MX9703592A

Supported catalyst component, supported catalyst, their preparation, and addition polymerization process.

Abstract

A supported catalyst component comprising a support material and an alumoxane, wherein the alumoxane is fixed onto the support, a supported catalyst comprising said supported catalyst component and a transition metal compound, a process for the preparation of the supported catalyst component and the supported catalyst, and a process for addition polymerization of addition polymerizable monomers using said supported catalyst.

MX9703592A, drawing sheet 1 — Sheet 1 of 8

Term

Term ended

Expired 2 November 2015, 10.9 years ago.

30 claims: 11 independent, 19 dependent

1
REIVINDICACIONES 1. Un componente de catalizador soportado que comprende un material de soporte y un alumoxano, cuyo componente contiene del 15 al 40 por ciento en peso de aluminio, basándose en el peso total del material de soporte y el alumoxano, y en donde no se puede extraer más del 10 por ciento del aluminio presente en el componente de catalizador soportado en una extracción de 1 hora con tolueno a 90°C, utilizando 10 mililitros de tolueno por gramo de componente de catalizador soportado, pudiéndose obtener este componente de catalizador soportado mediante:A. Calentar un material de soporte que contiene alumoxano en una forma de polvo de flujo libre, bajo una atmósfera inerte, durante un período y a una temperatura suficientes para fijar el alumoxano al material de soporte,
2
El componente de catalizador soportado de la reivindicación 1, en donde el paso de calentamiento A es seguido por:B. someter al material de soporte que contiene alumoxano, a uno o más pasos de lavado, para remover el alumoxano no fijado al material de soporte,
3
El componente de catalizador soportado de la reivindicación 2, en donde el paso de lavado se realiza bajo condiciones de reflujo del solvente de lavado, formando una -8888 pasta con el componente de catalizador soportado en un hidrocarburo aromático, y calentando la pasta hasta el punto de ebullición del hidrocarburo aromático.
4
El componente de catalizador soportado de acuerdo con cualquiera de las reivindicaciones 1 a 3, en donde no se puede extraer más del 9 por ciento del aluminio presente en el componente de catalizador soportado.
5
El componente de catalizador soportado de acuerdo con cualquiera de las reivindicaciones 1 a 4, en donde el material de soporte es sílice.
6
El componente de catalizador soportado de acuerdo con cualquiera de las reivindicaciones 1 a 5, en donde el alumoxano es alumoxano metílico.
7
El componente de catalizador soportado de acuerdo con cualquiera de las reivindicaciones 1 a 6, el cual contiene del 20 al 40 por ciento en peso de aluminio, basándose en el peso total del material de soporte y el alumoxano.
8
Un catalizador soportado, el cual comprende:un componente de catalizador soportado de acuerdo con cualquiera de las reivindicaciones 1 a 7;y un compuesto de metal de transición.
9
El catalizador soportado de la reivindicación 8, en donde el compuesto de metal de transición es un compuesto de metal de transición del Grupo 4 de monociclopentadienilo puenteado, o un compuesto de metal de transición del Grupo 4 -8989 de bis-ciclopentadienilo puenteado.
10
El catalizador soportado de acuerdo con la reivindicación 8 ó 9, en donde 1a, proporción molar del átomo de aluminio al átomo de metal de transición es de 1 a 5000.
11
El catalizador soportado de acuerdo con cualquiera de las reivindicaciones 8 a 10, el cual contiene de 0.1a 1000 micromoles de compuesto de metal de transición por gramo de material de soporte.
12
El catalizador soportado de acuerdo con cualquiera de las reivindicaciones 8 a 11;en una forma prepolimerizada, obtenido al someter a una defina, en la presencia del catalizador soportado, a condiciones de polimerización.
13
Un proceso para la preparación de un componente de catalizador soportado, el cual comprende:A. calentar un material de soporte que contiene alumoxano en forma de polvo de flujo libre bajo una atmósfera inerte, durante un período y a una temperatura suficientes para fijar el alumoxano al material de soporte;seleccionando de esta manera las condiciones, en el paso de calentamiento A, para formar un componente de catalizador soportado, cuyo componente contiene del 15 al 40 por ciento en peso de aluminio, basándose en el peso total del material de soporte y el alumoxano, y en donde no se puede extraer más del 10 por ciento del aluminio presente en el -9090 componente de catalizador soportado en una extracción de una hora con tolueno a 90°C, utilizando 10 mililitros de tolueno por gramo de componente de catalizador soportado.
14
El proceso de la reivindicación 13, en donde el paso de calentamiento A es seguido por:B. someter al material de soporte que contiene alumoxano, a uno o más pasos de lavado, para remover el alumoxano no fijado al material de soporte.
15
El proceso de la reivindicación 14, en donde el paso de lavado se realiza bajo condiciones de reflujo del solvente de lavado, formando una pasta con el componente de catalizador soportado en un hidrocarburo aromático, y calentando la pasta hasta el punto de ebullición del hidrocarburo aromático.
16
El proceso de acuerdo con cualquiera de las reivindicaciones 13 a 15, en donde el tratamiento por calor se realiza a una temperatura de 75°C a 250°C.
17
El proceso de acuerdo con cualquiera de las reivindicaciones 14 a 16, en donde el solvente de lavado es un solvente de hidrocarburo aromático.
18
El proceso de acuerdo con la reivindicación 17, en donde el solvente de hidrocarburo aromático es tolueno.
19
El proceso de acuerdo con cualquiera de las reivindicaciones 13 a 18, en donde el tratamiento por calor se realiza bajo presión reducida. -9191
20
El proceso de acuerdo con cualquiera de las reivindicaciones 13 a 19, en donde el material de soporte es sílice.
21
El proceso de acuerdo con cualquiera de las reivindicaciones 13 a 20, en donde el alumoxano es alumoxano metílico.
22
Un proceso para la preparación de un catalizador soportado, el cual comprende:preparar un componente de catalizador soportado de acuerdo con cualquiera de las reivindicaciones 13 a 21;y agregar, antes o después del paso de calentamiento A o del paso de lavado opcional Β, un compuesto de metal de transición, con la condición de que una vez que se haya agregado el compuesto de metal de transición, el producto así obtenido no se someta a temperaturas iguales a, o más altas que, la temperatura de descomposición del compuesto de metal de transición.
23
El proceso de la reivindicación 22, en donde el compuesto de metal de transición se agrega después del paso de calentamiento.
24
El proceso de acuerdo con la reivindicación 23, en donde el compuesto de metal de transición se agrega después del paso de lavado opcional.
25
El proceso de acuerdo con cualquiera de las reivindicaciones 22 a 24, en donde el compuesto de metal de transición es un compuesto de metal de transición del Grupo 4 -9292 de mono-ciclopentadienilo o mono (ciclopentadienilo sustituido) puenteado, o un compuesto de metal de transición del Grupo 4 de bis- (ciclopentadienilo) o bis (ciclopentadienilo sustituido) puenteado.
26
El proceso de acuerdo con cualquiera de las reivindicaciones 22 a 25, en donde la proporción molar del átomo de aluminio al átomo de metal de transición en el catalizador soportado, es de 1 a 5000.
27
El proceso de acuerdo con cualquiera de las reivindicaciones 22 a 26, en donde el catalizador soportado contiene de 0.1 a 1000 micromoles de compuesto de metal de transición por gramo de material de soporte.
28
El proceso de acuerdo con cualquiera de las reivindicaciones 22 a 27, el cual comprende además someter a una olefina, en la presencia de un catalizador soportado, a condiciones de polimerización, para proporcionar un catalizador soportado previamente polimerizado.
29
Un proceso de polimerización por adición, en donde uno o más monómeros polimerizables por adición se ponen en contacto con un catalizador soportado de acuerdo con cualquiera de las reivindicaciones 8 a 12, ó se pueden obtener de acuerdo con cualquiera de las reivindicaciones 22 a 28 bajo condiciones de polimerización por adición.
30
El proceso de polimerización por adición de acuerdo con la reivindicación 29, realizado bajo condiciones de polimerización en pasta o en fase de gas. -9393

Independent claims30

755 paragraphs in 32 sections, as filed

PCT

WORLD 1NTELLBCHJAL PROPERTY ORGANIZATION IfMntttiOMl Good

INTERNATIONAL APPLICATION PUBUSHÉD UNDER THE PATENT COOPERAHON TREATY (PCT)

<td>(51) hMMtauü Patent ClamMIrUt » 6 : C08F 1MOO, 4AS02</td><td>To the</td><td colspan="2">(11) International PubBeatf »Number: WO 96/16092 (43) InternatloHl Publication Date: May 30, 1996 (05.30.96)</td>

<td colspan="3">(21) Interudon ·] Application Number. PCT / US95 / 14192 (22) International flUng Date: 2 November 1995 (02.11.95) (3 ·) Priority Data: 08 / 340,989 17 November 1994 (17.11.94) US (71) Applicaat: THE DOW CHEMICAL COMPANY [US / US]; 2030 Dow Center. Atiban Ron !. Midland, MI 4860 (US). C? 2) Inventor: JACOBSEN, OflUlt, B .; Kreekiingel 9, NL-4542 BM Hoek (NL). SPENCER, Lee; 4903 Ctover Lañe. Peariand, TX 77584 (US). WAUTERABRTS, Peten U Wasseven 78, B-3945 Ham (BE). (74) Agent: DELINE, Douglai, N .; The Dow Chemical Company. Patent DepC. PO Boa 1967. Midland, MI 4864M 967 (US).</td><td>(81) Deaignated State »: AU. BR, CA, CN, CZ, FI, JP, KR, MX. NO, NZ. PL, RU, SO, European patent (AT, BE, CH, DE, DK, ES. FR, OB, GR, ΙΕ. ΓΓ, LU, MC, NL, PT. SE). Pubüsbed With inttmaiionaí search report.</td>

<td colspan="4">(54) Title: SUPPORTED CATALYST COMPONENT. SUPPORTED CATALYST, THE »PREPARATION, AND ADD1TION POLYMERIZATION PROCESS (57) Abetract A supported catalyst component comprising a support material and an alumoxane, where the alumoxane is fixed orno the suppoit, a supported catalyst comprising said supported catalyst componen! and a trantiticn metal compound, a procesa for the prepanufon of the supported catalyat component and the supported catalyst, and a procesa for edditíon polymerizition of additkm polymerizable monomera using said supponed catalyst</td>

0W1W1W7 1147: 40 PWJO-1-1 SUPPORTED CATALYST COMPONENT, SUPPORTED CATALYST,

YOUR PREPARATION AND ADDITIONAL POLYMERIZATION PROCESS

The present invention relates to a supported catalyst component comprising a support material and alumoxane, to a supported catalyst comprising a support material, alumoxane, and a metallocene compound, to a process for the preparation of this catalyst component supported and catalyst, and to an addition polymerization process using that supported catalyst.

Background of the Invention

Homogeneous or unsupported alumoxane-metallocene catalysts are known for their high catalytic activity in define polymerizations. Under the polymerization conditions in which the polymer forms as solid particles, these homogeneous (soluble) catalysts form polymer deposits on the reactor walls and in the stirrers, the deposits of which must be removed frequently, as they prevent heat exchange efficient, necessary to cool the reactor contents, and cause excessive wear of moving parts. The polymers produced by these soluble catalysts also have a low bulk density, which mimics the commercial utility of both the polymer and the process. In order to solve these problems, several supported alumoxane-metallocene catalysts have been proposed for use in particle-forming polymerization processes.

