluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride and the like thereof.

Therefore, a catalyst composition consistent with this invention may comprise (or consist essentially of a hybrid metallocene compound having the formula (I), and / or (IV), sulfated alumina (or silica-triethylaluminum triisobutylaluminum alumina).

In another aspect of the present invention, there is provided a catalyst composition comprising a hybrid metallocene compound having the formula (I), (II), (III) and / or (IV), an activating support and a compound of organoaluminum, wherein this catalyst composition is substantially free of aluminoxane, organoboron or organoborate compounds, ionizing ionic compounds and / or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, substantially free of organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has a catalyst activity, which will be described below,

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0110.tif" />

in the absence of these additional materials. For example, a catalyst composition of the present invention may consist essentially of a metallogen compound having the formula (I), (II), (III) and / or (IV), an activating support and an organoaluminum compound, where no other materials are present in the catalyst composition, which would increase / decrease the activity of the catalyst composition by more than about 10% of the catalyst activity of the catalyst composition in the absence of such materials.

However, in other aspects of this invention, these activators / co-catalysts can be employed. For example, a catalyst composition comprising a hybrid metallocene compound having the formula (I), (II), (III) and / or (IV), and an activating support may further comprise an optional cocatalyst. Suitable co-catalysts in this regard include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, and the like, or any combination thereof. More than one cocatalyst may be present in the catalyst composition.

In a different aspect, a catalyst composition is provided that does not require an activating support. Such a catalyst composition may comprise a hybrid metallocene compound having the formula

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OF THE INDUSTRIAL EROriEDAD (D, (II),

<img file="MX360528B_D0111.tif" />

(III) and / or (IV), and an activator, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound or combinations thereof.

This invention further encompasses methods for making these catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.

The hybrid metallocene compound having the formula (I), (II), (III) and / or (IV) can be pre-contacted with an olefinic monomer if desired, not necessarily the olefin monomer to be polymerized, and an organoaluminum compound for a first period of time before contacting this pre-contacted mixture with an activating support. The first time period for contact, the pre-contact time, between the metallocene compound, the olefin monomer and the organoaluminum compound typically ranges from about a time period of about 1 minute to about 24 hours, for example, from about 3 minutes to approximately 1 hour. Pre-contact times of from about 10 minutes to about 30 minutes are also employed.

Alternatively, the pre-contact process is carried out

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY in multiple stages, instead of a single stage, in which multiple mixtures are prepared, each comprising a different group of catalyst components. For example, at least two catalyst components that form a first mixture are contacted, followed by contact of the first mixture with at least one other catalyst component that forms a second mixture, and so on.

Multiple pre-contact steps can be carried out in a single container or in multiple containers. Furthermore, multiple pre-contact steps may be carried out in series (sequentially), in parallel, or a combination thereof. For example, a first mixture of two catalyst components can be formed in a first container, a second mixture comprising the first mixture plus an additional catalyst component can be formed in the first container or in a second container, which is typically placed downstream of the first container.

In another aspect, one or more of the catalyst components can be divided and used in different pre-contact treatments. For example, part of a catalyst component is fed into a first pre-contact container to pre-contact with at least one other catalyst component, while the rest of this same catalyst component is fed into a second pre-contact container to pre-contact

IMPI MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0112.tif" />

with at least one other catalyst component, or is fed directly into the reactor or a combination thereof. The pre-contact can be carried out on any appropriate equipment, such as tanks, stirred mixing tanks, various static mixing devices, a flask, a container of any type, or combinations of these apparatuses.

In another aspect of this invention, the different catalyst components (eg, a hybrid metallocene compound having formula (I), (II), (III) and / or (IV), activating support, organoaluminum co-catalyst and optionally an unsaturated hydrocarbon) can be contacted in the polymerization reactor simultaneously, while the polymerization reaction is proceeding. Alternatively, any one of two or more of these catalyst components can be pre-contacted in a container prior to entering the reaction zone. This pre-contact stage can be continuous, in which the pre-contacted product is continuously fed to the reactor, or it can be a staged or batch process, in which a batch of pre-contacted product is added to make a composition of catalyst. This pre-contact stage can be carried out for a period of time that can range from a few seconds to as many as several days or more. In this

INSTITUTO MEXICANO DE LA PSOHEDAD INDUSTRIAL aspect, the continuous pre-contact stage generally lasts from about 1 second to about 1 hour. In another aspect, the continuous pre-contact stage lasts from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Once the precontacted mixture of the metallocene compound having formula (I), (II), (III) and / or (IV), the olefin monomer and the organoaluminum co-catalyst are contacted with the support activator, this composition (with the addition of the activator support) is called the post-contacted mixture. Optionally, the post-contacted mixture can remain in contact for a second period of time, the post-contact time, before starting the polymerization process. The pre-contact times between the pre-contacted mixture and the activator support generally range from about 1 minute to about 24 hours. In a further aspect, the post-contact time ranges from about 3 minutes to about 1 hour. The pre-contact stage, the post-contact stage, or both, can increase the productivity of the polymer, compared to the same catalyst composition, which is prepared without pre-contact or post-contact. However, a pre-contact stage and a post-contact stage are not required.

IMPI

<img file="MX360528B_D0113.tif" />

The post-contacted mixture can be heated to a temperature and for a period of time sufficient to allow adsorption, impregnation, or interaction of the pre-contacted mixture and the activator support such that a portion of the components is immobilized, adsorbed, or deposited of the pre-contacted mixture in it. When heating is employed, the post-contacted mixture is generally heated to a temperature of from about -15 ° C to about 7 0 ° C or from about 0 ° C to about 4 0 ° C.

When using a pre-contacted mixture, the molar ratio of the total moles of olefin monomer to the total moles of metallocene (s) in the pre-contacted mixture can typically be from about 1:10 to about 100,000: 1. . The total moles of each component are used in this relationship to represent the aspects of this invention, where more than one olefin monomer and / or more than one metallocene compound is used in a precontact step. Furthermore, this molar ratio may be in a range of about 10: 1 to 1,000: 1 metallocene in another aspect of the invention.

In general, the weight ratio of the organoaluminum compound to the activator support can be in a range from about 10: 1 to about 1: 1000.

