AU2001275932A1 - Supported catalyst systems - Google Patents
Supported catalyst systemsInfo
- Publication number
- AU2001275932A1 AU2001275932A1 AU2001275932A AU7593201A AU2001275932A1 AU 2001275932 A1 AU2001275932 A1 AU 2001275932A1 AU 2001275932 A AU2001275932 A AU 2001275932A AU 7593201 A AU7593201 A AU 7593201A AU 2001275932 A1 AU2001275932 A1 AU 2001275932A1
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- Australia
- Prior art keywords
- solvent
- catalyst
- supercritical
- organic catalyst
- metallocene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F4/025—Metal oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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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
- 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
- C08F4/6592—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
- C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- 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
- C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
SUPPORTED CATALYST SYSTEMS
FIELD OF INVENTION
The present invention relates generally to the preparation of supported catalyst
systems. More specifically, the invention relates to methods for producing supported
organic catalyst systems, especially metallocene catalyst systems, and the supported
catalyst systems made therefrom.
BACKGROUND OF THE INVENTION
Supported organic catalyst systems, particularly metallocene catalyst systems, are of interest for use in polymerization reactions. These catalyst systems typically contain one or
more metallocene compounds on a porous support media, such as silica. Supporting the metallocene compounds in this manner improves the handling characteristics of the
polymer product and gives better control of reaction rates.
Typically, the supported systems have heretofore been formed by dissolving the
catalyst compounds in solvent and attempting to permeate the pores of the support with
catalyst solution to form a uniform film of catalyst on the support. For example, U.S.
Patent Nos. 5,665,665 and 5,721,184 disclose the use of toluene to dissolve and transfer
metallocene catalyst to the surface of a support material.
The present inventors have come to appreciate that such prior processes are
disadvantageous for several reasons. One such disadvantage is that the prior art methods
result in relatively uneven distribution of the catalyst on the support. It is believed that this
uneven distribution results from non-uniform evaporation of the solvent, which produces
concentration gradients and creates uneven layers on the support. This uneven deposition
can lead to fouling of the reactor in which the catalyst is used. In addition, the use of
solvents having relatively high surface tension inhibits penetration of the solution into the
fine pores on a support. Another disadvantage is that the solvents used in the prior art
processes require excessive energy and time to remove.
Recognizing these and other drawbacks of the prior art, the present inventors have
perceived a need for a new, efficient and more desirable method for producing a wide
range of supported organic catalyst systems. These and other objects are achieved by the
present invention as described below.
DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
The present invention is directed to methods for producing supported organic catalyst systems and the catalyst systems produced therefrom. As used herein, the term
"organic catalyst" refers to a compound which exhibits catalytic properties and which is comprised of at least about 20% by weight of aliphatic or aromatic carbon chains or rings
(including the non-carbon substituents thereof). Examples of particularly preferred organic
catalysts include metallocene catalyst compounds. One important aspect of the present
invention is the discovery that such catalysts, and particularly metallocene catalysts, can be
incorporated into a catalyst support by methods which include the step of removing solvent
from the support by using one or more supercritical solvents. As used herein, the term
Asupercritical solvent® refers to a solvent in its supercritical state and also refers to any
liquid solvent having a boiling point below about 14EC at atmospheric pressure. The
present inventors believe that such liquid solvents act in certain respects like solvents in
their supercritical state for many embodiments of the present invention.
According to an important aspect of certain embodiments of the invention, the catalyst compound is deposited on the catalyst support using a supercritical solvent. This
aspect of the present invention can be used to great advantage to insure maximum and
uniform distribution of the catalyst compound, and particularly metallocene compounds, on
support materials.
Although applicants do not intend to be bound by or to any particular theory of
operation, it is believed that solvents in their supercritical state possess a number of
properties that produce the desirable results of the present invention. For example,
applicants have discovered that many metallocene catalysts are soluble, and often highly
soluble, in solvents which are in their supercritical state. This relatively high solubility
allows a greater amount of catalyst to be introduced to the support to achieve a more even
deposition of catalyst on the support. Additionally, it is believed that solvents in their
supercritical state have relatively low surface tension properties, which allows greater
penetration of support pores by catalyst solutions. Furthermore, solvents in their supercritical state generally exhibit high- volatility, which facilitates removal of solvents from the catalyst/support systems and which in turn is believed to contribute to a more
even deposition of catalyst on the support than is achieved with conventional high boiling
liquids.
According to preferred embodiments of the present invention, the methods of
producing a supported organic, and preferably metallocene, catalyst system comprise the
steps of: (a) providing an organic catalyst compound dissolved in a supercritical solvent;
(b) contacting a support material with said organic catalyst solution; and (c) removing
substantially all of the supercritical solvent from the catalyst support.