The United States of America Patent

No. 5,057,475 describes a supported metallocene alumoxane catalyst, wherein the alumoxane may be a commercial alumoxane, or an on-site generated alumoxane on the solid support, for example, by adding a trialkyl aluminum compound to a water-containing support, such as by adding trimethyl aluminum to a silica containing water. In the preferred methods of the United States Patent Number

5,057,475, the metallocene component and alumoxane (which may previously have been combined with a modifying compound) are combined in a first step in a suitable solvent, in a subsequent step, this solution is contacted with the support. The solvent can then be removed, typically by applying a vacuum. The solution can be heated in order to aid in the removal of the solvent. In an alternative method, a non-dehydrated silica gel is added to a trialkyl aluminum solution to produce an alumoxane, which is deposited on the surface of the silica gel particles. The solvent is then removed, and the residual solids are dried until a free-flowing powder is obtained. In typical examples, dry silica is formed into a paste with an alumoxane in toluene, filtered, washed with pentane, and then vacuum dried. The metallocene compound is typically combined with an alumoxane in toluene or heptane, the solution of which is subsequently combined with the previously treated silica. Finally, toluene or heptane is removed under vacuum to recover the supported catalyst.

United States Patent No. 5,026,797 describes the treatment of a porous support in water-insoluble inorganic oxide particles with an alumoxane in a solvent for alumoxane, such as an aromatic hydrocarbon, followed by rinsing of the treated support with a aromatic hydrocarbon solvent until alumoxane is no longer detected in the supernatant. Accordingly, it is said that it is possible to adjust the amount of aluminum atoms of the fixed alumoxane on the treated oxide support on the scale of 2 to 10 weight percent. Subsequently, the treated support is combined with a zirconium compound. The support material thus formed containing alumoxane and the zirconium compound is used together with additional alumoxane in solution in a polymerization reaction.

The United States of America Patent

No. 5,147,949 describes unsupported metallocene-alumoxa-44 catalysts prepared by adding a catalyst support impregnated with water to a stirred solution of a trialkyl aluminum, and adding to the reaction product thereof, a metallocene component.

United States Patent No. 5,240,894, describes a method of producing a supported catalyst by forming a metallocene / alumoxane reaction solution, adding to a porous carrier, evaporating the resulting paste to remove solvent carrier residual, and optionally prepolymerization of the catalyst with an olefinic monomer. A good bulk density of the polymer is only obtained using a previously polymerized supported catalyst.

United States Patent No. 5,252,529 describes solid catalysts for olefin polymerization, which comprise a particulate carrier containing at least 1 weight percent of water, an alumoxane compound, and a metallocene compound. In preparing this catalyst, the particulate carrier reaction product and alumoxane are separated from the diluent (toluene) by decantation or drying under reduced pressure.

European Patent Application Number 368,644 describes a process for the preparation of a supported metallocene-alumoxane catalyst, in which a non-dehydrated silica gel is added to a stirred solution of triethyl aluminum, to whose reaction mixture a solution of a metallocene to which trimethyl aluminum has been added. Following the addition of the trimethyl aluminum treated metallocene to the solids of the triethyl aluminum treated silica gel, the catalyst is dried to a free-flowing powder. The catalyst can be dried by filtration or evaporation of the solvent at a temperature of up to 85 ° C,

European Patent Application Number 323,716 describes a process for the preparation of a supported metallocene-alumoxane catalyst, by adding non-dehydrated silica gel to a stirred solution of a trialkyl aluminum, adding a metallocene to the mixture of reaction, removal of the solvent, and drying of the solids to obtain a free-flowing powder. After the metallocene has been added, the solvent is removed, and the residual solids are dried at a temperature of up to 85 ° C.

European Patent Application Number 523,416 describes a supported catalyst component for olefin polymerization prepared from an inorganic support and a metallocene. The metallocene and the support are mixed intensively in a solvent. Preferably, the catalyst component thus obtained is extracted into a suitable solvent, such as toluene, to remove the metalloce-66 no, which is not fixed. Subsequently, alumoxane can be added as a cocatalyst.

European Patent Application Number 567,952 describes a supported polymerization catalyst comprising the reaction product of a supported organic aluminum compound and a metallocene catalyst compound. This supported catalyst is prepared by combining trimethyl aluminum with a previously dried support material in an inert aliphatic suspension medium, to which water is added. This suspension can be used as it is, or can be filtered, and the solids thus obtained can be resuspended in an aliphatic inert suspension medium, and then combined with the metallocene compound. When the reaction is complete, the supernatant solution is removed, and the remaining solid is washed once to five times with an inert suspending medium, such as toluene, normal decane, diesel oil, or dichloromethane.

It would be desirable to provide a supported catalyst component, a supported catalyst, and a polymerization process that prevents or substantially reduces the problem of reactor contamination, including the formation of polymer deposits on the reactor walls and on the reactor stirrer, especially in gas phase polymerization or paste polymerization processes. Furthermore, it is preferred that the polymeric products produced by the gas phase polymerization or paste polymerization processes remain in a free-flowing form, and, conveniently, have high bulk densities.

Compendium of the Invention

In one aspect of the present invention, there is provided a supported catalyst component comprising a support material and an alumoxane, the component of which contains 15 to 40 weight percent aluminum, based on the total weight of the support material and the alumoxane, and where no more than 10 percent of the aluminum present in the supported catalyst component can be extracted in a one hour extraction with toluene at 90 ° C using 10 milliliters of toluene per gram of supported catalyst component, being able to obtain this component of catalyst supported by:

A. heating an alumoxane-containing support material under an inert atmosphere for a period and at a temperature sufficient to fix the alumoxane to the support material.

In a second aspect, a supported catalyst is provided comprising: the supported catalyst component in accordance with the present invention, and a transition metal compound containing at least one cyclic or non-cyclic n-linked anionic ligand group.

In accordance with a further aspect, a process is provided for the preparation of a supported catalyst component, which comprises:

A. heating an alumoxane-containing support material under an inert atmosphere, for a period and at a temperature sufficient to fix the alumoxane to the support material;

thereby selecting the conditions in heating step A, to form a supported catalyst component, the component of which contains 15 to 40 percent by weight aluminum, based on the total weight of the support material, and the alumoxane, and where it is not possible to extract more than 10 percent of the aluminum present in the supported catalyst component in a one hour extraction with toluene at 90 ° C, using 10 milliliters of toluene per gram of supported catalyst component.

In another aspect, the invention provides a process for the preparation of a supported catalyst, which comprises:

A. heating a support material containing alumoxane under an inert atmosphere, for a period and at a temperature sufficient to fix the. alumoxane to the support material; and optionally followed by:

B. subjecting the support material containing alumoxane to one or more washing steps to remove the alumoxane not attached to the support material;

thus, select the conditions in heating step A, and optional wash step B, to form a supported catalyst component, the component of which contains 15 to 40 weight percent aluminum, based on total weight of the support material and alumoxane, and where no more than 10 percent of the aluminum present in the supported catalyst component can be extracted in a one hour extraction with toluene at 90 ° C, using 10 milliliters of toluene per gram of supported catalyst component; and adding, before or after step A or step B, a transition metal compound containing at least one cyclic or non-cyclic n-linked anionic ligand group, provided that, once the transition metal compound, the product thus obtained is not subjected to temperatures equal to, or higher than, the decomposition temperature of the transition metal compound.

In a still further aspect, an addition polymerization process is provided, wherein one or more addition polymerizable monomers are contacted with a supported catalyst in accordance with the present invention, under addition polymerization conditions.

-1010

Detailed description of the invention

All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Also, any reference to the Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements, using the IUPAC system to number the groups. The term hydrocarbyl as used herein, means any aiphatic, cycloaliphatic, aromatic group, or any combination thereof. The term hydrocarbyloxy means a hydrocarbyl group that has an oxygen bond between it and the element to which it is attached. Where the term "substituted cyclopentadienyl" is used in the specification and claims, this includes ring-substituted or polynuclear derivatives of the cyclopentadienyl moiety, where this substituent is hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, cyano, halogen, silyl, germyl, siloxy. , or mixtures thereof, or two of these substituents with a hydrocarbylene group, this substituent (or two substituents together) having up to 30 non-hydrogen atoms. The term substituted cyclopentadienyl specifically includes the indenyl, tetraindenyl, fluorenyl, and octahydrofluorenyl groups.

Surprisingly, it has been found that

-1111 can prepare polymers that have a good bulk density in a particle formation polymerization process, without or with substantially reduced reactor contamination, by using a supported catalyst, where the alumoxane is attached to the support material . In accordance with the present invention, good bulk densities, for ethylene-based polymers and interpolymers, are bulk densities of at least 0.20 grams / cubic centimeter, preferably at least 0.25 grams / cubic centimeter, and more preferably of at least 0.30 grams / cubic centimeter. The extent of reactor contamination is believed to be related to the amount of alumoxane that is leached from the support during polymerization conditions, which can lead to active catalyst being present in the homogeneous phase, and therefore dissolved in the diluent, that under particle formation conditions it can give very small polymer particles, or polymer particles of poor morphology that can adhere to metal parts or static parts of the reactor. Furthermore, it is believed that the bulk density of a polymer is related to the way in which the alumoxane is fixed to the support, and to the amount of alumoxane not fixed on the support, that is, the amount of aluminum that can be extracted of the support with toluene at 90 ° C. Fixing the alumoxane on the support

-1212, in accordance with the specific treatment of the present invention, results in that substantially no alumoxane is leached from the support under the polymerization conditions, and that substantially no soluble active catalyst species are present in the polymerization mixture. It has been found that the present supported catalysts can be supported not only to prepare polymers and copolymers of ethylene on the traditional high density polyethylene density scale (0.970 to 0.940 grams / cubic centimeter) in phase and paste polymerization processes gas, but also copolymers with densities less than 0.940 grams / cubic centimeter and down to 0.880 grams / cubic centimeter or less, while good bulk density properties are retained, and while reactor contamination is prevented or substantially decreased.

The supported catalyst component in the present invention comprises a support material and an alumoxane, where, in general, no more than 10 percent of the aluminum present in the supported catalyst component can be removed in a one hour extraction with toluene. at 90 ° C, using 10 milliliters of toluene per gram of supported catalyst component. Preferably, no more than 9 percent of the aluminum present in the supported catalyst component can be removed, and more preferably, no more than 8 percent can be removed. It has been discovered that,

-1313 when the amount of extractables is less than these levels, a good bulk density of the polymer is obtained with the supported catalysts based on these supported catalyst components.

The toluene extraction test is performed as follows. 1 gram of supported catalyst or supported catalyst component, with a known aluminum content, is added to 10 milliliters of toluene, and then the mixture is heated to 90 ° C under an inert atmosphere. The suspension is stirred well at this temperature for 1 hour. The suspension is then filtered by applying reduced pressure to aid in the filtration step. The solids are washed twice with 3 to 5 milliliters of toluene at 90 ° C per gram of solids. The solids are then dried at 120 ° C for 1 hour, and the aluminum content of the solids is subsequently measured. The difference between the initial aluminum content and the aluminum content after extraction, divided by the initial aluminum content, and multiplied by 100 percent, gives the amount of aluminum that can be extracted.

Aluminum content is determined by forming a 0.5 gram paste of supported catalyst or supported catalyst component in 10 milliliters of hexane. The paste is treated with 10 to 15 milliliters of 6N sulfuric acid followed by the addition of a known excess of EDTA. The amount

-1414 excessive EDTA is then titrated back with zinc chloride.