IMPI

<img file="MX360528B_D0114.tif" />

If more than one organoaluminum compound and / or more than one activating support is used, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminum compound to the activator support may be in a range of from about 3: 1 to about 1: 100, or from about 1: 1 to about 1:50.

In some aspects of this invention, the weight ratio of the metallocene compound (s) to activator support may be in the range of from about 1: 1 to about 1: 1,000,000. If more than one activating support is used, this ratio is based on the total weight of the activating support. In another aspect, the weight ratio may be in a range of about 1: 5 to about

1: 100,000, or from about 1:10 to about

1:10,000. Even in another aspect, the weight ratio of the metallocene compound (s) to the activator support may be in a range of about 1:20 to about

1:1000.

In general, the catalyst compositions of the present invention have a catalyst activity greater than about 100 grams of polyethylene (homopolymer, copolymer, etc., as the context requires) per gram of activator support per hour (abbreviated g / g / hr). In other

Aspect, the catalyst compositions of this invention can be characterized as having a catalyst activity of greater than about 550, greater than about 650 or greater than about 750 g / g / hr. Even in another aspect, the catalyst activity may be greater than about 1000 g / g / hr. This activity is measured under suspension polymerization conditions using isobutane as the diluent, at a polymerization temperature of approximately 90 ° C and a reactor pressure of approximately 400 psig (2.75 MPa).

In accordance with another aspect of the present invention, the catalyst compositions described herein may have a catalyst activity of greater than about 500 kilograms of polyethylene (homopolymer, copolymer, etc., as the context requires) per mole of metallocene per hour (abbreviated kg / mol / hr). In another aspect, the catalyst activity of the catalyst composition may be greater than about 1000, greater than about 2000, or greater than about 3000 kg / mol / hr. In another aspect, the catalyst compositions of this invention can be characterized as having a catalyst activity of greater than about 5000, greater than about 8000, or greater than about 10,000 kg / mol / hr. Even, in another aspect, the activity of

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0115.tif" />

100 catalyst can be greater than about 15,000 kg / mol / hr. This activity is measured under suspension polymerization conditions using isobutane as the diluent, at a polymerization temperature of approximately 90 ° C and a reactor pressure of approximately

400 psig (2.75 MPa).

As described above, any combination of the metallocene compound having the formula (I), (II), (III) and / or (IV), the activating support, the organoaluminum compound and the olefin monomer, can be precontacted in some aspects of this invention. When pre-contact with an olefinic monomer occurs, the olefin monomer used in the pre-contact step need not be the same as the olefin to be polymerized. Furthermore, when a pre-contact stage is employed between any combination of the catalyst components for a first period of time, this pre-contacted mixture can be used in a subsequent post-contact stage between any other combination of catalyst components for a second period of weather. For example, the metallocene compound, the organoaluminum compound and 1-hexene can be used in a pre-contact step for a first period of time, and this pre-contacted mixture can then be contacted with the

<img file="MX360528B_D0116.tif" />

101 activator support to form a

IMPI

INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL post-contacted mixture that is contacted for a second period of time before starting the polymerization reaction.

For example, the first period of time for contact, the pre-contact time, between any combination of the metallocene compound, the olefin monomer, the activator support and the organoaluminum compound can be from about minute to about hours, from about minutes approximately hour, or approximately minutes approximately minutes.

Optionally, the post-contacted mixture is allowed to remain in contact for a second period of time, the post-contact time, before starting the polymerization process. In accordance with one aspect of this invention, the post-contact times between the pre-contacted mixture and any remaining catalyst components is from about 1 minute to about 24 hours, or from about 5 minutes to about 1 hour.

POLYMERIZATION PROCESS

The catalyst compositions of the present invention can be used to polymerize definites to form homopolymers, copolymers, terpolymers, and the like. One such process to polymerize olefins in the presence of a

<img file="MX360528B_D0117.tif" />

102 The catalyst composition of the present invention may comprise contacting the catalyst composition with an olefin monomer and, optionally, an olefin comonomer (one or more) under polymerization conditions to produce an olefin polymer, wherein the catalyst composition it may comprise a metallocene compound having the formula (I), (II), (III) and / or (IV), and an activator. Metallocene compounds having the formula (I), (II), (III) and / or (IV), were described above.

In accordance with one aspect of the invention, the polymerization process may employ a catalyst composition comprising a hybrid metallocene compound having the formula (I), (II), (III) and / or (IV), and a activator, wherein the activator comprises an activator support. Activator supports useful in the polymerization processes of the present invention were described above. The catalyst composition may further comprise one or more than one organoaluminum compound (s) (the appropriate organoaluminum compounds are also described above). Thus, a process for polymerizing olefins in the presence of a catalyst composition can employ a catalyst composition comprising a hybrid metallocene compound having the formula (I), (II), (III) and / or (IV) , an activating support and a

IMPI (jn MEXICAN INSTITUTE

-¹- ^or Dt THE PROPERTY

INDUSTRIAL organoaluminum compound. In some aspects, the activating support may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, brominated alumina, sulphated alumina, fluorinated silica-alumina, brominated silica-alumina, silica-sulfated alumina, silica -fluorinated zirconia, chlorinated silicon-zirconia, brominated silica-zirconia, sulphated silica-zirconia, fluorinated silica-titanium, fluorinated silica-coated alumina, sulphated silica-coated alumina, phosphated silica-coated alumina, and the like, or combinations thereof. In some respects, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-nhexylaluminum, tri-n-octylaluminum, hydride of diisobutylaluminum, diethylaluminum ethoxide, diethylaluminum chloride and the like, or combinations thereof.

In accordance with another aspect of the invention, the polymerization process may employ a catalyst composition comprising a hybrid metallocene compound having the formula (I), (II), (III) and / or (IV), and a activator, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound or combinations thereof. The

<img file="MX360528B_D0118.tif" />

104 catalyst compositions of

<img file="MX360528B_D0119.tif" />

IMPI

MEXICAN INSTITUTE MIA PROPERTY

INDUSTRIAL The present invention is intended for any olefin polymerization method using various types of polymerization reactors.