According to another embodiment of the present invention, the methods comprise
the steps of: (a) providing an organic catalyst compound, preferably a metallocene
compound, dissolved in a first solvent; (b) contacting a support material with said catalyst
solution; and (c) removing substantially all of said first solvent from the catalyst support,
said removing step including evaporating a supercritical solvent from the catalyst support .
According to one version of this method, the first solvent of step (a) comprises a
supercritical solvent and the removing step comprises evaporating said supercritical solvent
from the catalyst support. In another version of this method, the removing step comprises
contacting the catalyst support with a second solvent comprising a supercritical solvent. In
methods utilizing the second contacting step, the first solvent may or may not include a
supercritical solvent.
It is contemplated that any compound which satisfies the above definition of "organic catalyst" may be used as an organic catalyst in the present invention.
The term "metallocene catalyst", as used herein, refers generally to a catalyst comprising at least one metallocene compound which exhibits catalytic properties. The
metallocene catalysts of the present invention may optionally contain additional catalytic metallocene compounds, co-catalysts, activator compounds and/or additives, such as those
described in U.S. Patent Nos. 5,665,665, 5,786,291 and 5,721,184, each of which is incorporated herein by reference. Accordingly, any single catalytic metallocene compound
or combination of a single catalytic metallocene compound with other metallocene
compounds, co-catalysts, activator compounds and/or additives will be a "metallocene
catalyst" for purposes of the present invention.
The metallocene compound or compounds used in the preferred aspects of the
present invention can be any metallocene known to possess catalytic activity. For example,
U.S. Patent Nos. 5,665,665, 5,786,291 and 5,721,184 describe a wide range of metallocene
compounds which are used as catalysts in various applications and are suitable for use in
the present invention. Such suitable metallocene compounds include zirconium
metallocene compounds such as dichloro(bis(n-butylcyclopentadienyl) zirconium (IV) and
dichlorobis(cyclopentadienyl) zirconium (TV), and halfiiium compounds such as
dimethylbis(t-butylcyclopentadienyl) hafnium (TV).
Co-catalysts are often used in conjunction with metallocene compounds such co-
catalysts generally serving to activate the metallocene compound. Examples of co-catalysts
suitable for use in the present invention are described in U.S. Patent Nos. 5,625,015,
5,665,665 and 5,153,157, which are incorporated herein by reference, and include aryl
boron compounds, such as tri-(n-butyl) ammonium bis (pentafluorophenyl) boron and tris
(pentafluorophenyl) borane, as well as alumoxane, methylalumoxane and their derivatives.
Any of these co-catalysts and any other metallocene co-catalysts known in the art can be ι ■■
used in the present invention. ' '
As mentioned above, an important aspect of the preferred embodiments of the
present invention is the use of supercritical solvents. A wide range of solvents in their
supercritical state, and a wide range of solvents in their liquid state and having a boiling
point below about 14EC, may be used in the present invention. Examples of: solvents
which can be utilized in the present invention in their supercritical state, at temperatures and pressures commonly used industrially, include: hydrocarbons such as methane, ethane,
propane, butane, pentane, hexane, ethylene, and propylene, chlorofluorocarbons such as
trifluorochloromethane, hydrofluorocarons such as difluoromethane, isomers of
tetrafluoroethane, pentafluoroethane, isomers of trifluoroethane, isomers of
pentafluoropropane, hydrochlorofluorocarbons such as difluorochloromethane, and isomers
of tetrafluorochloroethane, and other compounds such as ethers, aliphatic alcohols, water,
carbon dioxide, ammonia, sulfur dioxide and nitrous oxide. Mixtures of the
aforementioned solvents may also be used in their supercritical state as supercritical
solvents of the present invention. The critical temperatures and pressures for some selected
fluids that are adaptable for use as supercritical fluids according to the present invention
are listed in Table 1, below.
Table 1
Critical Temperatures and Pressures For Selected Fluids
Examples of solvents which can be used in their liquid state in the present invention
include: hydrocarbons such as methane, ethane, propane, butane, ethylene, and propylene,
chlorofluorocarbons such as trifluorochloromethane, hydrofluorocarons such as
difluoromethane, isomers of tetrafluoroethane, pentafluoroethane, isomers of
trifluoroethane, isomers of pentafluoropropane, hydrochlorofluorocarbons such as difluorochloromethane, and isomers of tetrafluorochloroethane, and other compounds such
as carbon dioxide, and ammonia.
In preferred embodiments, the supercritical solvent is a solvent in its supercritical state.