At a 10 percent level of extraials, the bulk density of the polymer obtained by polymerization using the supported catalysts (components) described herein is highly sensitive with respect to small changes in the percentage of aluminum extractables. In view of the sensitivity of the bulk density of the polymer, and the margin of error in determining the percentage of aluminum extractables (estimated to be absolute percent), an alternative test to distinguish the supported catalyst component and the supported catalyst according to the present invention is to use a supported catalyst in an ethylene polymerization process in a hydrocarbon diluent at 80 ° C and at 15 bar, and determining the degree of contamination of the reactor and / or the bulk density of the produced ethylene polymer. The substantial absence of contamination from the reactor, i.e. if there are substantially no polymer deposits on the reactor walls or on the stirrer, and / or if the bulk densities are at least 0.20 grams / cubic centimeter, and preferably at least 0.25 grams / cubic centimeter, this is a characteristic of supported catalyst components and catalysts of the invention.

Suitable support materials for this

-1515 invention preferably have a surface area determined by nitrogen porosimetry using the BET method, from 10 to 1000 square meters / gram, and preferably from 100 to 600 square meters / gram. The porosity of the support is conveniently between 0.5 and 5 cubic centimeters / gram, preferably 0.1 to 3 cubic centimeters / gram, and most preferably 0.2 to 2 cubic centimeters / gram. Average particle size is not critical, but is typically 1 to 200 microns.

Suitable support materials for the supported catalyst component of the present invention include porous resinous materials, for example, styrene-divinylbenzene copolymers, and solid inorganic oxides, such as silica, alumina, magnesium oxide, titanium oxide, oxide of thorium, as well as mixed silica oxides and one or more Group 2 or 13 metal oxides, such as mixed silica-magnesia and silica-alumina oxides. Silica, alumina, and mixed silica oxides and one or more Group 2 or 13 metal oxides are the preferred support materials. Preferred examples of these mixed oxides are silicas-aluminas. Silica is more preferred. The silica can be in granular, agglomerated, vaporized form, or in another form. Suitable silicas include those available from Grace Davison (division of WR Grace & Co.) under the designations SD 3216.30, Devison Syloid 245, Davison

-1616

8 and Davison 952, and at Degussa AG, under the designation Aerosil 812.

Before use, if desired, the support material can be subjected to heat treatment and / or chemical treatment, to reduce the water content or the hydroxyl content of the support material. Typical thermal pretreatments are performed at a temperature of 30 ° C to 1000 ° C for a duration of 10 minutes to 50 hours in an inert atmosphere or under reduced pressure.

The supported catalyst component further comprises an alumoxane component. An alumoxane (also referred to as aluminoxane) is an oligomeric or polymeric oxyaluminium compound containing alternating chains of aluminum and oxygen atoms, whereby aluminum carries a substituent, preferably an alkyl group. The exact structure of alumoxane is not known, but is generally believed to be represented by the following general formulas: (-A1 (R) -O)m, for a cyclic alumoxane, and R2A10 (-Al (R) -O)m-A1R2, for a linear compound, where R, independently in each presentation is a hydrocarbyl with 1 to 10 carbon atoms, preferably alkyl, or a halide, and m is an integer from 1 to 50, preferably at least 4 Alumoxanes are typically the reaction products of water and an alkyl aluminum, which in addition to an alkyl group may contain halide or alkoxide groups. The reaction

-1717 of various different alkyl aluminum compounds, such as, for example, trimethyl aluminum and triisobutyl aluminum, with water produces so-called modified or mixed alumoxanes. Preferred alumoxanes are methyl alumoxane and modified methyl alumoxane with minor amounts of other lower alkyl groups, such as isobutyl. Alumoxanes generally contain less than substantial amounts of the starting alkyl aluminum compound.

The manner in which the alumoxane is prepared is not critical to the present invention. When prepared by the reaction between water and alkyl aluminum, water can be combined with alkyl aluminum in different forms, such as liquid, vapor, or solid, for example in the form of water of crystallization. Particular techniques for the preparation of alumoxane-type compounds by contacting an alkyl aluminum compound with an inorganic salt containing crystallization water are described in United States Patent No. 4,542,199. In a particular preferred embodiment, an alkyl aluminum compound is contacted with a regenerable water-containing substantial, such as hydrated alumina, silica, or other substance. This is described in European Patent Application Number 338,044.

The supported catalyst component of the present invention generally contains 15 to 40 per

-1818 percent by weight, preferably 20 to 40 percent by weight, and more preferably 25 to 40 percent by weight of aluminum, based on the total weight of the support material and the alumoxane. Amounts of aluminum of at least 15 percent by weight, preferably at least 20 percent by weight, and more preferably at least 25 percent by weight, are convenient because these make it possible to deposit amounts relatively high levels of transition metal compound on the support, and thus enable relatively high activity to be obtained. This improves the overall efficiency of the catalyst, especially when expressed based on the support material.

The supported catalyst component as such, or formed into a paste in a diluent, can be stored or shipped under inert conditions, or can be used to generate the supported catalyst of the present invention.

In accordance with a further aspect, the present invention provides a supported catalyst comprising the supported catalyst component according to the present invention, and a transition metal compound, preferably a transition metal compound containing at least one group of cyclic or non-cyclic n-linked anionic ligand, preferably a fraction of cyclopentadienyl, or substituted cyclopentadienyl. The suitable 1919 complexes are derived from any transition metal, including lantaniides, but preferably from Group 3, 4, 5, or lantaniide metals, which are in the formal oxidation state of +2, +3, or +4. Preferred compounds include metal complexes containing 1 to 3 n-linked anionic ligand groups, which can be cyclic or non-cyclic delocalized delocalized anionic ligand groups. Examples of these n-linked anionic ligand groups are dienyl groups, ring groups, and conjugated or unconjugated, cyclic or non-cyclic arene groups. The term "n-linked" means that the ligand group is linked to the transition metal via an n-bond. Each atom in the delocalized n-linked group may be independently substituted by a radical selected from halogen, hydrocarbyl, halohydrocarbyl, and hydrocarbyl-substituted metalloid radicals, wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements. The term hydrocarbyl preferably includes linear, branched, and cyclic alkyl radicals of 1 to 20 carbon atoms, aromatic radicals of 6 to 20 carbon atoms, alkyl substituted aromatic radicals of 7 to 20 carbon atoms , and aryl-substituted alkyl radicals of 7 to 20 carbon atoms. In addition, two or more of these radicals can together form a fused ring system or a

-2020 hydrogenated cast ring. Suitable hydrocarbyl-substituted organometaloid radicals include the di- and tri-substituted organometaloid radicals of Group 14 elements, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups.

Examples of suitable anionic delocalized n-linked groups include the cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrafluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl and decahydroanthracenyl atoms as well thereof. Preferred anionic delocalized n-linked groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, and

2-methyl-4-phenylindenyl.

The term metallocene compound as used herein, refers to transition metal compounds that contain a derivative of a cyclopentadienyl moiety. Suitable metallocenes for use in the present invention are the transition metal compounds of

-2121 substituted or mono-, bis-, and tri-cyclopentadienyl substituted or bridged cyclopentadienyl.

Suitable non-bridging monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal derivatives are represented by the general formula

CpMXn, where Cp is cyclopentadienyl or a derivative thereof; M is a Group 3, 4, or 5 transition metal, having a formal oxidation state of 2, 3, or 4; X independently in each presentation represents an anionic ligand group (different from a cyclic aromatic n-linked anionic ligand group), said X having up to 50 non-hydrogen atoms; and n is a number equal to, or less than, the formal oxidation state of M, and is 1, 2, or 3, preferably 3. Examples of these X ligand groups are hydrocarbyl, hydrocarbyloxy, hydride, halogen, silyl, germyl, amide, and siloxy, or two X groups can together form a hydrocarbylene (including hydrocarbylidene).

Suitable bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compounds include well known limited geometry complexes.

Examples of these complexes and methods for their preparation are described in US Patent Application Serial Number 545,403, filed July 3, 1990, (corresponding to

-2222

European Patent Number EP-A-416,815), in US Patent Number 5,374,696 (which corresponds to International Patent Number WO-93/19104), as well as in US Patent Numbers

5,055,438; 5,057,475; 5,096,867; 5,064,802 and 5,132,380.

More particularly, the preferred bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compounds correspond to formula I:

<z’\

Cp * -Μ T \

(X)n where:

M is a Group 3 to 5 metal, especially a Group 4 metal, particularly titanium;

Cp * is a substituted cyclopentadienyl group linked with 2 'and in a jj bonding mode5, with M, or this group is further substituted by 1 to 4 substituents selected from hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two of these additional substituents (with the

25. exception of halogen or amino) together make Cp * have a

-2323 cast ring structure;

Z 'is a different bivalent fraction of a cyclic or non-cyclic n-linked anion ligand, said Z' boron comprising, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorous, sulfur, or oxygen, having this fraction up to 2 0 that are not hydrogen, and optionally Cp and Z1 together they form a fused ring system, X, independently in each presentation, is an anionic ligand group (different from a cyclic n-linked group) having up to 50 non-hydrogen atoms; and n is 1 or 2, depending on the valence of M.

Consistent with the above explanation, M is preferably a Group 4 metal, especially titanium; n is 1 or 2; and X is a monovalent ligand group of up to 30 non-hydrogen atoms, more preferably hydrocarbyl of 1 to 20 carbon atoms.

When a is 1 and the Group 3 to 5 metal (preferably Group 4 metal) is in the +3 formal oxidation state, X is preferably a stabilizing ligand.

The term stabilizing ligand means that the ligand group stabilizes the metal complex through:

1) a chelation bond of nitrogen, phosphorous, oxygen, or sulfur, or

2) an ip link with an n-electronic structure

-2424 resonant delocalized.

Examples of the Group 1 stabilizing ligands include silyl, hydrocarbyl, amido, or phosphide ligands, substituted by one or more functional aliphatic or aromatic ether, thioether, amine, or phosphine groups, especially amine or phosphine groups. which are tertiary substituted, this stabilizing ligand having 3 to 30 non-hydrogen atoms. The most preferred Group 1 stabilizing ligands are 2-dialkylaminobenzyl or 2- (dialkylaminomethyl) phenyl groups containing 1 to 4 carbon atoms in the alkyl groups.

Examples of group 2 stabilizing ligands include hydrocarbyl groups of 3 to 10 carbon atoms containing ethylenic unsaturation, such as allyl, 1-methylallyl, 2-methylallyl, 1,1-dimethylallyl group, or 1,2, 3-trimethylallyl.

Even more preferably, the metal coordination complexes correspond to formula II:

-2525 wherein R 'in each presentation is independently selected from hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen, and combinations thereof, having up to 20 non-hydrogen atoms, or two R' groups (with the exception of cyano or halogen) together form a divalent derivative thereof.

X, in each presentation, is independently selected from hydride, halogen, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof having up to 20 non-hydrogen atoms;

Y is a divalent anionic ligand group comprising nitrogen, phosphorous, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, said Y linking with Z and M through nitrogen, phosphorous, oxygen, or sulfur, and optionally Y and Z together form a fused ring system;

M is a Group 4 metal, especially titanium, Z is SíR 2 / CR 2, S iR 1R 2r CR 2GR 21 GR = CR, CR 2 ^ iR 2 / GeR 2 # BR 1 θ BR 2 i where:

* .

R in each presentation is independently selected from the groups hydrogen, hydrocarbyl, silyl, halogenated alkyl, halogenated aryl having up to 20 non-hydrogen atoms, and mixtures thereof,

-2626 s {c or two or more R groups from Z, or one R group from Z together with Y form a fused ring system; and

Furthermore, more preferably, Y is -O-, -S-, * *

-NR -, -PR In a highly preferable way, Y is a nitrogen or phosphorous containing group corresponding to the formula -N (R ') - or -P (R') -, where R 'is as previously described , that is, an amido or phosphide group.