As used herein, polymerization reactor includes any polymerization reactor capable of polymerizing monomers olefin comonomers (one more than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like. Different types of reactors include what may be referred to as a batch reactor, suspension reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations thereof. Polymerization conditions for different types of reactors are well known to those skilled in the art.

The gas phase reactors can comprise fluidized bed reactors or horizontal phased reactors.

Suspension reactors can comprise vertical or horizontal circuits. High pressure reactors can comprise autoclave or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes could use continuous or intermittent product download. Processes may also include partial or total direct recirculation of the unreacted monomer, unreacted comonomer and / or diluent.

105

Reactor systems

IMPI

MEXICAN INSTITUTE OF LA MONEDAD. . INDUSTRIAL · polymerization

<img file="MX360528B_D0120.tif" />

The present invention may comprise one type of reactor in a system or multiple reactors of the same or different type. Polymer production in multiple reactors can include multiple steps in at least two separate polymerization reactors interconnected by a transfer device that makes it possible to transfer the polymers resulting from the first polymerization reactor into the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors can include manual transfer of polymer from one reactor to subsequent reactors for continuous polymerization. Multiple reactor systems can include any combination including, but not limited to, multiple circuit reactors, multiple gas phase reactors, a combination of circuit and gas phase reactors, multiple high pressure reactors, or a combination of high pressure reactors with circuit and / or in gas phase. Multiple reactors can be operated in series, in parallel, or both.

In accordance with one aspect of the invention, the polymerization reactor system may comprise at least

106

ΙΜΡΙ

XSTTTUTO MEXICANO DB LA FROMF.DAD INDUSTRIAL

<img file="MX360528B_D0121.tif" />

a circuit suspension reactor comprising vertical or horizontal circuits. Monomer, diluent, catalyst and comonomer can be continuously fed into a loop reactor, where polymerization is carried out. In general, continuous processes may comprise the continuous introduction of monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of a suspension comprising polymer particles and the diluent from this reactor. The effluent from the reactor can be expanded to remove the solid polymer from the liquids comprising the diluent, monomer and / or comonomer. Different technologies can be used for this separation stage, including, but not limited to, expansion which can include any combination of heat addition and pressure reduction; separation by cyclonic action in any cyclone or hydrocyclone; or separation by centrifugation.

A typical suspension polymerization process (also known as the particle formation process) is described, for example, in US Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415, each of which incorporated herein by reference in its entirety.

The appropriate diluents used in the polymerization in

<img file="MX360528B_D0122.tif" />

suspension include,

107 but they are not limited

IMPI

MEXICAN INSTITUTE »AND THE PROPERTY

INDUSTRY), ______ a, the monomer that polymerizes and the hydrocarbons that are liquid under reaction conditions. Examples of appropriate diluents include, but are not limited to, hydrocarbons, such as propane, cyclohexane, isobutane, n-butane, n pentane, isopentane, neopentane, and n-hexane. Some circuit polymerization reactions can occur under volumetric conditions where no diluent is used. An example is the polymerization of the propylene monomer, as described in US Patent No. 5, 455,314, which is incorporated by reference in its entirety.

In accordance with another aspect of the present invention, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recirculating stream containing one or more monomers continuously recirculated through a fluidized bed in the presence of the catalyst under polymerization conditions. A recirculation stream can be withdrawn from the fluidized bed and recirculated back into the reactor. Simultaneously, the polymeric product can be removed from the reactor and fresh or new monomer can be added to replace the polymerized monomer. These gas phase reactors may comprise a process for the multi-stage gas phase polymerization of olefins, in

108

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY in which olefins polymerize in the gas phase in at least two independent gas phase polymerization zones, while feeding a polymer containing a catalyst formed in a first polymerization zone to a second zone polymerization. One type of gas phase reactor is described in US Patent Nos. 5,352,749, 4,588,790 and 5,436,304, each of which is incorporated herein by reference in its entirety.

In accordance with yet another aspect of the invention, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones, where fresh monomer, initiators or catalysts are added. The monomer can be entrained in a stream of inert gas and introduced into an area of ​​the reactor. Initiators, catalysts, and / or catalyst components can be entrained in a gas stream and introduced into another zone of the reactor. The gas streams can be intermixed for polymerization. Heat can be used

<td colspan="2">and pressure</td><td>properly</td><td>to get the</td><td>terms</td><td>of</td>

<td>reaction</td><td>of</td><td>polymerization</td><td>optimal.</td><td></td><td></td>

<td>Of</td><td colspan="2">according to still ·</td><td>another aspect of the</td><td>invention,</td><td>the</td>

<td>reactor</td><td>of</td><td>polymerization</td><td>can understand</td><td>a reactor</td><td>of</td>

solution polymerization, where the monomer / comonomer

109

IMPI

MEXICAN INSTITUTE

OF THE PROPERTY

INDUSTRIAL

<img file="MX360528B_D0123.tif" />

They are contacted with the catalyst composition by appropriate stirring or other means. A vehicle comprising an inert organic diluent or excess monomer can be used. If desired, the monomer / comonomer can be contacted in the vapor phase with the production of the catalytic reaction, in the presence or absence of a liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Agitation can be used to obtain better temperature control and maintain uniform polymerization mixtures at

<td>through</td><td>the</td><td>Zone of</td><td>polymerization. I know</td><td>they use media</td><td>suitable</td>

<td colspan="2">to dispel</td><td>the heat</td><td>polymerization</td><td>exothermic.</td><td></td>

<td>The</td><td colspan="2">reactors</td><td>polymerization</td><td>appropriate</td><td>for the</td>

<td>Present</td><td colspan="2">invention</td><td>they can also</td><td>understand</td><td>any</td>

combination of at least one feedstock feed system, at least one feed system for the catalyst or catalyst components and / or at least one polymer recovery system. Reactor systems suitable for the present invention may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recirculation, storage, discharge,

IMPI

one n MEXICAN INSTITUTE

-L J- C OE LA MONEDAD

INDUSTRIAL laboratory analysis and process control.