The selection of a solvent for use in preferred embodiments of the present invention will generally depend on the organic catalyst used. With respect to the metallocenes, for
example, different metallocene catalysts dissolve to varying degrees in different
supercritical solvents. Thus, for any metallocene catalyst used, it is desirable to utilize a
solvent in which the metallocene catalyst will dissolve. sufficiently to satisfy the objects of
the present invention, such as providing a relatively high rate of uniform deposition of
catalyst compound on the catalyst support. According to certain preferred embodiments,
the organic catalyst compound, and preferably the metallocene compound, has a solubility
in the supercritical solvent of at least about 0.005 wt%, more preferably at least about 0.35
wt%, and even more preferably at least about 2.5 wt%, all as measured under the
conditions under which the supercritical solvent initially contacts the catalyst support.
The metallocene catalyst can be dissolved in the solvent via any method known in
the art. For example, in embodiments of the present invention where the solvent is in its
supercritical state, the metallocene catalyst and solvent can be added together under
subcritical conditions and then subjected to conditions sufficient to bring the solvent into
its supercritical state. Alternatively, the metallocene catalyst can be added to the solvent
under supercritical conditions.
Those of skill in the art will be readily able to determine the temperature and
pressure under which organic catalysts are to be added to supercritical solvents according to the present invention. The temperature will depend, in part, on both the solvent used to
dissolve the catalyst and upon the pressure. In general, organic catalysts are added to
supercritical solvents according to the present invention at a temperature of from about -
lOlC to about 200lC. Preferably, the temperature is from about 30lC to about lOOlC. In
certain preferred embodiments, the pressure at which the solvent and catalyst are added is
generally from about 25 psia to about 5,000 psia, and more preferably from about 100 to
3,500 psia.
To identify metallocene/solvent and co-catalyst/solvent pairs which may be used in
preferred embodiments of the present invention, the present inventors conducted initial
solubility studies at about room temperature. The solubility studies were conducted by
dissolving small amounts of metallocene or co-catalyst in liquid-state solvents at about
40 lC to determine whether the selected compound had any solubility in the solvent at that
temperature. Table 2, below, indicates several solvents, including 1,1,1 trifluoroethane
("HFC-143a") and chlorotetrafluoroethane ("HCFC-124"), in which three metallocene
compounds, dichloro(bis(n-butylcyclopentadienyl) zirconium (IV),
dichlorobis(cyclopentadienyl) zirconium (IV) and ferrocene and a co-catalyst
tris(pentafluorophenyl) borane were found to be soluble. Because the solubility of organic
compounds in a solvent at low temperatures generally increases as the solvent is made
supercritical, it is believed that the compound/solvent pairs in Table 2 are useful as
supercritical solvents of the present invention.
Table 2
Compounds Soluble in Room Temperature Solvents
Moreover, the present inventors have further identified metallocene/supercritical
solvent and co-catalyst/supercritical solvent pairs of varying solubilities which might be
used in the method of the present invention. For example, dimethylbis(t-
butylcyclopentadienyl) hafnium (TV) was found to have a solubility of at least about 2.8
wt.% in 1,1,1,2-tetrafluoroethane ("HFC-134a") at 1001C and 2000psia and
dichloro(bis(n-butylcyclopentadienyl) zirconium (IV) was found to have solubility of at
least about 0.35 wt% in pentafluoroethane ("HFC-125") at 76lC and 2000psia and about
0.25 wt% in carbon dioxide at 551 C and 3500psia. On the other hand, rac-
ethylenebis(indenyl) zirconium (TV) dichloride was found to be substantially insoluble in
HFC-125 at 761 C and 2000psia. The co-catalyst tris(pentafluorophenyl) borane was found
to be highly soluble in both supercritical HFC- 134a and carbon dioxide.
In certain embodiments of the present invention, the providing step (a) comprises
dissolving an organic catalyst in a first solvent comprising a non-supercritical solvent. The
first solvent may be any non-supercritical solvent, a mixture of non-supercritical solvents or a mixture of non-supercritical and supercritical solvents. Preferably, the first solvent
should be chosen such that the organic catalyst to be deposited is sufficiently soluble in the solvent. For example, Patent Nos. 5,665,665 and 5,721,184 describe a number of non-
supercritical solvents including toluene, xylene, hexane, pentane and the like, which can be
used to dissolve a wide variety of metallocene catalysts. In addition, a wide range of other non-supercritical solvents are known in the art and are available commercially.
In light of the disclosure contained herein, those of ordinary skill in the art can
determine catalyst/solvent pairs for use in the present invention without undue
experimentation.
According to preferred embodiments, the step of contacting a porous support
material with the organic catalyst solution comprises coating substantially the entire
surface area of the support material with the catalyst solution such that the catalyst solution
penetrates substantially all of the pores of the support and such that removal of the solvent
results in substantially uniform deposition of catalyst in the pores and on the surface of the
support material. Any known method for coating the surface of the support can be used in the present invention including, for example, immersion of the support in the catalyst
solution, adding the catalyst solution dropwise to the support, spraying the support, or the
like.