The most highly preferred metal coordination complexes correspond to formula III:

R

M

III

where:

M is titanium;

R ', in each presentation, is independently selected from hydrogen, silyl, hydrocarbyl, and combinations thereof having up to 20, preferably up to 10 carbon or silicon atoms, or two R groups1 of the substituted cyclopentadienyl moiety bind between

E is silicon or carbon;

X, independently in each presentation, is

-2727 hydride, halogen, alkyl, aryl, aryloxy, or alkoxy of up to 10 carbon atoms;

m is 1 or 2; and n is 1 or 2.

Examples of the above more highly preferred metal coordination compounds include compounds wherein R 'on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl (including its isomers), norbornyl, benzyl, phenyl, or cyclododecyl; (ER '2)m is dimethylsilane or

1,2-ethylene; R 'on the cyclic n-linked group, independently in each presentation, is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl, or phenyl, or two R' groups are joined forming an indenyl moiety, tetraindenyl, fluorenyl, or octahydrofluorenyl; and

X is chlorine, bromine, iodine, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl, or phenyl.

Specific highly preferred compounds include: (tertiary butyl amido) (tetramethyl-η5-cyclocyclopentadienyl) -1,2-ethanediolitanium-dimethyl, (tertiary butyl20 amido) (tetramethyl-T /5-cyclocyclopentadienyl) -1,2-ethanediolitanium dibenzyl, (tertiary butyl amido) (tetramethyl-i?5-cyclocyclopentadienyl) -dimethylsilanetitanium-dimethyl, (butyl tertiary amido) (tetramethyl-i /5-cyclocyclopentadienyl) dimethylsilanetitaniodibenzyl, (methylamido) (tetramethyl-i /5-cyclocyclopentadienyl) dime-2828 tilsilanotitanio-dimetil, (methylamido) (tetrametil-Tj5-cyclocyclopentadienyl) dimethylsilanetitanium-dibenzyl, (phenylamido) (tetramethyl -η5-cyclocyclopentadienyl) dimethylsilanetitanium-dimethyl, (phenylamido) (tetramethyl-i /5-cyclocyclopentadienyl) dimethylsilanotite5 nio-dibenzyl, (benzylamido) (tetramethyl-η5-cyclocyclopentadienyl) dimethylsilanetitanium-dimethyl, (benzylamido) (tetramethyl175-cyclocyclopentadienyl) dimethylsilanetitanium-dibenzyl, (tertiary butyl-amido) (i?5-cyclocyclopentadienyl) -1, 2-ethanediolitanium dimethyl, (tertiary butyl amido) (tj5-cyclocyclopentadienyl) -1,210 ethanediolitanium-dibenzyl, (tertiary butyl amido) (η5~ cyclopentadienyl) dimethylsilanetitanium-dimethyl, (tertiary butyl-amido) (T)5-cyclocyclopentadienyl) dimethylsilanetitaniodibenzyl, (methylamido) (^ -cyclopentadienyl) dimethylsilanetitanium-dimethyl, (tertiary butyl amido) (i?5-cyclopentadie15 nyl) dimethylsilanetitanium-dibenzyl, (tertiary butyl-amido) (indenyldimethylsilanetitanium-dimethyl, (tertiary butyl amido) indenyldimethylsilanetitanium-dibenzyl, corresponding (decyl amido) indenyldimethylsilanetitanium-dibenyl);

Transition metal compounds where the transition metal is in the +2 formal oxidation state, and the processes for their preparation, are described in detail in International Patent Number WO 9500526, which corresponds to the Patent Application of the United States of

-2929

North America Serial Number 241,523, filed May 12, 1994. Suitable complexes include those containing one, and only one n-linked, anionic, delocalized, cyclic group, these complexes corresponding to formula IV:

IV

X * where:

M is titanium or zirconium in the +2 formal oxidation state;

L is a group containing an anionic, delocalized, cyclic n system, through which the group is linked with M, and whose group is also linked with Z;

Z is a fraction linked to M by means of a σ bond, comprising boron, or a member of group 14 of the Periodic Table of the Elements, and which also comprises nitrogen, phosphorous, sulfur, or oxygen, this fraction having up to 60 non-hydrogen atoms; and

X * is a neutral diene, conjugated or non-conjugated, optionally substituted by one or more hydrocarbyl groups, said X having up to 40 carbon atoms, and forming a complex n with M.

-3030

Preferred transition metal compounds of formula IV include those where Z, M, and X are as defined above; and L is a group C5H4 linked with Z, and linked in a link mode η5 with M, or is a group linked with 175 substituted by one to four substituents independently selected from hydrocarbyl, silyl, germyl, halogen, cyano, and combinations thereof, this substituent having up to 20 non-hydrogen atoms, and optionally, two of these substituents (with the except cyano or halogen) together make L have a fused ring structure.

The most preferred transition metal +2 compounds according to the present invention correspond to formula V:

where:

R 'in each presentation is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halogen, cyano, and combinations thereof, said R' having up to 20 non-hydrogen atoms, and optionally,

-3131 two groups R '(where R1 not hydrogen, halogen, or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure;

X is a neutral η * bonded diene group having up to 30 non-hydrogen atoms, which forms a complex n with M;

Y is -0-, -S-, -NR * -, -PR * -;

M is titanium or zirconium in the +2 formal oxidation state; and

Z is SrR, CR 2 / SiR 2S1R 2 / CR 2 ^ -R 2 * CR —CR,

CR * 2SiR * 2, or GeR * 2; where:

R, in each presentation, is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R * having up to 10 non-φ φ hydrogen atoms, and optionally two group R from Z (in φ φ * where R is not hydrogen), or one group R from Z and one group R * from Y, form a ring system.

0 Preferably, R 'independently in each presentation, is hydrogen, hydrocarbyl, silyl, halogen, and combinations thereof, said R' having up to 10 non-hydrogen atoms, or two R groups1 (when R1 not hydrogen or halogen) together form a bivalent derivative of

-3232 the same; more preferably R1 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl (including where appropriate all isomers), cyclopentyl, cyclohexyl, norbornyl, benzyl, or phenyl, or two R 'groups (with the exception of hydrogen) are linked each other, all group C being5R'4 in this way, for example, an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group.

More preferably, at least one of R 'or R * is an electron donating fraction. The term electron donor means that the fraction is more electron donating than hydrogen. Therefore, in a highly preferable manner, Y is a nitrogen or phosphorous-containing group corresponding to the formula -N (R) - or -P (R) -, where R is hydrocarbyl of 1 to 10 carbon atoms.

I have

Examples of suitable X groups include: strans-i74-l, 4-diphenyl-l, 3-butadiene; s-trans -? /4-3-methyl-l, 3-pentadiene; s-trans-í /4-l, 4-dibenzyl-l, 3-butadiene; s-trans-1742,4-hexadiene; s-trans-i)4-l, 3-pentadiene; s-trans-17 ^ -1,4ditolyl-1,3-butadiene; s-trans-tZ-l, 4-bis (trimethylsilyl) -1,3-butadiene; s-cis-rj4-l, 4-diphenyl-l, 3-butadiene, - s-cis-i74-3methyl-1,3-pentadiene; s-cís-t?4-1,4-dibenzyl-l, 3-butadiene; s- * cís-t)4-2,4-hexadiene; s-cis-ij4-l, 3-pentadiene; s-cis-i74-l, 4ditolyl-1,3-butadiene; and s-cis-ij4-l, 4-bis (trimethylsilyl) -1,3-3333 butadiene, the s-cis-diene group forming a complex n as defined herein with the metal.

The most highly preferred +2 transition metal compounds are the amidosilane or amidoalkandiyl compounds of formula V, wherein:

-Z * -Y- is - (ER ”'2)m-N (R) -, and RF in each presentation, it is independently selected from hydrogen, silyl, hydrocarbyl, and combinations thereof, said R 'having up to 10 carbon or silicon atoms, or two of these R' groups on the substituted cyclopentadienyl group (wherein R1 not hydrogen) together form a bivalent derivative thereof, connected to adjacent positions of the cyclopentadienyl ring;

R is hydrocarbyl with 1 to 10 carbon atoms;

R ', independently in each presentation, is hydrogen or hydrocarbyl with 1 to 10 carbon atoms;

And, independently in each presentation, it is silicon or carbon; and m is 1 or 2.

Examples of the metal compounds according to the present invention include compounds where R is methyl, ethyl, propyl, butyl, pentyl, hexyl (including all isomers of the above where applicable), cyclododecyl, norbornyl, benzyl, or phenyl; (ER'2)m it is dimethylsilane, or ethandiyl; and the cyclocyclic 3434 dellocalized n-linked group is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl.

Suitable bis5 cyclopentadienyl or substituted cyclopentadienyl transition metal compounds include those containing a bridging group linking the cyclopentadienyl groups, and those without bridging groups.

Suitable non-bridged bis-cyclopentadienyl or bis (substituted cyclopentadienyl) transition metal derivatives are represented by the general formula Cp2MXn»Where Cp is a n-linked cyclopentadienyl group, or an n-linked substituted cyclopentadienyl group, and M and X are as defined with respect to formula II, and n1 is 1 or 2, and is two less than the formal oxidation state of

M. Preferably n · is 2. Examples of unbridged bis-cyclopentadienyl transition metal derivatives are: Cis-cyclopentadienylzirconium-dimethyl, bis-cyclopentadienylzirconium-dibenzyl, bis (methylcyclopentadienyl) zirconiodimethyl, bis (butyl-normal-cyclopentadienyl) zirconium-dimethyl-dimethyl-zirconium-dimethyl-zirconium-zirconium-dimethyl-zirconium-zirconium-dimethyl) (indenyl) zirconium-dibenzyl, bis (fluorenyl) zirconium-dimethyl, bis (pentamethylcyclopentadienyl) zirconium-bis [2- (N, N-dimethylamino) benzyl], and the corresponding titanium and hafnium derivatives.

-3535

Preferred bridging groups are those corresponding to the formula (ER2)X, where E is silicon or carbon, R, independently in each presentation, is hydrogen or a group selected from silyl, hydro5carbyl, and combinations thereof, said R "having up to 30 carbon or silicon atoms, and x is from 1 to 8. Preferably, R ", independently in each presentation, is methyl, benzyl, tertiary butyl, or phenyl.

The example bridged ligands containing two n-linked groups are: (dimethylsilyl-bis-cyclopentadienyl), (dimethylsilyl-bis-methylcyclopentadienyl), (dimethylsilyl-bisethyl-cyclopentadienyl), (dimethylsilyl-bis-butyl-tertiarycyclopentadinyl), (dimethylsilyl-bis-tetramethylcyclo-diethyl) -dimethyl-15-dimethyl) -bis-tetrahydroindenyl), (dimethylsilyl-bis-fluorenyl), (dimethylsilylbis-tetrahydrofluorenyl), (dimethylsilyl-bis-2-methyl-4-phenylindenyl), (dimethylsilyl-bis-2-methylindenyl), (dimethylsilyl-cyclopentadienyl) {1,1,2,2-tetramethyl-l, 220-disilyl-bis-cyclopentadienyl), (1,2-bis (cyclopentadienyl) ethane, and (isopropylidene-cyclopentadienyl-fluorenyl).

Examples of the above bridged bis-cyclopentadienyl or bis (substituted cyclopentadienyl) complexes are the compounds corresponding to formula VI:

-3636

where:

Μ, X, E, R ', m and n are as defined for the complexes of formula III. Two of the X substituents can together form a neutral n-linked conjugated diene having 4 to 30 non-hydrogen atoms, forming an n complex with M, over which M, which is preferably zirconium or hafnium, is in the formal oxidation state +2.