The polymerization conditions that are controlled for efficiency and to provide the desired polymer properties can include temperature, pressure, and the concentrations of the different reagents. The polymerization temperature can affect the productivity of the catalyst, the molecular weight of the polymer, and the molecular weight distribution. An appropriate polymerization temperature can be any temperature less than the de-polymerization temperature according to the Gibbs free energy equation. Typically, this includes from about 60 ° C to about 280 ° C, for example, or from about 60 ° C to about 110 ° C, depending on the type of polymerization reactor. In some reactor systems, the overall polymerization temperature is within about 7 0 ° C to about 90 ° C, or from about 75 ° C to about 85 ° C.

The appropriate pressures will also vary according to the reactor and the type of polymerization. The pressure for liquid phase polymerizations in a loop reactor is typically less than 1000 psig (6.9 MPa). The pressure for the gas phase polymerization is usually approximately 200 to 500 psig (1.4 to 3.4 MPa). In general, high pressure polymerization in tubular or

<img file="MX360528B_D0124.tif" />

111 autoclave it

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD

<img file="MX360528B_D0125.tif" />

it runs at approximately 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also be operated in a supercritical region that occurs at generally higher temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) may offer advantages.

Aspects of this invention relate to defined polymerization processes which comprise contacting a catalyst composition with a define monomer and optionally, an olefin monomer under polymerization conditions to produce a define polymer. The olefin polymer produced by the process may have less than about 0.002 long chain branches per 1000 total carbon atoms, and / or a ratio of Mw / Mn in a range of about 3 to about 20, and / or a ratio of vinyl end groups to saturated end groups in a range of about 0.4 to about 0.9. In addition, or alternatively, the olefin polymer may have a melt index of less than 2.5, and / or an Mn in a range of from about 15,000 to about 50,000, and / or a Mw in a range of about 100,000 to about

300,000, and / or one Mz in an interval of approximately 750,000

112

<img file="MX360528B_D0126.tif" />

IMPI

MEXICAN INSTITUTE

OE PROPERTY __ to approximately 3,500,000, and / or an Mw / Mn in ¿Tn ^ irítervalo ^ of approximately 5 to approximately id, and / or less than approximately 0.001 long chain branches per 1000 total carbon atoms.

Aspects of this invention also relate to olefin polymerization processes carried out in the absence of added hydrogen. In this description, added hydrogen will be represented as the ratio of hydrogen feed to define monomer entering the reactor (in units of ppm). An olefin polymerization process of this invention may comprise contacting a catalyst composition with a define monomer and, optionally, an olefin comonomer, under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a hybrid metallocene compound and an activator, where the polymerization process is carried out in the absence of added hydrogen. As described above, the hybrid metallocene can have formula (I), formula (II), formula (III) and / or formula (IV). As one of skill in the art will recognize, hydrogen can be generated in situ by metallocene catalyst compositions in various olefin polymerization processes, and the amount generated can vary depending on the catalyst composition.

113

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0127.tif" />

specifies and mstalorgno compound (s) ρτηηΊ gave birth. αΊ type of polymerization process used, the conditions of the polymerization reaction used, etc.

In other aspects, it may be desirable to carry out the polymerization process in the presence of a certain amount of added hydrogen. Therefore, an olefin polymerization process of the present invention may comprise contacting a catalyst composition with an olefin monomer and, optionally, an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the Catalyst composition comprises a hybrid metallocene compound and an activator, wherein the polymerization process is carried out in the presence of added hydrogen. For example, the ratio of hydrogen to olefin monomer in the polymerization process can be controlled, often the ratio of hydrogen feed to olefin monomer entering the reactor.

The ratio of hydrogen added to the olefin monomer in the process can be controlled to a weight ratio that falls within a range of about

PPm at about 1500 ppm, from about 1000 ppm, or from about 100 ppm to about 750 ppm.

In some aspects of the present invention, the

114

<img file="MX360528B_D0128.tif" />

IMPI

INSTITUTO MEXICANO DE LA MONEDAD INDUSTRIAL feed or ratio of hydrogen reagent to olefin monomer, can be kept substantially constant during the polymerization run for a particular degree of polymer. That is, the hydrogen: olefin monomer ratio can be selected at a particular ratio within a range of from about ppm to about 1000 ppm or more, and kept at the ratio of about ± 25% during the polymerization run. For example, if the objective relationship is

100 ppm, then keeping the hydrogen: olefin monomer ratio substantially constant would cause maintaining the feed ratio between about 75 ppm and about 125 ppm. Furthermore, the addition of comonomer (or comonomers) can be, and generally is, substantially constant throughout the polymerization run for a particular polymer grade.

However, in other aspects, it is contemplated that the monomer, comonomer (or comonomers) and / or hydrogen may be periodically pulsed into the reactor, eg, in a manner similar to that employed in the patent.

US No. 5,739,220 and Patent Publication

US No.

2004/0059070, the descriptions of which are incorporated by reference herein in their entirety.

The concentration of the reagents entering the reactor

<img file="MX360528B_D0129.tif" />

115 polymerization can be controlled

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY to produce constant physical and mechanical properties. The proposed end use product to be formed by the polymeric resin and the method of forming such a product can ultimately determine the desired properties and attributes of the polymer. Mechanical properties include stress, flex, impact, tear, stress relaxation, and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, fracture growth, long chain branching, and rheological measurements.

This invention also relates to, and encompasses, the polymers produced by any of the polymerization processes described herein. Articles of manufacture may be formed from, and / or may comprise, the polymers produced in accordance with this invention.

POLYMERS AND ARTICLES

If the resulting polymer produced according to the present invention is, for example, an ethylene polymer or copolymer, its properties can be characterized by various analytical techniques known and used in the industry of

<img file="MX360528B_D0130.tif" />

_n6 IMPI

J- o INSTITUTO MEXICANO BtLA PROPIEDAD

INDUSTRIAL polyolefins. Articles of manufacture may be formed from, and / or may comprise, the ethylene polymers of this invention, the typical properties of which are provided below.

In general, the ethylene polymers (copolymers, terpolymers, etc.) produced in accordance with this invention can have a melt index of 0 to about 100 g / 10 minutes. Melt indices in the range of 0 to about 7 5 g / 10 min, 0 to about 50 g / 10 min, or 0 to about 30 g / 10 min are contemplated in some aspects of this invention. For example, a polymer of the present invention may have a melt index (MI) in a range of 0 to about 25, 0 to about 10, 0 to about 5, 0 to about 2, or 0 to about 1 g / 10 min.

