US20060247397A1 - Supported olefin polymerization catalyst - Google Patents

Supported olefin polymerization catalyst Download PDF

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US20060247397A1
US20060247397A1 US10/539,573 US53957305A US2006247397A1 US 20060247397 A1 US20060247397 A1 US 20060247397A1 US 53957305 A US53957305 A US 53957305A US 2006247397 A1 US2006247397 A1 US 2006247397A1
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catalyst system
supported catalyst
activator
group
support material
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Grant Jacobsen
Brian Kimberley
Sergio Mastroianni
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PetroIneos Europe Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to supported catalysts suitable for the polymerisation of olefins and in particular to supported catalysts suitable for the preparation of polymers having broad molecular weight distributions and improved melt strengths.
  • Metallocene catalysts offer the advantage of generally higher activity than traditional Ziegler catalysts and are usually described as catalysts which are single-site in nature. Because of their single-site nature the polyolefin copolymers produced by metallocene catalysts often are quite uniform in their molecular structure. For example, in comparison to traditional Ziegler produced materials, they have relatively narrow molecular weight distributions (MWD) and narrow Short Chain Branching Distribution (SCBD). Although certain properties of metallocene products are enhanced by narrow MWD, difficulties are often encountered in the processing of these materials into useful articles and films relative to Ziegler produced materials. In addition, the uniform nature of the SCBD of metallocene produced materials does not readily permit certain structures to be obtained.
  • MWD molecular weight distributions
  • SCBD Short Chain Branching Distribution
  • the metallocene complex comprises a bis(cyclopentadienyl) zirconium complex for example bis(cyclopentadienyl) zirconium dichloride or bis(tetramethylcyclopentadienyl) zirconium dichloride.
  • bis(cyclopentadienyl) zirconium complex for example bis(cyclopentadienyl) zirconium dichloride or bis(tetramethylcyclopentadienyl) zirconium dichloride. Examples of such complexes may be found in EP 129368, EP 206794, and EP 260130.
  • the metal complex is used in the presence of a suitable activator.
  • the activators most suitably used with such metallocene complexes are aluminoxanes, most suitably methyl aluminoxane (MAO).
  • Other suitable activators are boron compounds, in particular perfluorinated boron compounds.
  • complexes having a single or mono cyclopentadienyl ring have been developed. Such complexes have been referred to as ‘constrained geometry’ complexes and examples of these complexes may be found in EP 416815 or EP 420436. In such complexes the metal atom eg. zirconium or titanium is in the highest oxidation state.
  • activators are aluminoxanes, in particular methyl aluminoxane or compounds based on boron compounds.
  • boranes for example tris(pentafluorophenyl) borane, or borates such as trialkyl-substituted ammonium tetraphenyl- or tetrafluorophenyl-borates.
  • Catalyst systems incorporating such borate activators are described in EP 561479, EP 418044 and EP 551277.
  • metallocene complexes When used for the gas phase polymerisation of olefins, metallocene complexes may typically be supported for example on an inorganic oxide such as silica. Such supports may be typically dehydrated by calcining before use or may be pretreated with an organoaluminium compound to passivate the surface of the silica.
  • EP 495849 describes a silica supported catalyst system produced by reacting a mixture of triisobutylaluminium and trimethylaluminium with the water contained in an undehydrated support.
  • U.S. Pat. No. 5,834,393 describes in general terms the treatment of support materials with organomagnesium, organozinc, organoboron or organoaluminium compounds including mixtures thereof.
  • the reference generally describes the use of both dehydrated and hydrdrated supports.
  • WO 91/05810 describes the treatment of undehydrated silica with mixtures of trimethylaluminium and trisisobutylaluminium to produce silica-aluminoxane products subsequently treated with Group IVB and/or Group VB metallocenes.
  • WO 97/43323 describes in example 7 the addition of triethylaluminium to a calcined silica in the presence of a borate activator. The resultant silica is then further treated with trihexylaluminium.
  • dehydrated support material is meant support material substantially free of water.
  • Preferred support materials for use in the present invention are particulated solid support materials.