The above metal complexes are especially suitable for the preparation of polymers having a stereoregular molecular structure. In this capacity, it is preferred that the complex possess a Cs symmetry, or possess a stereorigid chiral structure. Examples of the first type are compounds that have different delocalized penlate systems, such as a cyclopentadieni-3737 lo group and a fluorenyl group. Similar Ti (IV) or Zr (IV) based systems for the preparation of syndiotactic olefin polymers were described in Ewen et al. J. Am. Chem. Soc., Volume 110, pages 6255-6256 (1980). Examples of chiral structures include bis-indenyl complexes. Similar systems based on Ti (IV) or Zr (IV) for the preparation of isotactic olefin polymers were described in Wild et al. J. Organomet. Chem. Volume 232, pages 233-47, (1982).

The example complexes of formula IV are: (dimethylsilyl-bis-cyclopentadienyl) zirconium-dimethyl, (dimethylsilyl-bis-tetramethylcyclopentadienyl) zirconium-dimethyl, (dimethylsilyl-bis-butyl-tertiary-cyclopentadien.yl-zirconiodiphenyl-dylethyl-bis-tetra cyl) -indenyl) zirconium-bis (2-dimethylaminobenzyl), (isopropylidene-cyclopentadienyl-fluorenyl) zirconium-dimethyl, [2,2'-biphenyldiylbis (3,4-dimethyl-1-cyclopentadienyl)] titanium-dibenzyl, [6,6-dimethyl-2,2'-biphenyl-bis (3,4-dimethyl-1-cyclopentadienyl)] zirconium-dimethyl, and the corresponding titanium and hafnium complexes.

Suitable tricyclopentadienyl or substituted cyclopentadienyl transition metal compounds include those that contain a bridging group linking two cyclopentadienyl groups, and those without those bridging groups.

-3838

Suitable unbridged tricyclopentadienyl transition metal derivatives are represented by the general formula Cp3MXn-, where Cp, M, and X are as defined above, and n is three less than the formal oxidation state of M, and is 0 or 1, preferably 1. Preferred X ligand groups are hydrocarbyl, hydrocarbyloxy, hydride, halogen, silyl, germyl, amido, and siloxy.

Preferably, the transition metal compound is a bridged monocyclopentadienyl Group 4 transition metal compound, or a bridged bis-cyclopentadienyl Group 4 transition metal compound, more preferably a bridged monocyclopentadienyl transition metal compound , especially a compound where the metal is titanium.

Other compounds that are useful in the preparation of catalyst compositions in accordance with this invention, especially compounds containing other Group 4 metals, will, of course, be apparent to those skilled in this field.

In general, the molar ratio of the aluminum atom (from the alumoxane component) to the transition metal atom in the supported catalyst is from 1 to 5000, preferably from 25 to 1000, and more preferably from 50 to 500. In too low proportions, the supported catalyst will not be very active, while in proportions

-3939 too high, the catalyst becomes less economical due to the relatively high cost associated with the use of large amounts of alumoxane.

The amount of transition metal compound in the supported catalyst of the present invention is not critical, but is typically 0.1 to 1000 micromoles of transition metal compound per gram of support material. Preferably, the supported catalyst contains from 1 to 250 micromoles of transition metal compound per gram of support material. It has been found that the higher aluminum loads on the support result in catalysts that have higher efficiencies, when expressed on a transition metal basis, compared to catalysts that have lower aluminum loads but approximately the same proportion of aluminum to transition metal. These higher aluminum-bearing support components also provide supported catalysts that have higher efficiencies, expressed as aluminum or support material.

The supported catalyst of the present invention can be used as such, or in a pre-polymerized form obtained by subjecting an olefin, in the presence of the supported catalyst, to polymerization conditions.

The supported catalyst component of the invention can be obtained by heating a

-4040 support material containing alumoxane, under an inert atmosphere, for a period and at a temperature sufficient to fix the alumoxane to the support material.

The alumoxane containing support material can be obtained by combining, in a diluent, an alumoxane with a support material containing from 0 to no more than 20 weight percent water, preferably from 0 to no more than 6 weight percent water, based on the total weight of the support material and water. Support materials that are substantially water-free give good results with respect to the catalytic properties of the supported catalyst. In addition, it has been discovered that the support materials containing relatively small amounts of water can be used without problem in the present process. The water-containing support materials, when combined under identical conditions with the same amount of alumoxane, give, in the present process, a supported catalyst component having a slightly higher aluminum content than the substantially water-free support material. Water is believed to react with the residual amounts of alkyl aluminum present in the alumoxane, to convert the alkyl aluminum into extra alumoxane. An additional advantage is that less alkyl aluminum will be lost to waste or recycle streams in this way. Alumoxane

-4141 is desirably used in a dissolved form.

Alternatively, the support material-containing alumoxane may be obtained by combining, in a diluent, a support material containing 5 to 30 weight percent water, preferably 6 to 20 percent by weight in weight of water, based on the total weight of the support material and water, with a compound of formula Rn* AlXn3_n* where R ", independently in each presentation, is a hydrocarbyl radical, X" is halogen or hydro10-carbyloxy, and n * is an integer from 1 to 3. Preferably, n * is

3. When alumoxane is prepared on site by reaction of the compound of formula R ''or* AlX3_n* with water, the molar ratio of Rn* AlXn3_n* Water is typically 10: 1 to 1: 1, preferably 5: 1 to 1: 1.

The support material is added to the alumoxane or to the compound of formula R "n* AlX3_n*, preferably dissolved in a solvent, more preferably a hydrocarbon solvent or the alumoxane solution or the compound of the formula R ''n* AlX ”3_n* is added to the support material. The support material can be used as such in dry form or as a paste in a hydrocarbon diluent. Both aliphatic and aromatic hydrocarbons can be used. Suitable aliphatic hydrocarbons include, for example, pentane, isopentane, hexane, heptane, octane, isooctane, nonane,

-4242 combines ononan, dean, cyclohexane, me t i1c and chlohexane, and two or more of these diluents. Suitable examples of aromatic diluents are benzene, toluene, xylene, and other alkyl or halogen substituted aromatic compounds. More preferably, the diluent is an aromatic hydrocarbon, especially toluene. Suitable concentrations of solid support in the hydrocarbon medium are 0.1 to 15, preferably 0.5 to 10, more preferably 1 to 7 weight percent. Contact time and temperature are not critical. Preferably the temperature is from 0 ° C to 60 ° C, more preferably from 10 ° C to 40 ° C. The contact time is from 15 minutes to 40 hours, preferably from 1 hour to 20 hours.

Before subjecting the alumoxane containing support material to the heating step, the diluent or solvent is removed to obtain a free-flowing powder. This is preferably done by applying a technique that only removes the liquid and leaves the aluminum compounds on the solid, such as by applying heat, reduced pressure, evaporation, or combinations of these techniques.

Heating step A followed by optional washing step B is conducted in such a way that a very large proportion (more than 90 weight percent) of the alumoxane remaining on the catalyst component is fixed.

-4343 supported. In the heating step, the alumoxane is attached to the support material, while, in the optional washing step, the non-fixed alumoxane is removed to a substantial degree to provide the supported catalyst component of the present invention. The upper temperature for heat treatment is preferably less than the temperature at which the support material begins to agglomerate and form lumps that are difficult to disperse again, and less than the decomposition temperature of alumoxane. When the metallocene compound is added prior to heat treatment, as will be explained herein, the heating temperature should be less than the decomposition temperature of the metallocene compound. The alumoxane containing support material in free-flowing or powder form is preferably subjected to heat treatment at a temperature of at least 75 ° C, preferably at least 85 ° C, more preferably at least 100 ° C, up to 250 ° C, more preferably up to 200 ° C, over a period of 15 minutes to 72 hours, preferably

0 up to 24 hours. More preferably, the heat treatment is performed at a temperature of 160 ° C to 200 ° C for a period of 30 minutes to 4 hours. Good results have been obtained while heating for 8 hours at 100 ° C, as well as while heating for 2 hours at 175 ° C. Through preliminary experiments, a person skilled in this

-4444 field can define the conditions of the heat treatment that provide the desired result. It is noted that the longer the heat treatment takes, the higher the amount of alumoxane fixed to the support material. Heat treatment is carried out under reduced pressure or under an inert atmosphere, such as nitrogen gas, but preferably under reduced pressure. Depending on the conditions in the heating step, the alumoxane can be attached to the support material to such a high degree that the washing step can be skipped.

In optional wash step B, the number of washes and the solvent used are such that sufficient amounts of unbound alumoxane are removed to give the supported catalyst component of the invention. The washing conditions should be such that the unbound alumoxane is soluble in the washing solvent. The alumoxane containing support material, already subjected to heat treatment, preferably undergoes one to five washing steps using an aromatic hydrocarbon solvent, at a temperature of 0 ° C to 110 ° C. More preferably, the temperature is from 20 ° C to 1OO ° C. Preferred examples of aromatic solvents include toluene, benzene, and xylenes. More preferably, the aromatic hydrocarbon solvent is toluene. At the end of the washing treatment, the solvent is removed using a technique that also removes the alumoxane

-4545 dissolved in the solvent, such as by filtration or decantation. Preferably, the wash solvent is removed to provide a free flowing powder of the supported catalyst component.

The wash step can conveniently be performed under reflux conditions of the wash solvent. The wash step under reflux conditions allows to control the particle size distribution properties, preferably to give a distribution similar to that of the starting support material, and has also been found to give a supported catalyst that has a higher polymerization activity. Typically, the supported catalyst component, after the heating step, is formed into a paste in an aromatic hydrocarbon, and the paste is refluxed or heated to the boiling point of the aromatic hydrocarbon. The paste is kept under these reflux conditions for 5 minutes up to 72 hours. Any agglomerated particles that may have formed during the heating step will deagglomerate or disperse during the wash step in the reflux condition. The longer the reflux conditions are maintained, the better the dispersion obtained. The concentration of the supported catalyst component in the aromatic hydrocarbon is not critical, but is typically on the scale of 1 to 500 grams per liter of hydrocarbon, preferably 10

-4646 to 250 grams per liter. Preferred examples of aromatic hydrocarbons include toluene, benzene, and xylenes. More preferably, the aromatic hydrocarbon solvent is toluene. During the reflux step, agitation can be applied.

The supported catalyst component of the present invention, after the wash or reflux steps described above, is preferably subjected to a dispersion treatment before combining the supported catalyst component with the transition metal compound. This has been found to increase the catalytic activity of the final supported catalyst. In general, a hydrocarbon is used as a dispersion medium, such as aliphatic, cycloaliphatic, or aromatic hydrocarbons. Suitable examples are aliphatic hydrocarbons of 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or mixtures thereof. Temperature is not critical, but is conveniently on the scale of 0 ° C to 50 ° C. The duration is generally from at least 5 minutes to 72 hours. The upper limit is not critical, but is determined by practical considerations.

The preferred transition metal compound is added after the heating step, and more preferably after both the heating step and the optional washing and dispersing steps. If the metal compound

Transition -4747 is added before any of these steps, care must be taken not to subject the transition metal to temperatures that are too high to cause decomposition or inactivation. Conveniently, the transition metal compound is added after the washing step, in order to prevent the transition metal from fading from the support material along with the alumoxane.