Ethylene polymers produced in accordance with this invention may have an HLMI / MI ratio of greater than about 25, such as, for example, greater than approximately 30, greater than approximately 40, or greater than approximately 50. The ranges contemplated for HLMI / MI include, but are not limited to, from about 50 to about 5000, from about 50 to about 4000, from about 50 to about 3000, from about 75 to about 3000, or from

117 about 75 to about 2750.

IMPI

MEXICAN INSTITUTE OE INDUSTRIAL PROPERTY

<img file="MX360528B_D0131.tif" />

The density of the ethylene-based polymers produced using one or more hybrid metallocene compounds of the present invention can typically fall within the range of about 0.88 to about 0.97 g / cc. In one aspect of this invention, the density of the polymer can be in a range of about 0.90 to about 0.97 g / cc. Even, in another aspect, in general, the density can be in a range of about 0.91 to about 0.96 g / cc.

Ethylene polymers, such as copolymers and terpolymers, within the scope of the present invention, in general, can have a polydispersity index - a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) - in a range from about 3 to about 20. In some aspects described herein, the Mw / Mn ratio may be in a range of from about 3.5 to about 20, from about 4 to about 20, from about 4 to about 18, from about 5 to about

18, from about 5 to about 16, from about 5 to about 14, from about 6 to about 14, or from about 6 to about 13.

118

The relationship of

Mz / Mw for

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0132.tif" />

the polymers of this invention can often be in the range of about 3 to about 20. Mz is the average molecular weight z. According to one aspect, the Mz / Mw of the ethylene polymers of this invention can be in a range of from about 3.5 to about 20, from about 4 to about 20, from about 6 to about 20, from about 6 to about 18 or from about 6 to about 16.

In general, the olefin polymers of the present invention have low levels of long chain branching, typically with less than 0.01 long chain branching (LCB's) per 1000 total carbon atoms. In some respects, the number of LCB's per 1,000 total carbon atoms may be less than about 0.008, or less than about 0.005. Furthermore, the olefin polymers of the present invention (for example, ethylene polymers) can have less than about 0.004, less than about 0.003, less than about 0.002, or less than about 0.001 LCB's per 1000 total carbon atoms, in other aspects of this invention.

Ethylene polymers can have a ratio of vinyl end groups to saturated end groups that generally falls within a range of about

119

IMPI

MEXICAN INSTITUTE

DS INDUSTRIAL PROPERTY

<img file="MX360528B_D0133.tif" />

0.4 to about 0.9. In some respects, this ratio of vinyl groups to saturated end groups can be in the range of about 0.5 to about 0.9, from about 0.6 to about 0.9, or from about 0.65 to about 0.85.

The ethylene polymers described herein can have less than about 0.002 long chain branches per 1000 total carbon atoms, and / or a ratio of Mw / Mn in a range of about 3 to about 20, and / or a ratio of vinyl end groups to saturated end groups in a range of about 0.4 (or about 0.6) to about 0.9, and / or a melt index of less than 2.5, and / or a Mn in a range of about 15,000 to about 50,000, and / or a Mw in a range of about 100,000 to about 300,000, and / or a Mz in a range of about 750,000 to about 3,500,000. Furthermore, some polymers can have an Mw / Mn in a range of from about 5 to about 15, and / or less than about 0.001 long chain branches per 1000 total carbon atoms.

Ethylene polymers, whether homopolymers, copolymers, terpolymers, etc., can be formed into various articles of manufacture. Items that can

<img file="MX360528B_D0134.tif" />

IMPI

9 n MEXICAN INSTITUTE

OF INDUSTRIAL PROPERTY comprising polymers of this invention include, but are not limited to, an agricultural film, an automotive part, a bottle, a drum, a fiber or cloth, a film for packaging food or containers, a food service article , a fuel tank, a geomembrane, a household container, a coating, a molded product, a medical device or material, a pipe, a film tape, a toy, and the like.

Various processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, coating extrusion, profile extrusion, thermoforming, and the like.

Furthermore, modifying additives are often added to these polymers to provide beneficial polymer processing or end-use product attributes. These processes and materials are described in Modera Plastics Encyclopedia, Mid-November 1995 Issue, Vol. 72, No. 12; and Film Extrusion Manual - Piocess, Materials, Properties, TAPPI Press, 1992; the descriptions of which are incorporated herein by reference in their entirety.

Applicants also contemplate a method of forming or preparing an article of manufacture comprising a polymer produced by any of the processes of

121 Present. For example, contacting an olefin monomer and,

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0135.tif" />

Polymerization described in the method may comprise: (i) catalyst composition with optionally, an olefin comonomer (one or more) under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise a metallocene compound which it has the formula (I), (II), (III) and / or (IV), and an activator (for example, an activating support); and (ii) forming an article of manufacture comprising the olefin polymer. The forming step may comprise mixing, melting processing, extrusion, molding or thermoforming, and the like, including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, which are not to be construed in any way as limitations imposed on the scope of this invention. The different aspects, modalities, modifications and equivalents thereof, after reading the description of the present, could suggest to a person skilled in the art without departing from the spirit of the present invention or the scope of the appended claims.

Figure 1 presents the structures and corresponding abbreviations for the

122 composed of

IMPI MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0136.tif" />

Hybrid metallocene described in the following examples. Synthesis of the hybrid metallocene compounds was performed under a purified nitrogen atmosphere using standard Schlenk's line or glove 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 alumina. All solvents were degassed and stored under nitrogen. MET-A (q5-cyclopentadienyl titanium tetrachloride), MET-B (q5-pentamethylcyclopentadienyl titanium trichloride), and all organic ligands were purchased from Aldrich Chemical Company. The products were analyzed by 1H NMR (300 MHz, C6D6, with reference against the residual C6D6 peak at 7.15 ppm).