In embodiments of the present invention wherein the organic catalyst compound is
dissolved in a supercritical solvent, the preferred coating method is immersion.
In other embodiments of the invention, it is desirable to minimize the amount of
catalyst solution solvent used to contact the support. This is especially true when a
relatively non-volatile solvent like toluene is used. In general, the lower the amount of solvent used to contact the support, the more rapidly and easily the solvent can be removed
from the support to form the supported catalyst system. Accordingly, a preferred method for contacting the catalyst support comprises adding the solution dropwise to the solid
support until the support is at an "incipient wetness" state. As used herein, the term "incipient wetness" refers generally to a free flowing porous powder becoming wetted to
the point at which a further small addition of liquid brings about a marked decrease in its
ability to flow, [see W.B. Innes, Analytical Chemistry, Vol. 28, No. 3, March 1956, page 332, which is incorporated herein by reference]. In this manner, the metallocene catalyst
can be introduced to the solid support using a minimal amount of solvent which, in turn,
can be more easily removed to form a supported catalyst system.
The contacting step also preferably comprises maintaining the support and solution
at a temperature such that the solvent is in a supercritical or liquid state, with the
supercritical state being preferred. In the case where the solvent is to be used in its
supercritical state, this requires that the temperature and pressure be maintained about at or
above the critical temperature of the solvent. In the case where the solvent used is not in
its supercritical state, it is preferred that the temperature and pressure of the contacting step
be maintained such that the solvent is in a liquid state. Accordingly, the step of contacting the porous support with the catalyst solution is preferably carried out in a temperature-
controlled high-pressure vessel, such as a high pressure tube, an autoclave or similar
chamber.
For contacting steps which comprise coating, the time required to coat the support
depends on a number of factors including the support pore size and surface area. However,
because supercritical solvents generally have lower surface tension than non-supercritical
solvents, such as toluene, it is believed that they will penetrate the pores of the support in a
relatively shorter time than non-supercritical solvents.
The porous support material used in the present invention can be any conventional support material known in the art. The support can be a powder or a single piece of solid
material that is porous. Suitable support materials include, for example, inorganic solvents
such as alumina, magnesia, titania, zirconia, silica and silica compounds that have been reacted with halogenated organic compounds, as described in U.S. Patent No. 5,885,924,
incorporated herein by reference. In addition, talc, polymeric materials and other organic
support, such as those described in U.S. Patent No. 5,665,665, can be used as support
material in the present invention.
The step of removing the solvent from the support material preferably comprises
evaporating a supercritical solvent from the catalyst support. According to preferred
embodiments, the evaporating step comprises changing the pressure and/or temperature to
which the support material is exposed such that the supercritical solvent is converted to the
gaseous state.
As those of skill in the art will recognize, solvents in their supercritical state can be readily converted to the gaseous state by changing the pressure, the temperature or both
pressure and temperature such that the solvent is no longer under supercritical conditions.
Furthermore, liquid supercritical solvents (solvents whose atmospheric boiling point is
14lC or lower) of the present invention can generally be converted to gasses by lowering
the pressure or by increasing the temperature. Once the solvents are converted to gasses,
they can be readily removed from the supported catalyst system.
Moreover, the change in conditions surrounding the catalyst solution results in
deposition of the catalyst out of solution and onto the porous support. The solubility of the
catalysts and co-catalysts in various solvents can be decreased dramatically as the
surrounding conditions are changed. Thus, by varying conditions, the catalyst can be
uniformly deposited on the support. Thereafter, the supercritical solvent is converted to the gaseous state by evaporation. This process also facilitates removal of solvent from the
catalyst support. Table 3 illustrates the variable solubility of a metallocene co-catalyst in HFC-125 under various pressures.
Table 3 Solubility at Various Pressures of tris(pentafluorophenyl borane in HFC-125 at 761 C
In embodiments of the present invention wherein the organic catalyst is dissolved in
a first solvent comprising a non-supercritical solvent, the removing step comprises
contacting the catalyst support with a second solvent comprising a supercritical solvent and
evaporating said supercritical solvent. In such embodiments, the supercritical solvent takes
the non-supercritical solvent into solution very readily and thereby removes the non-
supercritical solvent from the catalyst and its support. This can be done under conditions
of temperature and pressure such that the catalyst and co-catalyst are practically insoluble
in the supercritical solvent while the supercritical solvent selectively retains its solubility
for the non-supercritical solvent. This is possible because the solubility of a catalyst or co-
catalyst in supercritical solvent can vary dramatically with temperature and pressure.