  • the support material may be any organic or inorganic inert solid. However particularly porous supports such as talc, inorganic oxides and resinous support materials such as polyolefins, which have well-known advantages in catalysis, are preferred. Suitable inorganic oxide materials which may be used include Group 2, 13, 14 or 15 metal oxides such as silica, alumina, silica-alumina and mixtures thereof.
  • inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania or zirconia.
  • suitable support materials may be employed such as finely divided polyolefins such as polyethylene.
  • Suitable volume average particle sizes of the support are from 1 to 1000 ⁇ m and preferably from 10 to 100 ⁇ m.
  • the most preferred support material for use with the supported catalysts according to the process of the present invention is silica.
  • Suitable silicas include Ineos ES70 and Davidson 948 silicas.
  • the support material may for example be subjected to a heat treatment in order to reduce the water content or the hydroxyl content of the support material.
  • the support material may be subjected to treatment at 100° C. to 1000° C. and preferably at 200 to 850° C. in an inert atmosphere under reduced pressure, for example, for 5 hrs.
  • the support material is contacted with the organoaluminium compounds at room temperature in a suitable solvent, for example hexane.
  • Preferred organoaluminium compounds are trialkyl aluminium compounds containing from 1 to 20 carbons atoms in each alkyl group.
  • Preferred trialkylaluminium compounds are trimethylaluminium, triethylaluminium, triisopropylaluminium and triisobutylaluminium.
  • the support material is contacted sequentially with the organoaluminium compounds.
  • the transition metal compound may be a compound of Groups IIIA to IIB of the Periodic Table of Elements (IUPAC Version). Examples of such transition metal compounds are traditional Ziegler Natta, vanadium and Phillips-type catalysts well known in the art.
  • the traditional Ziegler Natta catalysts include transition metal compounds from Groups IVA-VIA, in particular catalysts based on titanium compounds of formula MRx where M is titanium and R is halogen or a bydrocarbyloxy group and x is the oxidation state of the metal.
  • Such conventional type catalysts include TiCl 4 , TiBr 4 , Ti(OEt) 3 Cl, Ti(OEt) 2 Br 2 and similar.
  • Traditional Ziegler Natta catalysts are described in more detail in “Ziegler-Natta Catalysts and Polymerisation” by J. Boor, Academic Press, New York, 1979.
  • Vanadium based catalysts include vanadyl halides eg. VCl 4 , and alkoxy halides and alkoxides such as VOCl 3 , VOCl 2 (OBu), VCl 3 (OBu) and similar.
  • chromium catalyst compounds referred to as Phillips type catalysts include CrO 3 , chromocene, silyl chromate and similar and are described in U.S. Pat. No. 4,124,532, U.S. Pat. No. 4,302,565.
  • transition metal compounds are those based on the late transition metals (LTM) of Group VIII for example compounds containing iron, nickel, manganese, ruthenium, cobalt or palladium metals. Examples of such compounds are described in WO 98/27124 and WO 99/12981 and may be illustrated by [2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl 2 ], 2.6-diacetylpyridinebis (2,4,6-trimethylanil) FeCl 2 and [2,6-diacetylpyridinebis(2,6-diisopropylanil)CoCl 2 ].
  • LTM late transition metals
  • transition metal compounds include derivatives of Group IIIA, IVA or Lanthanide metals which are in the +2, +3 or +4 formal oxidation state.
  • Preferred compounds include metal complexes containing from 1 to 3 anionic or neutral ligand groups which may be cyclic or non-cyclic delocalized ⁇ -bonded anionic ligand groups. Examples of such ⁇ -bonded anionic ligand groups are conjugated or non-conjugated, cyclic or non-cyclic dienyl groups, allyl groups, boratabenzene groups, phosphole and arene groups.
  • ⁇ -bonded is meant that the ligand group is bonded to the metal by a sharing of electrons from a partially delocalised ⁇ -bond.