Three general synthesis procedures were used. In general procedure 1, an equivalent of LiORA was added in one portion to a toluene solution of CpTiC13 (or Cp * TiC13) in a glove box at room temperature (approximately 22-25 ° C). The reaction mixture was stirred at 50 ° C overnight (approximately 12-16 hours). After the white solid (LiCl) was removed by centrifugation or by filtration, the solvent was removed in vacuo, resulting in a red or orange solid. The solid was recrystallized from

123

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solvent mixture of heptane and toluene to produce crystals of the respective hybrid titanium compound. In general procedure 2, a slight excess of NEt3 in THF (or diethyl ether) was added dropwise to a solution of THF (or diethyl ether) of CpTiC13 (or Cp * TiC13) and an equivalent of HOUR. The resulting suspension was stirred overnight at room temperature. After the white solid was removed (NEt3'HCl) by centrifugation or by filtration, the solvent was removed in vacuo, resulting in a red or orange solid. The solid was recrystallized from a mixture of heptane and toluene solvent to produce crystals of the respective hybrid titanium compound. In general procedure 3, one equivalent of HOUR in toluene was added to a toluene solution of CpTiC13, in a glove box at room temperature. The reaction mixture was stirred overnight at 90 ° C. The solvent was removed in vacuo, resulting in an orange solid. The solid was recrystallized from a mixture of heptane and toluene solvent to produce crystals of the respective hybrid titanium compounds. Synthesis schemes analogous to these three general synthesis procedures can be employed to produce hybrid zirconium or hybrid hafnium compounds (eg, using CpZrC13 or

CpHfC13).

124

ΙΜΡΙ nSTtTUTO MEXICANO

DB LA MONEDAD

INDUSTRIAL

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MET-D, MET-E, and MET-F were produced according to one of these general synthesis procedures. The synthesis procedures for MET-C, MET-H, MET-I, MET-J, and MET-K are described in more detail in the examples that follow. MET-G was prepared in a similar manner to that of MET-H, but triphenylsilanol was used instead of 1,1,3-triphenyl-2-propin-l-ol.

In general, the polymerization experiments were carried out as follows. Polymerizations were carried out for one hour in a one gallon (3,788 L) stainless steel autoclave reactor containing two liters of isobutane as diluent, and added hydrogen from a 325 cc auxiliary vessel. The detail P for hydrogen refers to the pressure drop in the auxiliary vessel from a starting pressure of 600 psig (4.1 MPa). Hybrid metallocene solutions (1 mg / mL) were prepared by dissolving 20 mg of the respective metallocene in 20 mL of toluene. Under an isobutane purge, a solution of triisobutylaluminum (TIBA) (25% in heptanes) was charged to a cold reactor, followed by the solution of hybrid metallocene and sulfated alumina in toluene. The reactor was closed and 2 L of isobutane were added. The reactor was heated to within about 5 degrees of the target run temperature, and the ethylene feed was opened. Ethylene was fed on demand to maintain reactor pressure

IMPI

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125 objective. The reactor was maintained at the desired run temperature through the run by an automated heating-cooling system. Hydrogen was then introduced into the reactor during the polymerization process.

hexene with the

For hourly charge, the dry reactor was vented.

The copolymerization agreement, expanded initial ethylene. At the isobutane and ethylene termination of the reactor,

1a the was opened and the melt index product (MI, of the polymer was g / 10 min) was collected and determined with ASTM D1238 condition F at 190 ° C with a weight

2,160 grams.

The high load melt index (HLMI, g / 10 min) determined according to ASTM D1238 condition a weight of 21,600 grams.

The density of the polymer was determined by centimeter compression, conditioned by cooling with cubic se

E at 190 ° C in grams with per (g / cc) in a molded sample at about 15 ° C per hour, and is about hours at room temperature according to ASTM

D1505 and ASTM D1928, procedure C.

Molecular weights and molecular weight distributions were obtained using a PL 220 SEC (Polymer Laboratories) high temperature chromatography unit with

126

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

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trichlorobenzene (TCB) as the solvent, with a flow rate of 1 mL / minute at a temperature of 145 ° C. BHT (2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g / L was used as a stabilizer in TCB. An injection volume of

200 pL with a nominal polymer concentration of 1.5 mg / mL.

Dissolution of the sample in stabilized TCB was carried out by heating at 150 ° C for hours with moderate, occasional stirring. The columns used were three PLgel Mixed A LS columns (7.8x300 mm) and were calibrated with a wide linear polyethylene standard (Phillips Marlex® BHB 5003) for which

<td>had determined the</td><td>molecular weight.</td><td>In</td><td>the examples</td><td>than</td>

<td>continue, Mn is the weight</td><td colspan="3">molecular number average; Mw is</td><td>the</td>

<td>average molecular weight</td><td>or weight and Mz</td><td>is</td><td colspan="2">the molecular weight</td>

<td>average z.</td><td></td><td></td><td></td><td></td>

<td>SEC-MALS combines</td><td>the methods of</td><td>the</td><td>chromatography</td><td>of</td>

<td colspan="2">size exclusion (SEC) with detection</td><td>of</td><td>dispersion of</td><td>light</td>

multi-angle (MALS). An 18 angle DAWN EOS light scattering photometer (Wyatt Technology, Santa Barbara, CA) was attached to a PL-210 SEC system (Polymer Labs, UK) or a Waters 150 CV Plus system (Milford, ΜΆ) by a hot transfer line, thermally controlled at the same temperature as the SEC columns and its differential refractive index (DRI) detector (145 ° C). To one

127

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MEXICAN INSTITUTE • E LA MONEDAD INDUSTRIAL

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adjusted flow rate of 0.7 mL / min, the mobile phase,

1,2,4-Trichlorobenzene (TCB), eluted through three 7.5mm x 300mm columns, 20 pm Mixed A-LS (Polymer Labs).

Polyethylene (PE) solutions with concentrations of ~ 1.2 mg / mL, depending on samples, were prepared at 150 ° C for 4 h before being transferred to SEC injection vials, which are seated in a carousel heated to 145 ° C. For higher molecular weight polymers, longer heating times were necessary to obtain real homogeneous solutions. In addition to acquiring a concentration chromatogram, seventeen light scattering chromatograms at different angles were also acquired for each injection using Wyatt's Astra® software. At each chromatographic slice, the absolute molecular weight (M) and the radius of the mean square root (RMS), also known as the radius of gyration (Rg), were obtained from an interception and slope of the Debye graph, respectively. The methods of this process are detailed in Wyatt, PJ, Anal. Chim. Acta, 272, 1 (1993), which is incorporated herein by reference in its entirety.