The transition metal is contacted with the support material-containing alumoxane and preferably with the supported catalyst component of the present invention, in a diluent, preferably under conditions such that the transition metal compound is soluble. Suitable diluents include aliphatic and aromatic hydrocarbons, preferably an aliphatic hydrocarbon such as, for example, hexane. The metallocene is preferably added to a paste of the support material, conveniently dissolved in the same diluent in which the paste of the support material was made. In general, the alumoxane containing support material is formed into a paste in the diluent in concentrations of 1 to 20, preferably 2 to 10 weight percent. Contact time and temperature are not critical. Preferably, the temperature is from 10 ° C to 60 ° C, more preferably from 20 ° C to 45 ° C. Contact time is 5 minutes to 100 hours, preferably 0.5 hours to 3 hours. Typically, the diluent is removed after adding the

-4848 metallocene. This can be done by any suitable technique, such as the application of heat and / or reduced pressure, evaporation, filtration, or decantation, or any combination thereof. If heat is applied, the temperature should not exceed the decomposition temperature of the metallocene.

It may be desirable to subject an olefin, in the presence of the supported catalyst, to polymerization conditions to provide a previously polymerized supported catalyst.

In a highly preferred embodiment, the process for preparing a supported catalyst comprises:

Heat, at a temperature of 75 ° C to 250 ° C, under an inert atmosphere, preferably under reduced pressure, a silica support material containing methylalumoxane;

optionally followed by subjecting the product from the heating step to one or more washing steps using toluene;

thereby selecting the conditions in the heating step and in the washing step, to form a supported catalyst component, where no more than 9 percent of the aluminum present in the supported catalyst component can be removed in one extraction hour with toluene at 90 ° C, using one gram of catalyst component supported by 10 milliliters of toluene; and

-4949 adding, after the heating step and optional washing step, a transition metal compound selected from a bridged monocyclopentadienyl Group 4 transition metal compound or mono (substituted cyclopentadienyl), or a compound of bridged bis-cyclopentadienyl or bis (substituted cyclopentadienyl) Group 4 transition metal, provided that once the transition metal compound has been added, the product thus obtained is not subjected to temperatures equal to, or higher than, its decomposition temperature.

Preferably, the supported catalyst thus prepared contains 20 to 40 weight percent aluminum, based on the total weight of the support material and alumoxane. Conveniently, the molar ratio of the aluminum atom to the transition metal atom in the supported catalyst thus formed is 25 to 1000. Preferably, the supported catalyst thus formed contains 0.1 to 1000 micromoles of metal compound of transition per gram of support material.

The supported catalyst thus obtained can be used as such, without isolation or purification, but is preferably recovered first in the form of free-flowing particles. The isolated catalyst can be stored under an inert atmosphere for an extended period of time, for example, for one to several months. Before use, the

-5050 supported catalyst can easily be re-formed into a paste in a diluent, preferably a hydrocarbon. The present supported catalyst does not require additional activators or cocatalysts.

In a further aspect, the present invention provides an addition polymerization process, wherein one or more addition polymerizable monomers are contacted with the supported catalyst according to the invention, under addition polymerization conditions.

Suitable addition polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or unconjugated dienes, polyenes, and carbon monoxide. Preferred monomers include olefins, for example, alpha-olefins having from 2 to 20, preferably from 2 to 12, more preferably, from 2 to 8 carbon atoms, and combinations of two or more of these alpha-olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-niene, 1-decene, 1undecene , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof. Preferably the alphaolefins are ethylene, propene, 1-butene, 4-methylpentene-l, 1hexene, 1-octene, and combinations of ethylene and / or propene with one or more of these other alpha-olefins. Other preferred monomers include styrene, styrenes substituted by

-5151 halogen or by alkyl, vinyl chloride, acrylonitrile, methyl acrylate, methyl methacrylate, tetrafluoroethylene, methacrylonitrile, vinylidene chloride, vinylcyclobutene, 1,4-hexadiene, and 1,7-octadiene. Suitable addition polymerizable monomers also include any mixtures of the aforementioned monomers.

The supported catalyst can be formed on site, in the polymerization mixture, by introducing into said mixture both a supported catalyst component of the present invention and a suitable metallocene component. The supported catalyst component and supported catalyst of the present invention can be conveniently employed in a high pressure, solution, paste, or gas phase polymerization process. A high pressure process is normally performed at temperatures from 100 ° C to 400 ° C, and at pressures greater than 500 bar. A paste process typically uses an inert hydrocarbon diluent and temperatures from 0 ° C to a temperature just less than the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. The preferred temperatures are from 20 ° C to 115 ° C, preferably from 60 ° C to 105 ° C. The solution process is performed at temperatures from the temperature at which the resulting polymer is soluble in an inert solvent to 275 ° C. In general, the solubility of the polymer depends on its

-5252 density. For ethylene copolymers having densities of 0.86 grams / cubic centimeter, solution polymerization can be accomplished at temperatures as low as 60 ° C. Preferably, the solution polymerization temperatures are from 75 ° C to 260 ° C, more preferably from 80 ° C to 170 ° C. As inert solvents, hydrocarbons are typically used, and preferably aliphatic hydrocarbons. Solution and paste processes are normally carried out at pressures between 1 and 100 bar. Typical operating conditions for gas phase polymerizations are from 20 ° C to 100 ° C, more preferably from 40 ° C to 80 ° C. In gas phase processes, the pressure is typically from sub-atmospheric to 100 bar. Typical gas phase polymerization processes are described in US Patent Nos. 4,588,790; 4,543,399; 5,352,749; 5,405,922, and in US Patent Application Serial Number 122,582, filed on September 17, 1993 (corresponding to International Patent Number WO 9507942).

Preferably, for use in gas phase polymerization processes, the support has an average particle diameter of 20 to 200 microns, more preferably 30 microns to 150 microns, and most preferably 35 microns to 100 microns. Preferably, for use in paste polymerization processes, the support has a diameter of

-5353 average particles from 1 to 200 micras, more preferably from 5 micras to 100 micras, and most preferably from 20 micras to 80 micras. Preferably, for use in solution or high pressure polymerization processes, the support has an average particle diameter of from 1 to 40 microns, more preferably from 2 microns to 30 microns, and most preferably from 3 microns to 20 microns.

The supported catalysts of the present invention, when used in a paste process or a gas phase process, can not only produce ethylene copolymers of typical densities for high-density polyethylene, on the scale of 0.970 to 0.940 grams / cubic centimeter, but surprisingly, they also make it possible to produce copolymers that have substantially lower densities. Copolymers of densities less than 0.940 grams / cubic centimeter and especially less than 0.930 grams / cubic centimeter can be made and down to 0.880 grams / cubic centimeter or less, while retaining good bulk density properties, and while preventing or contamination from the reactor is substantially eliminated. The present invention can produce polymers and copolymers of ethylene with weight average molecular weights of up to 1,000,000 and even higher.

In the polymerization process of the present invention, impurity removers can be used, the

-5454 which serve to protect the supported catalyst from catalyst poisons, such as water, oxygen, and polar compounds. These scavengers can generally be used in amounts dependent on the amounts of impurities, and are typically added to the monomer and diluent feed, or to the reactor. Typical scavengers include alkyl aluminum or boron compounds and alumoxanes.

In the present polymerization process, too, molecular weight control agents such as hydrogen or other chain transfer agents can be used.

Having described the invention, the following examples are provided as another illustration thereof, and are not to be construed as limiting. Unless otherwise stated, all parts and percentages are expressed on a weight basis.

Examples

In the examples, the following support materials were used: granular silica available from Grace GmbH under the designation SD 3216.30; a spherical agglomerated silica available as SYLOPOL 2212 from Grace Davison (division of WR Grace & Co) having a surface area of 250 square meters / gram, and a pore volume of 1.4 cubic centimeters / gram. Unless otherwise indicated

-5555 way, the silicas used have been heated at 250 ° C for 3 hours under vacuum, to give a final water content of substantially 0, determined by differential scanning calorimetry. Where water-containing silica was used, it was used as supplied, without prior heat treatment.

Alumoxane was used as a 10 weight percent solution of methyl alumoxane (MAO) in toluene, available from Witco GmbH. Metallocene was used as a 0.0714 M solution of {(tertiary butyl amido) (tetramethyl-η5cyclopentadienyl) (dimethyl) silane} titanium-dimethyl (hereinafter MCpTi) in ISOPARMR E (registered trademark of Exxon Chemical Company).

The bulk density of the polymers produced was determined according to ASTM 1895. The aluminum content on the support material was determined by its treatment with sulfuric acid, followed by addition of EDTA, and return titration with zinc chloride.

All experiments were performed under a nitrogen atmosphere, unless otherwise indicated.

Example 1

A 1000 milliliter flask was charged with 11.1 grams of silica SD 3216.30. 300 grams of a methyl alumoxane solution were added, and the mixture was stirred for

-5656 hours. The solvent was then removed under reduced pressure at 20 ° C, to give 38 grams of a free-flowing powder, with an aluminum content of 31.6%. The sample was divided into four equal 9-gram portions, and each was heated at a different temperature for 2 hours under reduced pressure. After this treatment, the aluminum content of each sample was measured, and then each was formed into a toluene paste (100 milliliters), and the mixture was stirred for 1 hour, filtered, and then the supports were washed with two 50 milliliter portions of fresh toluene, and vacuum dried at 120 ° C for 1 hour. The results of the aluminum analyzes are summarized below.

Table I - Heat Treatment / Toluene Wash at Room Temperature

<td>T [° C]</td><td>[Al] After Heating {% in weigh)</td><td>[Al] After Washed (% in weigh)</td>

The previous procedure was repeated, but with 12.1 grams of silica, and 327 grams of alumoxane solution

-5757 methyl to give 42 grams of a free-flowing powder that has an aluminum content of 31.3 percent. This sample was divided into four equal portions, and each was heated as described above, and then underwent the same washing procedure, except that toluene was used at 90 ° C. The results are summarized in Table II.

Table II - Heat Treatment / Washing with Toluene at 90 ° C

<td>TPC]</td><td>[Al] After Heating (% in weigh)</td><td>[Al] After Washed (% in weigh)</td>

These examples show that, for duration heat treatments, an increase in heat treatment temperature results in more alumoxane being fixed in the silica. Washing with toluene at 90 ° C results in a higher percentage of unfixed aluminum being removed, compared to washing with toluene at room temperature for washing treatments of the same duration.

-5858

Example ...... 2

A 250 milliliter flask was charged with 6.2 grams of SD 3216.30 silica. 168 grams of methyl alumoxane solution were added, and the mixture was stirred for 16 hours. After this time, toluene was removed under reduced pressure at 20 ° C, and then the solids were dried in vacuo for 16 hours at 20 ° C to give a free-flowing powder. The weight of the solid was 22.1 grams, and the aluminum content was 26.8 percent.

Example 3

The procedure of Example 2 was repeated, using 3 grams of silica and 56.6 grams of methyl alumoxane solution, to give 7.6 grams of a free-flowing powder, with an aluminum content of 26.1 percent. 5.2 grams of this support were formed into a toluene paste (50 milliliters) at 20 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 20 milliliter portions of fresh toluene, and then vacuum dried at 20 ° C for 1 hour. The weight was 3.0 grams, and the aluminum content was 18.2 percent.

Example 4

The procedure of Example 2 was repeated, using 3 grams of silica and 75.6 grams of alumoxane solution

-5959 methyl, to give a free-flowing powder. This powder was then heated at 100 ° C for 2 hours under vacuum. The weight was

8.4 grams, and the aluminum content was 29.0 percent. 4.4 grams of this support were formed into a toluene paste (50 milliliters) at 20 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 20 milliliter portions of fresh toluene, and then vacuum dried at 20 ° C for 1 hour. The weight was 2.2 grams, and the aluminum content was 17.3 percent.