  • Each atom in the delocalized n-bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl, substituted metalloid radicals wherein the metalloid is selected from Group IVB of the Periodic Table. Included in the term “hydrocarbyl” are C1-C20 straight, branched and cyclic alkyl radicals, C6-C20 aromatic radicals, etc. In addition two or more such radicals may together form a fused ring system or they may form a metallocycle with the metal.
  • anionic, delocalised ⁇ -bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, etc. as well as phospboles and boratabenzene groups.
  • Phospholes are anionic ligands that are phosphorus containing analogues to the cyclopentadienyl groups. They are known in the art and described in WO 98/50392.
  • the boratabenzenes are anionic ligands that are boron containing analogues to benzene. They are known in the art and are described in Organometallics, 14, 1, 471-480 (1995).
  • the preferred polymerisation catalyst of the present invention is a bulky ligand compound also referred to as a metallocene complex containing at least one of the aforementioned delocalized ⁇ -bonded group, in particular cyclopentadienyl ligands.
  • metallocene complexes are those based on Group IVA metals for example titanium, zirconium and hafnium.
  • Metallocene complexes may be represented by the general formula: LxMQn where L is a cyclopentadienyl ligand, M is a Group IVA metal, Q is a leaving group and x and n are dependent upon the oxidation state of the metal.
  • the Group IVA metal is titanium, zirconium or hafnium, x is either 1 or 2 and typical leaving groups include halogen or hydrocarbyl.
  • the cyclopentadienyl ligands may be substituted for example by alkyl or alkenyl groups or may comprise a fused ring system such as indenyl or fluorenyl.
  • Such complexes may be unbridged eg. bis(cyclopentadienyl) zirconium dichloride, bis(pentamethyl)cyclopentadienyl dichloride, or may be bridged eg. ethylene bis(indenyl) zirconium dichloride or dimethylsilyl(indenyl) zirconium dichloride.
  • bis(cyclopentadienyl) metallocene complexes are those bis(cyclopentadienyl) diene complexes described in WO 96/04290.
  • Examples of such complexes are bis(cyclopentadienyl) zirconium (2.3-dimethyl-1,3-butadiene) and ethylene bis(indenyl) zirconium 1,4-diphenyl butadiene.
  • Cp is a single cyclopentadienyl or substituted cyclopentadienyl group optionally covalently bonded to M through a substituent
  • M is a Group VIA metal bound in a ⁇ 5 bonding mode to the cyclopentadienyl or substituted cyclopentadienyl group
  • X each occurrence is hydride or a moiety selected from the group consisting of halo, alkyl, aryl, aryloxy, alkoxy, alkoxyalkyl, amidoalkyl, siloxyalkyl etc. having up to 20 non-hydrogen atoms and neutral Lewis base ligands having up to 20 non-hydrogen atoms or optionally one X together with Cp forms a metallocycle with M and n is dependent upon the valency of the metal.
  • Particularly preferred monocyclopentadienyl complexes have the formula: wherein:—
  • R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said
  • R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system,
  • n is 1 or 2 depending on the valence of M.
  • Suitable monocyclopentadienyl complexes are (tert-butylamido) dimethyl(tetramethyl- ⁇ 5 -cyclopentadienyl) silanetitanium dichloride and (2-methoxyphenylamido)dimethyl(tetramethyl- ⁇ 5 -cyclopentadienyl) silanetitanium dichloride.
  • Suitable monocyclopentadienyl complexes are those comprising phosphinimine ligands described in WO 99/40125, WO 00/05237, WO 00/05238 and WO00/32653.
  • a typical examples of such a complex is cyclopentadienyl titanium [tri (tertiary butyl) phosphinimine] dichloride.
  • polymerisation catalyst suitable for use in the present invention are monocyclopentadienyl complexes comprising heteroallyl moieties such as zirconium (cyclopentadienyl)tris(diethylcarbamates) as described in U.S. Pat. No. 5,527,752 and WO 99/61486.
  • metallocene complexes for use in the preparation of the supported catalysts of the present invention may be represented by the general formula:
  • R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said
  • R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system.