The Zimm-Stockmayer method was used to determine the amount of LCB. Since SEC-MALS measures M and Rg on each slice of a chromatogram simultaneously, the branching indices, gM, as a function of M, could be determined

128 in each cut, the average square linear Rg, in the

IMPI MEXICAN INSTITUTE BE THE INDUSTRIAL PROPERTY

<img file="MX360528B_D0142.tif" />

directly determining the ratio of the of the branched molecules to the same M, as shown in the equation (the subscripts br and lin represent branched and linear, respectively).

(r \²\ 8 / lin of the following polymers

At a given gM, the weight average number of LCB per molecule (B3w) was computed using the ZimmStockmayer equation, shown in the following equation, where the ramifications are assumed to be trifunctional or in shape.

AND.

ln

LCB frequency (LCBMi), the number of LCB per 1000

C, from section ith afterwards was actually computed using the

LCBMi

000 * 14 * B3w / Mi.

In this way, the LCB distribution (LCBD) through the molecular weight distribution (MWD) was established for a total polymer.

Example 1

Synthesis of butyl-4-methylphenoxy) titanium dichloride, MET-C of p5-cyclopentadienyl (2,6-di-ter129

MET-C was prepared as follows

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MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD

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Approximately 50 mL of toluene (~ 35oC) was added to a flask with a mixture of

0.97 grams (4.42 mmol) of q5-cyclopentadienyl titanium trichloride (MET-A) and 1 gram (4.42 mmol) of the lithium salt of 2,6-di-tert-butyl-4-methylphenol. The mixture was stirred at room temperature for 1-3 days. After the solid LiCl was removed by centrifugation, and the toluene was removed in vacuo, the resulting product was recrystallized from a mixture of toluene solvent and heptane. Approximately 1.39 g of MET-C was produced; the yield was 75%.

Example 2

Synthesis of r¡5-cyclopentadienyl (1,1,3-triphenyl2-propinoxy) titanium dichloride, MET-H

MET-H was prepared as follows. Approximately 1.1 g (5 mmol) of g5-cyclopentadienyl titanium trichloride (MET-A) was dissolved in 30 mL of diethyl ether, and the solution was cooled to -30 to -70 ° C. A mixture of 1.42 grams (5 mmol) of 1,1,3-triphenyl-2-propin-l-ol and 0.8 mL of dry Et3N in 30 mL of diethyl ether was added over 30 minutes. The reaction mixture was stirred at room temperature overnight. A white solid was removed by centrifugation. A light orange solid was obtained, then the diethyl ether was removed in vacuo. The resulting product was recrystallized from toluene. Approximately 1.75 g of MET-H was produced; performance

IMPI INSTITUI C MEXICANO MLArWmiDMJ INDUSTRIAL

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it was 80%. Figure 2 illustrates the 1H-NMR analysis of the MET-H product.

Example 3

Synthesis of q5-cyclopentadienyl (2,6-dimethoxyphenoxy) titanium dichloride, MET-I

MET-I was prepared as follows. Approximately 0.5 grams (2.28 mmol) of η5-cyclopentadienyl titanium trichloride (MET-A) and 0.35 grams (2.28 mmol) of 2,6'-dimethoxyphenol were mixed in a cold toluene solvent (~ 0 ° C). After the reaction mixture was stirred at room temperature for 30 minutes, the temperature was raised to 90 ° C and stirred overnight. The dark red solid was obtained, then the toluene was removed in vacuo. The product was recrystallized from toluene. Approximately 0.67 g of MET-I was produced; the yield was 91%.

Example 4

Synthesis of p5-cyclopentadienyl (6-allyl-2methoxyphenoxy) titanium dichloride, MET-J

MET-J was prepared as follows. A solution of 1.5 g (9.1 mmol) of 2-allyl-6-methoxyphenol in toluene was slowly added to a solution of 2 g (9.1 mmol) of q5-cyclopentadienyl titanium trichloride (MET-A) in toluene at room temperature. Then the reaction mixture was stirred at

131 room temperature for 1 hour, increased to 90 ° C and stirred during the orange solid, then the product toluene was recrystallized from about 2.84 g of MET-J;

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<img file="MX360528B_D0145.tif" />

night temperature. Vacuum stirring was obtained. Toluene. The yield was produced was 90%.

Figure 3 illustrates the analysis of

1H-NMR of the MET-J product.

Example 5

Synthesis of pS-pentamethylcyclopentadienyl (2alyl-6-methylphenox.i) titanium dichloride, MET-K

MET-K was prepared as follows. A solution of 1 g (6.9 mmol) of 2-allyl-6-methylphenol in toluene was slowly added to a solution of 2 g (6.9 mmol) of g5-pentamethylcyclopentadienyl titanium trichloride (MET-B) in toluene at room temperature. After the reaction mixture was stirred at room temperature for 1 hour, the temperature was raised to 90 ° C and stirred overnight. A red solid was obtained, then toluene was removed in vacuo. The product was recrystallized from heptane. Approximately 2.2 g of MET-K were produced; the yield was 80%. Figure 4 illustrates the 1H-NMR analysis of the MET-K product.

Example 6

Preparation of activating supports for sulfated alumina

Sulfated alumina activator supports were prepared as follows. Bohemite was obtained from WR Grace

Company under the designation

132

Alumina

IMPI Mexican institute OF LA MONEDAD

INDUSTRIAL

So what

<img file="MX360528B_D0146.tif" />

surface area of ​​approximately 300 m2 / g and a pore volume of approximately 1.3 mL / g. This material was obtained as a powder having an average particle size of approximately 100 microns. This material was impregnated at incipient humidity with an aqueous solution of ammonium sulfate to be equal to approximately 15% sulfate. This mixture was then placed on a flat tray and allowed to vacuum dry at approximately 110 ° C for approximately 16 hours.