Any of the supercritical solvents described hereinabove can be used to remove the
non-supercritical solvents used in the present invention. To maximize the amount of non- supercritical solvent removed while minimizing the removal of catalyst from the support,
the supercritical solvent selected is preferably one in which the non-supercritical solvent is
relatively soluble and the organic catalyst is relatively insoluble. For example, as described
above, rac-ethylenebis(indenyl) zirconium (IV) dichloride is relatively insoluble in HFC-
125. Accordingly, HFC-125 can be used in the present invention to effectively remove a
first solvent soluble in HFC-125, such as toluene or heptane, from a rac-
ethylenebis(indenyl) zirconium (IV) dichloride catalyst support system with minimal
removal of the catalyst from the support.
It is also believed that toluene is sufficiently soluble in HFC-134a at room
temperature to be used as a non-supercritical solvent of the present invention. At room
temperature, the solubility of many organic catalysts such as metallocenes is very low in
HFC-134a, and therefore toluene can be selectively removed by HFC-134a from a support
that has both the metallocene and toluene.
Furthermore, the relative solubilities of non-supercritical solvents in supercritical
solvents tend to vary at different temperatures and pressures in much the same way that the
solubilities of catalysts and co-catalysts in supercritical solvents vary at differing
conditions (as illustrated above). Accordingly, the conditions under which a supercritical
solvent is used to remove a first solvent according to present invention can be optimized to
afford a relatively high solubility of first solvent in supercritical solvent while minimizing
the solubility of the organic catalyst. In view of the disclosure contained herein, those of
skill in the art will be readily able to optimize the conditions under which the removal step
is conducted without undue experimentation.
Once an organic catalyst has been deposited according to the present invention, the
removed solvent can be recycled for further use. In this manner, the present invention
allows for uniform distribution of an organic catalyst on a porous support without the need
for time-consuming solvent-removing drying steps and excess clean-up.
Although applicants do not intend to be bound by or to any particular theory of
operation, it is believed that the organic catalyst is generally distributed onto the support
material by a combination of adsorption and precipitation. However, the predominant mechanism will depend on the nature of the support and of the catalyst or co-catalyst. It is
contemplated that in certain embodiments the catalyst chemically reacts with the support so that the catalyst or co-catalyst will be chemically bound to the support. Any of these
mechanisms will provide deposition of catalyst with solvents according to the present
invention.
Furthermore, the method of the present invention can be used to deposit any
number of organic catalysts or co-catalysts onto a support either simultaneously or
sequentially. Both methods, using sequential or simultaneous deposition, are acceptable
and practical.
When depositing multiple compounds and co-catalysts simultaneously it is highly preferred to use a solvent or combinations of solvents in which all materials are soluble. However,
catalysts and co-catalysts can be deposited sequentially, according to the present invention,
using the same or different solvents for each catalyst or co-catalyst deposited. For
example, after depositing a single metallocene compound onto a support via a supercritical
solvent according to the present invention, a co-catalyst for use with the metallocene
compound can be separately deposited on the support by dissolving it in the same or a
different supercritical solvent and depositing it on the support according to the present
invention. Alternatively, two or more metallocene catalysts, each having a metallocene
compound and a co-catalyst, could be deposited sequentially according to the present
invention in the same or in different solvents. Likewise, the sequential deposition of
several metallocene catalysts and co-catalysts in various sequences may be performed
according to the present invention.
In a preferred embodiment, the sequential addition of catalysts and co-catalysts is performed using supercritical solvents which are selective solvents for the catalyst or co-
catalyst dissolved therein. As used herein, the phrase "selective solvent" refers generally to a solvent in which one organic catalyst or co-catalyst to be deposited on a support is
relatively soluble and other catalysts or co-catalysts to be deposited on the support are
relatively insoluble. By using selective solvents, the removal of previously deposited
catalysts and co-catalysts by the solvents of subsequently deposited materials is minimized
or eliminated.
The organic catalyst systems formed by the methods of the present invention find
wide utility in the chemical arts. For example, metallocene catalyst systems are especially
useful in the polymerization of alkenes such as ethylene, propylene, butene and their
substituted derivatives.
EXAMPLES
In order that the invention may be more readily understood, reference is made to the
following examples which are intended to be illustrative of the invention, but are not
intended to be limiting in scope.
EXAMPLE 1
This example illustrates the solubility of dimethylbis(t-butylcyclopentadienyl) hafnium
(TV) in HFC-134a in its supercritical state at 1001C and 2000 psia.