Example 5

The procedure of Example 2 was repeated, using 3 grams of silica and 56.6 grams of methyl alumoxane solution, to give a free-flowing powder. The powder was heated for 2 hours at 150 ° C under vacuum. The weight obtained was 7.2 grams, and the aluminum content was 26.6 percent.

Example 6

The procedure of Example 2 was repeated, using a 1000 milliliter flask, 12.1 grams of silica, and 327 grams of methyl alumoxane solution, to give a free-flowing powder. Then 9.5 grams of this powder were heated at 175 ° C for 2 hours under vacuum. Aluminum content was measured as 30.7 percent. 2.7 grams of support se

-6060 formed into a paste in hexane (40 milliliters) at 20 ° C, and the mixture was stirred for 4 hours. The mixture was filtered, and the support was washed with two 30 milliliter portions of fresh hexane, and then vacuum dried at 20 ° C for 1 hour. The weight was 2.4 grams, and the aluminum content was

30.4 percent.

Example 7

The procedure of Example 2 was followed. This powder was then heated at 150 ° C for 2 hours under vacuum. The weight was 7.25 grams, and the aluminum content was 26.6 percent. 3 grams of the obtained support were formed into a toluene paste (40 milliliters) at 20 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 10 milliliter portions of fresh toluene, and then vacuum dried at 20 ° C for 1 hour. The weight was

2.4 grams, and the aluminum content was 24.1 percent.

Example 9

The procedure of Example 2 was repeated, using 3 grams of silica and 75.5 grams of methyl alumoxane solution, to give a free-flowing powder. This powder was heated at 150 ° C for 2 hours under vacuum. The weight was 8.4 grams, and the aluminum content was 29.8 percent.

-6161 grams of this support was formed into a toluene paste (40 milliliters) at 20 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 20 milliliter portions of fresh toluene, and then vacuum dried at 20 ° C for 1 hour. The weight was 4.5 grams, and the aluminum content was 28.9 percent.

Example 9

The procedure of Example 2 was repeated, using a 1000 milliliter flask, 9.1 grams of silica, and 246 grams of methyl alumoxane solution, to give a free-flowing powder. This powder was then heated at 150 ° C for 2 hours under vacuum. The weight was 29.0 grams, and the aluminum content was 29.6 percent. This support was formed into a toluene paste (300 milliliters) at 20 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 100 milliliter portions of fresh toluene, and then vacuum dried at 20 ° C for 1 hour. The weight was 24.3 grams and the aluminum content was 28.5 percent.

Example 10

The procedure of Example 2 was repeated, using 5 grams of silica and 101 grams of methyl alumoxane solution, to give a free-flowing powder. The dust will

-6262 heated at 175 ° C for 2 hours under vacuum. The aluminum content of this material was 28.8 percent. The powder (12.8 grams) was re-formed into a toluene paste (130 milliliters) and the mixture was heated to 90 ° C, and stirred for 1 hour. The mixture was filtered, and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. The support was then dried under vacuum at 120 ° C for 1 hour. 10.4 grams of support was obtained having an aluminum content of 26.3 percent.

Example 11

The procedure of Example 2 was repeated, using 10 grams of silica and 76 grams of methyl alumoxane solution, to give a free-flowing powder. This powder was heated at 175 ° C for 2 hours under vacuum. The aluminum content of this material was 17.2 percent. The powder (15.6 grams) was re-formed into a toluene paste (150 milliliters), and the mixture was heated to 90 ° C, and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. The support was then dried under vacuum at 120 ° C for 1 hour. 13.0 grams of support were obtained with an aluminum content of 16.3 percent.

-6363

Example 12

The procedure of Example 2 was repeated, using 5 grams of SD 3216.30 silica with a 2.8 percent water content, and 101 grams of methyl alumoxane solution, to give a free-flowing powder. This powder was heated at 175 ° C for 2 hours under vacuum. The aluminum content of this material was 29.4 percent. The powder (13 grams) was re-formed into a toluene paste (130 milliliters), and the mixture was heated to 90 ° C, and stirred for 1 hour. The mixture was filtered, and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. The support was then dried under vacuum at 120 ° C for 1 hour. 11.5 grams of support were obtained with an aluminum content of 29.0 percent.

Example 13

The procedure of Example 2 was repeated, using a 1000 milliliter flask, 9 grams of SYLOPOL 2212 and 243 grams of methyl alumoxane solution, to give a free-flowing powder. This powder was heated at 150 ° C for 2 hours under vacuum. The weight was 29.3 grams, and the aluminum content was 29.8 percent. This support was formed into a toluene paste (300 milliliters) at 20 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 100 milliliter portions of fresh toluene, and

-6464 then vacuum dried at 120 ° C for 1 hour. The weight was 25.9 grams, and the aluminum content was 29.3 percent.

Example 14

The procedure of Example 2 was repeated, using a 1000 milliliter flask, 9.1 grams of silica, and 246 grams of methyl alumoxane solution, to give a free-flowing powder. This powder was heated at 175 ° C for 2 hours under vacuum. The weight of 30.8 grams, and the aluminum content was 30.0 percent. This support was formed into a toluene paste (300 milliliters) at 20 ° C and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 100 milliliter portions of fresh toluene, and then dried under vacuum at 120 ° C for 1 hour. The weight was 27.1 grams, and the aluminum content was 29.0 percent.

Example 15

The procedure of Example 2 was repeated, using 5. 1 grams of silica and 101 grams of methyl alumoxane solution, to give a free-flowing powder. 6.8 grams of this powder were heated at 100 ° C for 2 hours under vacuum. The support was then formed into a toluene paste (100 milliliters) at 90 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two portions of 50

-6565 milliliters of fresh toluene (90 ° C), and then vacuum dried at 1OO ° C for 1 hour. The weight was 3.4 grams, and the aluminum content was 16.6 percent.

Example 16

The procedure of Example 2 was repeated, using 5. 1 grams of silica and 101 grams of methyl alumoxane solution, to give a free-flowing powder. 6.8 grams of this powder were formed into a toluene paste (100 milliliters) at 90 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 50 milliliter portions of fresh toluene (90 ° C), and then vacuum dried at 100 ° C for 1 hour. The weight was 3.0 grams, and the aluminum content was 13.4 percent.

Example 17

The procedure of Example 2 was repeated, using 5 grams of SD 3216.30 silica containing 2.8 percent water, and 101 grams of methyl alumoxane solution, to give a free-flowing powder. 6 grams of this powder were formed into a toluene paste (100 milliliters) at 90 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 50 milliliter portions of fresh toluene (90 ° C), and then vacuum dried at 20 ° C for 1 hour. The weight was 2.9 grams, and the aluminum content was

-6666

16.4 percent.

Example 18

The procedure of Example 2 was repeated, using 5 grams of SD 3216.30 silica, containing 2.8 percent water, and 101 grams of methyl alumoxane solution, to give a free-flowing powder. This powder was heated at 100 ° C for 2 hours, 6 grams of this powder was formed into a toluene paste (100 milliliters) at 90 ° C, and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 50 milliliter portions of fresh toluene (90 ° C), and then vacuum dried at 20 ° C for 1 hour. The weight was 3.8 grams, and the aluminum content was 22.2 percent.

Example 9

Preparation of supported catalysts

Supported catalysts were separated from the supported catalyst components prepared in Examples 2 to 18, according to the following procedure.

Typically, 1 gram of support component was formed into a paste in 20 milliliters of hexane, and the mixture was stirred for 30 minutes. An aliquot of MCpTi ¢ 0.0714 M) solution sufficient to give a transition metal charge was added as shown in Table III. This mixture is

-6767 was stirred for 30 minutes, and then transferred to a polymerization reactor.

Polymerization

A 10 liter autoclave reactor was charged with 6 liters of anhydrous hexane, comonomer if required, hydrogen gas if required, and the contents heated to 80 ° C, unless otherwise reported. Ethylene was added to raise the pressure to the desired level. The amount of the supported catalyst indicated in Table III was added through a pressurized addition cylinder. Ethylene was continuously supplied to the reactor on demand. After the desired polymerization time, the ethylene line was blocked, and the contents of the reactor were turned into a sample container. The hexane was decanted from the polymer, and the polymer was dried overnight, and then weighed to determine the yield.

In Test 22, the temperature was 70 ° C, and 100 milliliters of 1-octene comonomer was added to the reactor, to give an ethylene / l-octene copolymer of a density of 0.9266 grams / cubic centimeter. In Test 23, the temperature was 50 ° C, and 200 milliliters of l-octene comonomer was added to the reactor, to give an ethylene / loctene copolymer of a density of 0.9230 grams / cubic centimeter.

The specific polymerization conditions and the

-6868 results are summarized in Table III. The data in this table shows that high bulk density polymers can be prepared from supported catalyst components prepared with different combinations of heat and / or wash treatments. The highest efficiencies result from supported catalyst components and catalysts that contain more than 2 0 percent Al by weight. Superior efficiencies are obtained from supported catalyst components subjected to dispersion in toluene at 90 ° C. Poor bulk densities (test 1 to 3) result from the supported catalyst compon ents that have not been heat treated at a sufficiently high temperature, or for a sufficiently long time, or have not been sufficiently washed.

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-7171

Example 20

The procedure of Example 2 was repeated, using 6.2 grams of SD 3216.30 silica, and 68 grams of methyl alumoxane solution, to give 22.1 grams of free-flowing powder, with an aluminum content of 27.8 percent. 11 grams of this support was formed into a toluene paste (75 milliliters), and 440 micromoles of MCpTi (6.16 milliliters of a 0.0714M solution in hexane) were added. The mixture was stirred for 1 hour, and then the solvent was removed under reduced pressure, and the residue was heated at 150 ° C for 2 hours. This produced 11 grams of a free-flowing powder with an aluminum content of 28.2 percent. The material was formed into a toluene paste (100 milliliters), and the mixture was stirred for 1 hour, filtered, and the solids were washed with two 50 milliliter portions of fresh toluene, and then vacuum dried at 100 ° C for 1 hour. The weight was 9 grams, the aluminum content was 24.8 percent, and the Ti content was 40 micromoles / gram.

Example 21

The procedure of Example 6 was repeated, using 12.1 grams of SD 3216.30 silica, and 327 grams of methyl alumoxane solution, to give a free-flowing powder. 9.1 grams of this powder were heated at 150 ° C under vacuum for 2 hours, to give a material with an aluminum content of

-7272

30.7 percent. 3.5 grams of this powder were formed into a toluene paste (35 milliliters), and 140 micromoles of MCpTi (1.96 milliliters of a 0.0714M solution in hexane) were added and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with 6 50-milliliter portions of fresh toluene (at which point, the washes were colorless), and then vacuum dried at 20 ° C for 1 hour. The weight was 22.0 grams, the Ti content was 30 micromoles / gram.

Example 22

The procedure of Example 2 was repeated, using 3. 0 grams of SD 3216.30 silica, and 82 grams of methyl alumoxane solution, to give 10.5 grams of a free-flowing powder. 4.85 grams of this powder were formed into a toluene paste (50 milliliters), and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 20 milliliter portions of fresh toluene, and then heated under vacuum at 150 ° C for 2 hours. The weight was 2.1 grams, and the aluminum content was 14.9 percent. Added

MCpTi according to the procedure of Example 19.