Alumina A, from WR Grace Company, was impregnated at incipient humidity with an aqueous solution of 0.08 g of ammonium sulfate per mL of water. The alumina had a surface area of ​​approximately 330 m2 / g and a pore volume of approximately 1.3 mL / gram. The amount of ammonium sulfate used was equal to 20% of the starting alumina, by weight. The resulting mixture was dried in a vacuum oven overnight at 120 ° C, and then sieved through a 35 mesh screen. To calcine the resulting powdered mixture, the material was fluidized in a stream of dry air at 550 ° C for 6 hours. After this, the sulfated alumina was collected and stored under dry nitrogen, and used without exposure to the atmosphere. This sulfated alumina was used as the activating support in Examples 7-61.

<img file="MX360528B_D0147.tif" />

133

Examples 7-61

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Ββτττντο MUBCANC BE LA MOMEBAO INDUSTRIAL

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Polymerization experiments using hybrid metallocenes and sulfated alumina

Table 1 summarizes some polymerization reaction conditions and polymer properties for Examples 7-61. The catalyst activities listed are in kilograms of polymer per mol of hybrid metallocene per hour (kg of polymer / mol of Ti / hr).

A representative polymerization with MET-D and sulfated alumina was carried out as follows. Approximately 2 mg of MET-D in 2 mL of toluene was mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glass tube under nitrogen. After approximately one minute, this suspension was added to the reactor at less than 40 ° C. The reactor was sealed and 2 L of isobutane were added and the contents were stirred at 700 rpm. As the reactor temperature approached 85 ° C, the addition of ethylene was started, and the set point of 90 ° C was quickly obtained. The reactor was kept at 90 ° C for 60 min. The yield was 23,363 kg of polymer / mol of Ti / h. See example 10 in Table 1.

Representative polymerization with MET-E and sulfated alumina was performed as follows. Approximately 2 mg of MET-E in 2 mL of toluene was mixed with 300 mg of sulfated alumina in 2 mL of toluene in a low glass tube

134 nitrogen.

After suspension it was added to the sealed and added

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX360528B_D0149.tif" />

approximately one minute, this reactor at less than 40 ° C. The reactor

L of isobutane and the contents were stirred at about 700 rpm. As the reactor temperature becomes

85 ° C, the addition of ethylene was started, and the 90 ° C set point was quickly obtained. The reactor was kept at 90 ° C for 60 minutes. The yield was 27,776 kg of polymer / mol of Ti / h. See 14 in Table 1.

Representative polymerization was carried out with

MET-I and sulfated alumina. Approximately 2 mg of MET-I in 2 mL of toluene was mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glass tube under nitrogen. After approximately one minute, this suspension was added to the reactor at less than 40 ° C. The reactor was sealed and 2 L of isobutane were added and the contents were stirred at 700 rpm.

As the reactor temperature approached 85 ° C, the addition of ethylene was started, and the 90 ° C set point was quickly obtained. The reactor was kept at 90 ° C for minutes. The yield was 8,315 kg of polymer / mol of Ti / h. See Example 26 in Table 1.

A representative polymerization with MET-J and sulfated alumina was carried out as follows. Approximately 2 mg of MET-J in 2 mL of toluene was mixed with 300 mg of sulfated alumina in 2 mL of toluene in a low glass tube

<img file="MX360528B_D0150.tif" />

IMPI

MEXICAN INSTITUTE. _r PROPERTY 135 industrial nitrogen. After approximately ήπ. nánutn, for suspension was added to the reactor at less than 40 ° C. The reactor was sealed and 2 L of isobutane were added and the contents were stirred at 700 rpm. As the reactor temperature approached 85 ° C, the addition of ethylene was started, and the set point of 90 ° C was quickly reached. The reactor was kept at 90 ° C for 60 minutes. The yield was 22,994 kg of polymer / mol of Ti / h. See Example 27 in Table 1.

A representative copolymerization with MET-J, sulfated alumina and hydrogen was carried out as follows. Approximately 2 mg of MET-J in 2 mL of toluene was mixed with 300 mg of sulfated alumina in 2 mL of toluene in a glass tube under nitrogen. After approximately one minute, this suspension was added to the reactor at less than 40 ° C. The reactor was sealed and 2 L of isobutane were added and the contents were stirred at 700 rpm. As the reactor temperature approached 85 ° C, 25 g of 1hexene in ethylene and hydrogen (delta 45 psi or 0.31 MPa) were added and the set point of 90 ° C was quickly reached. The reactor was kept at 90 ° C for 60 minutes. The yield was 18,794 kg of polymer / mol of Ti / h. See Example 52 in Table 1.

A representative polymerization with MET-K and sulfated alumina

MET-K in sulfate nitrogen.

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY was carried out as follows. About 2 mg of

136

<img file="MX360528B_D0151.tif" />

mL of toluene was mixed with 300 mg of alumina in 2 mL of toluene in a low glass tube

After approximately one minute, this suspension was added to the reactor at less than 40 ° C.

The reactor was sealed and added

L of isobutane and the contents were stirred

700 rpm.

As the reactor temperature approached

85 ° C, the addition of ethylene was started, and the set point of

90 ° C. The reactor was kept at 90 ° C for 60 minutes. The performance was

27,623 kg of polymer / mole of

Ti / h.

See Example 28 in

Table 1.

Using the analysis of

1H-NMR, the ratio of vinyl end groups to saturated end groups was determined for some polymers produced, and V / S is abbreviated in Table 1. For these polymers, the ratio of vinyl end groups to end groups saturated was in a range of 0.6 to 0.9.

Figure 5 compares the molecular weight distribution of the polymer of Example 14, produced using the MET-E hybrid metallocene, and that of a conventional polymer produced using a standard metallocene catalyst system. The molecular weight distribution is much broader for the

Example 14.

<img file="MX360528B_D0152.tif" />

IMPI or ~ i INSTITUTO MEXICAN

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INDUSTRIAL

Figure 6 compares the molecular weight distributions of the polymers of Examples 20 and 22, while Figure 7 illustrates the molecular weight distribution of the polymer of Example 47. Each of these polymers had a relatively wide molecular weight distribution. .

Figure 8 illustrates the radius of gyration against the logarithm of the molecular weight for the linear standard and the polymers of Examples 34 and 56, with data from SEC-MALS. Figure 8 demonstrates that these polymers were substantially linear polymers with minimal amounts of LCB's (long chain branches).

138 i Table 1. Polymerization conditions and polymer properties for the examples

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