1.96 grams of dimethylbis(t-butylcyclopentadienyl) hafnium (IV) were placed into a
high pressure vessel having a vessel inlet connected to a source of HFC- 134a and a vessel
outlet connected to a micro-metering valve across which pressure can be reduced from
several thousand psia to one atmosphere. A high pressure pump was placed between the
high pressure vessel and the HFC-134a source and the vessel was thermostatted to lOOlC.
The micro-metering valve was heated to 180lC. HFC-134a was brought into the vessel
and the pressure was raised to 2000 psia. The HFC- 134a was allowed to pass through the vessel to dissolve the catalyst and through the micro-metering valve into an ice-cooled
vessel connected to the micro-metering valve wherein the catalyst was precipitated out of
HFC- 134a. After the HFC- 134a passed through the ice-cooled vessel, its flow rate was
measured and it was collected in a liquid nitrogen trap. After sufficient time for 63 grams
of HFC-134a to have flowed through the high pressure vessel, the flow of gas was stopped.
The weight changes of the high pressure vessel and the ice-cooled vessel were recorded
along with the amount of HFC-134a in the liquid nitrogen trap. Approximately 1.83 grams
of catalyst was lost from the high pressure vessel. The solubility was approximately 2.8
wt%.
EXAMPLE 2
This example illustrates the solubility of dichloro(bis(n-butylcyclopentadienyl) zirconium
(IV) in carbon dioxide at 55lC and 3500 psia.
1.0 gram of dichloro(bis(n-butylcyclopentadienyl) zirconium (IV) was placed into a
high pressure vessel having a vessel inlet connected to a source of carbon dioxide and a
vessel outlet connected to a micro-metering valve across which pressure can be reduced
from several thousand psia to one atmosphere. A high pressure pump was placed between
the high pressure vessel and the carbon dioxide source and the vessel was thermostatted to
55 lC. The micro-metering valve was heated to 1801C. Carbon dioxide was brought into
the vessel and the pressure was raised to 3500 psia. The carbon dioxide was allowed to
pass through the vessel to dissolve the catalyst and through the micro-metering valve into
an ice-cooled vessel connected to the micro-metering valve wherein the catalyst was precipitated out of carbon dioxide. After the carbon dioxide passed through the ice-cooled
vessel, its flow rate was measured and it was collected in a liquid nitrogen trap. After
sufficient time for 128 grams of carbon dioxide to have flowed through the high pressure vessel, the flow of gas was stopped. The weight changes of the high pressure vessel and
the ice-cooled vessel were recorded along with the amount of carbon dioxide in the liquid nitrogen trap. Approximately 0.32 grams of catalyst was lost from the high pressure
vessel. The solubility was approximately 0.25 wt%.
EXAMPLE 3
This example illustrates the solubility of tris(pentafluorophenyl) borane in HFC- 134a at
1001C and 2000 psia.
1.2 grams of tris(pentafluorophenyl) borane were placed into a high pressure vessel
having a vessel inlet connected to a source of HFC- 134a and a vessel outlet connected to a
micro-metering valve across which pressure can be reduced from several thousand psia to
one atmosphere. A high pressure pump was placed between the high pressure vessel and
the HFC- 134a source and the vessel was thermostatted to lOOlC. The micro-metering
valve was heated to 1801C. HFC-134a was brought into the vessel and the pressure was
raised to 2000 psia. The HFC-134a was allowed to pass through the vessel to dissolve the co-catalyst and through the micro-metering valve into an ice-cooled vessel connected to the
micro-metering valve wherein the co-catalyst was precipitated out of HFC- 134a. After the
HFC- 134a passed through the ice-cooled vessel, its flow rate was measured and it was
collected in a liquid nitrogen trap. After sufficient time for 73 grams of HFC-134a to have
flowed through the high pressure vessel, the flow of gas was stopped. The weight changes
of the high pressure vessel and the ice-cooled vessel were recorded along with the amount
of HFC-134a in the liquid nitrogen trap. All the material in the high pressure vessel was
lost and an equal amount of material was collected in the ice-cooled vessel.
EXAMPLE 4
This example illustrates the solubility dichloro(bis(n-butylcyclopentadienyl) zirconium
(IV) of in carbon dioxide at 55 lC and 3500 psia.
1.3 grams of dichloro(bis(n-butylcyclopentadienyl) zirconium (IV) was placed into a high pressure vessel having a vessel inlet connected to a source of carbon dioxide and a
vessel outlet connected to a micro-metering valve across which pressure can be reduced
from several thousand psia to one atmosphere. A high pressure pump was placed between
the high pressure vessel and the carbon dioxide source and the vessel was thermostatted to
55lC. The micro-metering valve was heated to 1801C. Carbon dioxide was brought into
the vessel and the pressure was raised to 3500 psia. The carbon dioxide was allowed to
pass through the vessel to dissolve the co-catalyst and through the micro-metering valve
into an ice-cooled vessel connected to the micro-metering valve wherein the co-catalyst
was precipitated out of carbon dioxide. After the carbon dioxide passed through the ice-
cooled vessel, its flow rate was measured and it was collected in a liquid nitrogen trap.