  • Suitable X groups include s-trans- ⁇ 4 -1,4-diphenyl-1,3-butadiene, s-trans- ⁇ 4 -3-methyl-1,3-pentadiene; s-trans- ⁇ 4 -2,4-hexadiene; s-trans- ⁇ 4 -1,3-pentadiene; s-trans- ⁇ 4 -1,4-ditolyl-1,3-butadiene; s-trans- ⁇ 4 -1,4-bis(trimethylsilyl)-1,3-butadiene; s-cis- ⁇ 4 -3-methyl-1,3-pentadiene; s-cis- ⁇ 4 -1,4-dibenzyl-1,3-butadiene; s-cis- ⁇ 4 -1,3-pentadiene; s-cis- ⁇ 4 -1,4-bis(trimethylsilyl)-1,3-butadiene, said s-cis diene group forming
  • R′ is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, or phenyl or 2R′ groups (except hydrogen) are linked together, the entire C 5 R′ 4 group thereby being, for example, an indenyl, tetrahydroindenyl, fluorenyl, terahydrofluorenyl, or octahydrofluorenyl group.
  • Highly preferred Y groups are nitrogen or phosphorus containing groups containing a group corresponding to the formula —N(R′′)— or —P(R′′)— wherein R′′ is C 1-10 hydrocarbyl.
  • Most preferred complexes are amidosilane—or amidoalkanediyl complexes.
  • a particularly preferred complex for use in the preparation of the supported catalysts of the present invention is (t-butylamido) (tetramethyl- ⁇ 5 -cyclopentadienyl)dimethyl silanetitanium- ⁇ 4 -1.3-pentadiene.
  • Suitable activators for use with the supports of the present invention include aluminoxanes and organoboron compounds for example boranes.
  • Aluminoxanes are well known as activators for metallocene complexes.
  • Suitable aluminoxanes, for use in the present invention, include polymeric or oligomeric aluminoxanes in particular methyl aluminoxane (MAO).
  • MAO methyl aluminoxane
  • aluminoxanes suitable for use in the present invention may be commercially available materials or may be such commercially available material that has been dried under vacuum prior to its use for the preparation of the supported catalyst compositions.
  • Preferred organoboron compounds are triarylboron compounds, in particular perfluorinated triarylboron compounds.
  • the most preferred organoboron compound is tris(pentafluorophenyl) borane (FAB).
  • a particularly preferred activator component comprises an organoboron compound and an organoaluminium compound.
  • the organoaluminium compounds are as described above.
  • the preferred organoaluminium compounds are triethylaluminium or triisobutylaluminium.
  • a triarylboron compound for example tris(pentafluorophenyl) borane and a trialkylaluminium compound for example triethylaluminium is preferred as activator.
  • the ratio of boron/transition metal in this aspect of the present invention is typically in the range 0.1 to 10 and most preferably in the range 1 to 4.
  • Other compounds suitable as activators are compounds which comprise a cation and an anion.
  • the cation is typically a Bronsted acid capable of donating a proton and the anion is typically a compatible non-coordinating bulky species capable ofstabilizing the cation.
  • Such activators may be represented by the formula: (L*-H) + d (A d ⁇ )
  • L* is a neutral Lewis base
  • a d ⁇ is a non-coordinating compatible anion having a charge of d ⁇ , and
  • d is an integer from 1 to 3.
  • the cation of the ionic compound may be selected from the group consisting of acidic cations, carbonium cations, silylium cations, oxonium cations, organometallic cations and cationic oxidizing agents.
  • Suitably preferred cations include trihydrocarbyl substituted ammonium cations eg. triethylammonium, tripropylammonium, tri(n-butyl)ammonium and similar. Also suitable are N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations.
  • the preferred ionic compounds used as activators are those wherein the cation of the ionic compound comprises a hydrocarbyl substituted ammonium salt and the anion comprises an aryl substituted borate.
  • Typical borates suitable as ionic compounds include:
  • the most preferred activators of this type are those wherein the anion comprises a boron atom.
  • a preferred type of activator suitable for use with the metallocene complexes of the present invention comprise ionic compounds comprising a cation and an anion wherein the anion has at least one substituent comprising a moiety having an active hydrogen.