Example 23

A 250 milliliter flask was charged with 3.3 grams 25 of silica SD 3216.30. Toluene (80 milliliters) was added to the

-7373 paste, followed by 130 micromoles of MCpTi (1.82 milliliters of a 0.0714M solution in hexane), and the mixture was stirred for 2 hours. 101 grams of methyl alumoxane solution were added, and the mixture was stirred for 16 hours. After this time, the solvent was removed under reduced pressure, at

20 ° C, to give a free flowing powder.

Following the general polymerization procedure of Example 19, using the specific conditions mentioned in Table IV, the results indicated in the same Table were obtained.

The data in this table shows that a low activity catalyst results when metallocene is added prior to heat treatment at 150 ° C (Example 20). Reasonable bulk density is obtained when metallocene is added after the heat step, but before the wash step (Example 21). A good bulk density results when the washing step is performed before the heating step (Example 22). An inactive catalyst results when the metallocene is first added to the silica (Example 23).

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Example 24

The procedure of Example 1 was repeated, except that after removing the solvent from the methyl alumoxane / silica mixture under reduced pressure at 20 ° C, parts of the resulting powder were subjected to 2-hour heat treatments, and optional wash treatments , as summarized in Table V. After these treatments, the catalyst components supported on the one hand, were extracted with toluene at 90 ° C to establish the percentage of aluminum extractables, and on the other hand, they were used in the polymerization reactions. All washing and extraction steps were performed with 1 gram of support per 10 milliliters of toluene, stirred for 1 hour, then filtered and washed twice with 5 milliliters of toluene per gram of initial support. The supported catalysts were prepared according to the general procedure described in Example 19. All polymerizations were carried out at a total pressure of 15 bar at 80 ° C for 1 hour. The results are given in Table VI. The examples show that at percentages of removable aluminum well below 10 percent, excellent bulk densities are obtained.

Heat treatment at 175 ° C in Test 1 alone, without wash treatment, enabled polymers of good bulk density to be made.

-7676

Table V Extraction Test

<td>Test No.</td><td>About- I lie by heat Temp. [° C]</td><td>Washed with Toluene at 20 ° C</td><td>Al in the support catalyst [%]</td><td>The after the removal [%]</td><td>To the extracted [%]</td><td>Density at bulk [g / cm3]</td>

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-7878

Example 25

The procedure of Example 2 was repeated, using 5 grams of silica and 101 grams of methyl alumoxane solution, to give a free-flowing powder. The powder was heated at 100 ° C for 8 hours under vacuum, to give 12.5 grams of the material. The support was then formed into a toluene paste (125 milliliters) at 90 ° C and the mixture was stirred for 1 hour. The mixture was filtered, and the support was washed with two 50 milliliter portions of fresh toluene (90 ° C), and then vacuum dried at 100 ° C for 1 hour. The weight was 11.1 grams and the aluminum content was measured as 26.1 weight percent. In accordance with the procedures of Example 19 and using the amounts in Table VII, a polymerization experiment was performed at a total pressure of 15 bar, 80 ° C for 1 hour. The results are included in the Table

VII.

Table VII - Polymerization Test

<td>You2[/ unol / g]</td><td>Al / Ti3</td><td>[You]4(μιηοΙ)</td><td>Surrender- I lie7(g)</td><td>E (Ti)8[gPEZg Ti / hr]</td><td>E (YES / [gPEZ- gSiO2/ hr]</td><td>E (A1)10[gPEZ- gAl / hr]</td><td>Density at bulk (gZcm3)</td>

The footers are the same as in Table IIL

-7979

Example 26

The procedure of Example 5 of US Patent No. 5,240,894 was essentially repeated to form a supported catalyst component as follows. 0.58 micromoles of MCpTi (8.1 milliliters of a 0.0714M solution) was added to 35 milliliters of toluene. To this were added 75 milliliters of 10 weight percent methyl alumoxane, in toluene, and the mixture was stirred for 15 minutes. Silica (5 grams, SD 3216.30, previously treated at 250 ° C for 3 hours) was added, and the mixture was stirred for 20 minutes. The mixture was heated at 65 ° C under vacuum for 75 minutes, and the dry solid was washed with 2 x 70 milliliters of pentane, filtered, and dried under high vacuum, to give a yellow solid (8 grams), with an aluminum content of 18.1 percent by weight. Extraction with toluene at 90 ° C, followed by drying, gave a yellow solid with an aluminum content of 16.2 weight percent. The percentage of removable aluminum is 10.5 percent. Upon washing, some MCpTi was lost, and also upon extraction with hot toluene, as indicated by the yellow color of the supernatant. Polymerization experiments were performed following the general procedure of Example 19, with a supported catalyst that was not treated with hot toluene (Test 1), and with one that was treated with hot toluene (Test 2). The results are given in Table VIII.

-8080

The results show that the untreated toluene catalyst (which has 10.5 percent removable Al) gives a poor bulk density. Submission of the supported catalyst obtained to a hot toluene extraction greatly improves bulk density (Test 2).

Table VIII

<td>Proof No.</td><td>To the (%)</td><td>Time (min.)</td><td>performance (g)</td><td>Density Bulk (g / cm3)</td>

Example 27

A 1000 milliliter flask was charged with 508 grams of 10 percent methyl alumoxane solution in toluene, and 2.5 grams of SYLOPOL 2212 silica, with a water content of 3.5 percent, was added while continuously stirring. The mixture was stirred for another two hours and then the solvent was removed under reduced pressure at 20 ° C, to give a free-flowing powder. This powder was then heated at 175 ° C for 2 hours under vacuum. The powder was re-formed into a toluene paste (700 milliliters), and the mixture was heated and refluxed for 1 hour. The mixture is

-8181 filtered, and the support was washed with two 200 milliliter portions of fresh toluene at 100 ° C. The support was then dried under vacuum at 12 ° C for 1 hour. 63.9 grams of support were obtained, with an aluminum content of 26.4 percent. A sample of the support was formed into a toluene paste, stirred for 1 hour, and then the particle size distribution was measured on a Malvern mastersizer X instrument. This indicated that d (v, 0.5) was approximately 12 microns. In accordance with this procedure, other supported catalyst components were prepared with slightly different aluminum loads.

A weighted amount of the support components was formed into a hexane paste, and the mixture was stirred for 16 hours before the addition of the MCpTi component (tests 1 to 3) or {(tertiary butyl amido) (tetramethyl-T75-cyclocyclopentadienyl) (dimethyl) silane} titanium-i74-'l, 3-pentadiene (later in this MCpTi (II) in test 4). Subsequently, MCpTi or MCpTi (II) was added (in ISOPARMR Ξ) in the amounts indicated in Table IX. The supported catalysts thus prepared were subjected to paste polymerization, as generally described in Example 19, at 80 ° C. The other conditions and results are mentioned in Table IX. These results show that, by employing an extensive dispersion period before the transition metal compound is added, increased catalytic activity results (compare with Table III).

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-8383

Example 28

A 3 liter autoclave reactor was charged with an amount of 1-octene as indicated in Table X, followed by an amount of IsoparMR E enough to give a total volume of 1500 milliliters. 300 milliliters of hydrogen gas were added, and the contents of the reactor were heated to the desired temperature. Then ethylene was added, enough to bring the system pressure up to 30 bar. A supported catalyst was added to initiate polymerization, and ethylene was continuously supplied to the reactor on demand. After the desired polymerization time, the ethylene line was blocked, and the contents of the reactor were turned into a sample container. The polymer was dried overnight, and then weighed to determine catalyst efficiencies. The results are described in Table X, where the molecular weight distribution (1 ^ / ^) is derived from gel permeation chromatography, and fusion index I2 it is determined according to ASRM D-1238-65T (at 190 ° C and with a load of 2.16 kilograms).

The following supported catalysts were used in the polymerizations. A support containing 23.8 percent aluminum on dehydrated SD 3216.30 silica was prepared in a similar manner to Example 10. In tests 1 to 3, 0.075 grams of support was formed into a paste in Isopar ^ R, and stirred for a few minutes.

-8484

An aliquot of MCpTi solution (0.0714M) was added, enough to give a titanium charge of 20 micromoles / gram. This mixture was stirred for a few minutes, and then transferred to the polymerization reactor. In tests 4 to 6, 0.3 grams of support was used, and the same load of titanium.

Table X

<td>Test No.</td><td>1-octe- not [me]</td><td>Weather [min]</td><td>Surrender- I lie [thank- mos]</td><td>Tempe- race I promise it gave [° C]</td><td>Efficien- Inc [gPE / - gTi]</td><td>h [g / 10 min]</td><td>Densi- give [g / cm3]</td><td>"TO</td>

When used in a solution polymerization process, supported catalysts show good efficiencies, and make polymers of a narrow molecular weight distribution.

Example 29

In the present example, continuous polymerization tests are described. These tests were performed using a supported catalyst prepared according to a procedure similar to that of Example 27. The support contained 25 weight percent aluminum. In all tests, the MCpTi load was 40 micromol / gram.

Isopentane, ethylene, 1-butene, hydrogen, and supported catalyst were continuously fed into a continuously stirred 10-liter jacketed tank reactor, and the formed pulp product was continuously stirred. The total pressure in all polymerization tests was 15 bar. The removed paste was fed into an evaporation tank, to remove the diluent, and the dry free flowing polymer powder was collected. Table XI summarizes the conditions and properties of the products made. Melt index values were measured according to ASTM

D-1238-65T (at 190 ° C, and with a load of 21.6 kilograms, abbreviated as I2i). The butene content of the polymer was determined by infrared spectroscopy. The results indicate that high density polymer powders can be produced in bulk over a wide density range, retaining the morphology of the particles.

-8686

Table XI

<td>Prue- ba No.</td><td>Isopentane flow [g / h]</td><td>Hugo of ethylene [g / h]</td><td>Flow of butene [g / h]</td><td>Flow of Hydro- Gen [1 hour]</td><td>T (° C)</td><td>[g / io min]</td><td>Densi- give [g / - cm3]</td><td>Butene content in the polymer [% by weight]</td><td>Bulk density(fi\ cmq</td>

-8787

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34098994	United States of America	A	1994-11-17
9514192	United States of America	W	1995-11-02

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CA2205376A1	Canada	A1	1996-05-30
WO9616092A1	World Intellectual Property Organization (WIPO)	A1	1996-05-30
AU4019795A	Australia	A	1996-06-17
IL117408D0	Israel	D0	1996-07-23
CA2214885A1	Canada	A1	1996-09-19
WO9628480A1	World Intellectual Property Organization (WIPO)	A1	1996-09-19
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CN1164241A	China	A	1997-11-05
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PL322177A1	Poland	A1	1998-01-19
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CZ285397A3	Czechia	A3	1998-02-18
CN1181091A	China	A	1998-05-06
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EP0856014A1	European Patent Office (EPO)	A1	1998-08-05
HU9801224A2	Hungary	A2	1998-08-28
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MY113329A	Malaysia	A	2002-01-31
EP0792297B1	European Patent Office (EPO)	B1	2002-12-18
US6506866B2	United States of America	B2	2003-01-14
AT229987T	Austria	T	2003-01-15
ATE229987T1	Austria	T1	2003-01-15
DE69529230D1	Germany	D1	2003-01-30
EP0856014B1	European Patent Office (EPO)	B1	2003-03-05
AT233790T	Austria	T	2003-03-15
ATE233790T1	Austria	T1	2003-03-15
DE69626531D1	Germany	D1	2003-04-10
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Abstract

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PCT

0W1W1W7 1147: 40 PWJO-1-1 SUPPORTED CATALYST COMPONENT, SUPPORTED CATALYST,

YOUR PREPARATION AND ADDITIONAL POLYMERIZATION PROCESS

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