After sufficient time for 55 grams of carbon dioxide to have flowed through the high
pressure vessel, the flow of gas was stopped. The weight changes of the high pressure
vessel and the ice-cooled vessel were recorded along with the amount of carbon dioxide in
the liquid nitrogen trap. All the material in the high pressure vessel was lost and an equal
amount of material was collected in the ice-cooled vessel.
EXAMPLE 5
This example illustrates the solubility of dichloro(bis(n-butylcyclopentadienyl)
zirconium (TV) of in HFC-125 at 76lC and 2000 psia.
1.3 grams of dichloro(bis(n-butylcyclopentadienyl) zirconium (IV) was placed into
a high pressure vessel having a vessel inlet connected to a source of HFC-125 and a vessel
outlet connected to a micro-metering valve across which pressure can be reduced from
several thousand psia to one atmosphere. A high pressure pump was placed between the
high pressure vessel and the HFC-125 source and the vessel was thermostatted to 76lC.
The micro-metering valve was heated to 180lC. HFC-125 was brought into the vessel
and the pressure was raised to 2000 psia. The HFC-125 was allowed to pass through the
vessel to dissolve the co-catalyst and through the micro-metering valve into an ice-cooled vessel connected to the micro-metering valve wherein the co-catalyst was precipitated out
of HFC-125. After the HFC-125 passed through the ice-cooled vessel, its flow rate was
measured and it was collected in a liquid nitrogen trap. After sufficient time for 55 grams of HFC-125 to have flowed through the high pressure vessel, the flow of gas was stopped.
The weight changes of the high pressure vessel and the ice-cooled vessel were recorded
along with the amount of HFC-125 in the liquid nitrogen trap. All the material in the high
pressure vessel was lost and an equal amount of material was collected in the ice-cooled
vessel. The solubility was approximately 0.35 wt%.
EXAMPLE 6
This example illustrates the room temperature solubility of ferrocene in a number of liquid solvents.
A small amount of ferrocene, the simplest of the metallocenes, was placed in a
glass tube and a liquid solvent was added using a vacuum transfer manifold. After the
liquid was transfered, the tube and its contents were brought to room temperature. The
tube was observed for complete dissolution of the solid. Table 4, below, indicates the
weight percent of ferrocene dissolved and the solvents into which the ferrocene completely
dissolved.
Table 4
Room Temperature Solvation of Ferrocene
EXAMPLE 7
This example illustrates the deposition of a catalyst onto a silica support.
A catalyst is placed in a high pressure tube that is connected in series to a second
vessel containing a solid silica support. The two vessels are separately thermostatted such
that the vessel containing the solid support is at a lower temperature than the high pressure
tube. Between the two vessels there is a valve that allows the pressure in the second vessel
to be lower than in the tube. The second vessel is connected to a cooled recycle loop that
leads to a pump that feeds the high pressure tube. A supply vessel containing virgin
solvent is also connected to the pump which feeds the high pressure tube. Solvent is
pumped into the high pressure tube and brought up to the required temperature and
pressure such that the solvent is in a supercritical state and catalyst is dissolved therein.
The catalyst-laden solvent then passes into the second vessel containing the support where
the support is immersed in the solvent for a time sufficient to ensure that the solvent
substantially penetrates uniformly into the pores of the catalyst support. The temperature is
subsequently dropped and the pressure is lowered to precipitate substantially all of the
catalyst onto the support. The substantially catalyst-free solvent is then evaporated and
recycled to the pump.
Having thus described a few particular embodiments of the invention, various
alterations, modifications and improvements will readily occur to those skilled in the art.
Such alterations, modifications and improvements as are made obvious by this disclosure are intended to be part of this description though not expressly stated herein, and are
intended to be within the spirit and scope of the invention. Accordingly, the foregoing
description is by way of example only, and not limiting. The invention is limited only as defined in the following claims and equivalents thereto.