  • Suitable cations for this type of activator include triethylammonium, triisopropylammonium, diethylmethylammonium, dibutylethylammonium and similar.
  • Particularly suitable are those cations having longer alkyl chains such as dihexyldecylmethylaammonium, dioctadecylmethylammonium, ditetradecylmethylammonium, bis(hydrogentated tallow alkyl)methylammonium and similar.
  • Particular preferred activators of this type are alkylammonium tris(pentafluorophenyl) 4-(hydroxyphenyl)borates.
  • a particularly preferred activator is bis(hydrogenated tallow alkyl)methyl ammonium tris(pentafluorophenyl) (4 hydroxyphenyl)borate.
  • a preferred compound is the reaction product of an alkylammonium tris(pentaflurophenyl)-4-(hydroxyphenyl)borate and an organometallic compound, for example triethylaluminium.
  • the supported catalyst systems of the present invention are most suitable for operation in processes which typically employ supported polymerisation catalysts.
  • the supported catalysts of the present invention may be suitable for the polymerisation of olefin monomers selected from (a) ethylene, (b) propylene (c) mixtures of ethylene and propylene and (d) mixtures of (a), (b) or (c) with one or more other alpha-olefins.
  • olefin monomers selected from (a) ethylene, (b) propylene (c) mixtures of ethylene and propylene and (d) mixtures of (a), (b) or (c) with one or more other alpha-olefins.
  • olefin monomers selected from (a) ethylene, (b) propylene (c) mixtures of ethylene and propylene and (d) mixtures of (a), (b) or (c) with one or more other alpha-olefins, said process performed in the presence of a supported catalyst system as hereinbefore described.
  • the supported catalyst systems of the present invention are however most suitable for use in slurry or gas phase processes.
  • a slurry process typically uses an inert hydrocarbon diluent and temperatures from about 0° C. up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerisation medium.
  • Suitable diluents include toluene or alkanes such as hexane, propane or isobutane.
  • Preferred temperatures are from about 30° C. up to about 200° C. but preferably from about 60° C. to 100° C.
  • Loop reactors are widely used in slurry polymerisation processes.
  • Typical operating conditions for the gas phase are from 20° C. to 100° C. and most preferably from 40° C. to 85° C. with pressures from subatmospheric to 100 bar.
  • Particularly preferred gas phase processes are those operating in a fliidised bed. Examples of such processes are described in EP 89691 and EP 699213 the latter being a particularly preferred process for use with the supported catalysts of the present invention.
  • Particularly preferred polymerisation processes are those comprising the polymerisation of ethylene or the copolymerisation of ethylene and ⁇ -olefins having from 3 to 10 carbon atoms.
  • the preferred ⁇ -olefins are 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
  • the supported catalysts prepared according to the present invention may also be suitable for the preparation of other polymers for example polypropylene, polystyrene, etc.
  • the supported catalyst systems described herein may be used to prepare copolymers having a broad molecular weight distribution as well as improved melt strengths.
  • Copolymers may be prepared which exhibit a molecular weight distribution (Mw/Mn) of >2 and preferably >3.
  • the copolymers also exhibit melt strength values (16 Mpa) in the range 3-12 cN and preferably in the range 3-9 cN.
  • copolymers are preferably prepared by use of a supported metallocene catalyst system as hereinbefore described.
  • said process comprising contacting ethylene and one or more alpha-olefins in the presence of a supported metallocene catalyst system as hereinbefore described.
  • the preferred supported catalyst system for this aspect of the present invention is that wherein the transition metal compound is a monocyclopentadienyl metallocene complex as hereinbefore described.
  • the preferred process for the preparation of such copolymers is a gas phase process.
  • the present invention also encompasses a dehydrated catalyst support material characterised in that the support-material has been treated with at least two different organoaluminium compounds prior to the addition of further catalytic components.
  • a 2.5 l double jacketed thermostatic stainless steel autoclave was purged with nitrogen at 70° C. for at least one hour. PE pellets previously dried under vacuum at 80° C. for 12 hours were introduced and the reactor was then purged three times with nitrogen (7 bar to atmospheric pressure). ⁇ 0.13 g of TEA treated silica (1.5 mmol TEA/g) was added under pressure and allowed to scavenge impurities for at least 15 minutes under agitation. The gas phase was then composed (addition of ethylene, 1-hexene and hydrogen) and a mixture of supported catalyst ( ⁇ 0.1 g) and silica/TEA ( ⁇ 0.1 g) was injected.
  • a constant pressure of ethylene and a constant pressure ratio of ethylene/co-monomer were maintained during the run.
  • the run was terminated by venting the reactor and then purging the reactor 3 times with nitrogen.
  • the PE powder produced during the run was then separated from the PE seed bed by simple sieving.
  • SiO2/TEA impregnated used as scavenger SiO2/TEA impregnated used as scavenger.
  • SiO2/TEA impregnated used as scavenger SiO2/TEA impregnated used as scavenger.
  • the melt flow rate (OR) of the polymers was measured under conditions which conform to ISO 1133 (1991) and BS 2782:PART 720A:1979 procedures.
  • the weight of polymer extruded through a die of 2.095 mm diameter, at a temperature of 190° C., during a 600 second time period and under a standard load of 2.16 kg is recorded.
  • the melt strength of the polymer is measured at 190° C., using a Göttfert Rheotens extensional rheometer in conjunction with a Rosand RH 7 Capillary Rheometer. This is achieved by extruding the polymer at a constant pressure (P) through a die of 1.5 mm diameter and 30 mm in length, with a 90° entry angle. Once a given extrusion pressure is selected, the piston of the capillary rheometer will travel through its 15 mm diameter barrel at a speed that is sufficient to maintain that pressure constant. The nominal wall shear rate ( ⁇ dot over ( ⁇ ) ⁇ ) for a given extrusion pressure can then be computed for the polymer at the selected pressure using the constant pressure ratio system of the rheometer.
  • the extrudate is drawn with a pair of gear wheels at an accelerating speed (V).
  • the acceleration ranges from 0.12 to 1.2 cm/s 2 depending on the flow properties of the polymer under test.
  • the drawing force (F) experienced by the extrudate is measured with a transducer and recorded on a chart recorder together with the drawing speed.
  • the maximum force at break is defined as melt strength (MS) at aconstant extrusion pressure (P) or at its corresponding extrusion rate ( ⁇ dot over ( ⁇ ) ⁇ ).
  • Three or four extrusion pressures (6, 8, 12, 16 MPa) are typically selected for each polymer depending on its flow properties. For each extrusion pressure, a minimum of 3 MS measurements is performed and an average MS value is then obtained.
  • the derivative function of the extrusion pressure dependent melt strength, ⁇ (MS)/ ⁇ (P) for each polymer is computed from the slope (by a least square line fitting) of the plot of the average MS against pressure.
  • the mean melt strength at an extrusion pressure of 16 MPa, MS (16 MPa), can be computed from the plot.

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US6982306B2 (en) 2003-11-26 2006-01-03 Chevron Phillips Chemical Company, L.P. Stannoxy-substituted metallocene catalysts for olefin and acetylene polymerization
US7119153B2 (en) 2004-01-21 2006-10-10 Jensen Michael D Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength
US7094857B2 (en) 2004-03-10 2006-08-22 Chevron Phillips Chemical Company, L.P. Ethylene polymers and copolymers with high optical opacity
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CN106632751B (zh) * 2015-10-29 2019-12-24 中国石油化工股份有限公司 一种催化剂的制备方法和制得的催化剂及其应用
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MY136117A (en) 2008-08-29
US20090043058A1 (en) 2009-02-12
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WO2004055061A8 (en) 2004-09-02
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AU2003288399A8 (en) 2004-07-09
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JP5362168B2 (ja) 2013-12-11
ATE360037T1 (de) 2007-05-15
US7811956B2 (en) 2010-10-12
JP2006509868A (ja) 2006-03-23
AU2003288399A1 (en) 2004-07-09
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TWI357907B (en) 2012-02-11
CN100355793C (zh) 2007-12-19

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