Claims (1)
- CLATMSWhat is claimed is:1. A method of producing a supported organic catalyst system comprising thesteps of:(a) providing an organic catalyst solution comprising an organic catalystdissolved in a supercritical solvent;(b) contacting a support material with said organic catalyst solution; and(c) removing substantially all of said supercritical solvent from saidorganic catalyst and said support material.2. The method of claim 1 wherein said organic catalyst comprises ametallocene catalyst.3. The method of claim 2, wherein said metallocene catalyst comprises azirconium metallocene compound.4. The method of claim 3, wherein said zirconium metallocene compound isselected from the group consisting of dichloro(bis(n-butylcyclopentadienyl) zirconium(IV), dichlorobis(cyclopentadienyl) zirconium (IV) and mixtures thereof.5. The method of claim 1 wherein said supercritical solvent is a solvent in itssupercritical state.6. The method of claim 1 wherein said supercritical solvent comprises a liquid solvent in a subcritical state.7. The method of claim 6 wherein said liquid solvent comprises liquid carbon dioxide.8. The method of claim 1 wherein said providing step (a) comprises dissolvingsaid organic catalyst in said supercritical solvent at a temperature of from about -lOlC toabout 2001C.9. The method of claim 8 wherein said providing step (a) comprises comprisesdissolving said organic catalyst in said supercritical solvent at a temperature of from about 301C to about lOOlC.10. The method of claim 8 wherein said providing step (a) comprises comprises dissolving said organic catalyst in said supercritical solvent at a pressure of from about 25psia to about 5,000 psia.11. The method of claim 9 wherein said providing step (a) comprises dissolving said organic catalyst in said supercritical solvent at a pressure of from about 100 psia toabout 3,500 psia.12. The method of claim 2, wherein said metallocene catalyst comprises ametallocene co-catalyst.13. The method of claim 12, wherein said metallocene co-catalyst is selectedfrom the group consisting of tri-(n-butyl) ammonium bis (pentafluorophenyl) boron, tris(pentafluorophenyl) borane, alumoxane, methylalumoxane and mixtures thereof.14. The method of claim 1 wherein said porous support is selected from thegroup consisting of alumina, silica and silica treated with a halogenated organic compound.15. The method of claim 14 wherein said porous support comprises a pluralityof particles.16. The method of claim 14 wherein said porous support comprises a singleunitary body.17. The method of claim 1 wherein said removing step (c) comprises converting said supercritical solvent to a gaseous state.18. The method of claim 17 wherein said supercritical solvent is converted to a gaseous state by adjusting the temperature of said solvent.19. The method of claim 17 wherein said supercritical solvent is converted to agaseous state by adjusting the pressure of said solvent.20. The method of claim 1 further comprising the steps of:d. providing a second organic catalyst solution comprising a secondorganic catalyst dissolved in a supercritical solvent;e. contacting said porous support material with said second organiccatalyst solution; and f. removing substantially all of said supercritical solvent of said secondsolution from said second organic catalyst and said support material.21. The method of claim 20, wherein said organic catalyst solution and saidsecond organic catalyst solution are contacted with said porous support substantiallysimultaneously.22. The method of claim 20, wherein said solvent of said second solution is aselective solvent for said second organic catalyst.23. A polymerization reaction using the catalyst formed from the method ofclaim 1.24. A method for producing a supported metallocene catalyst systemcomprising the steps of:(a) providing an organic catalyst solution comprising an organic catalystdissolved in a first solvent;(b) contacting a support material with said catalyst solution; and(c) removing substantially all of said first solvent by contacting saidfirst solvent with a supercritical solvent and evaporating said supercritical solvent.25. The method of claim 24, wherein said first solvent is a non-supercritical •solvent.26. The method of claim 24, wherein said removing step (c) further comprisescontacting said first solvent with said supercritical solvent.27. The method of claim 24 further comprising the steps of:d. providing a second organic catalyst solution comprising a secondorganic catalyst dissolved in a second solvent;e. contacting said porous support material with said second organiccatalyst solution; andf. removing substantially all of said second solvent by contacting saidsecond solvent with a supercritical solvent and evaporating said supercritical solvent.28. The method of claim 27, wherein said organic catalyst solution and saidsecond organic catalyst solution are contacted with said porous support substantiallysimultaneously.
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US7557073B2 (en) * | 2001-12-31 | 2009-07-07 | Advanced Technology Materials, Inc. | Non-fluoride containing supercritical fluid composition for removal of ion-implant photoresist |
US7326673B2 (en) * | 2001-12-31 | 2008-02-05 | Advanced Technology Materials, Inc. | Treatment of semiconductor substrates using long-chain organothiols or long-chain acetates |
US9796848B2 (en) * | 2002-10-25 | 2017-10-24 | Honeywell International Inc. | Foaming agents and compositions containing fluorine substituted olefins and methods of foaming |
US8033120B2 (en) | 2002-10-25 | 2011-10-11 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
US20090253820A1 (en) * | 2006-03-21 | 2009-10-08 | Honeywell International Inc. | Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming |
US7279451B2 (en) | 2002-10-25 | 2007-10-09 | Honeywell International Inc. | Compositions containing fluorine substituted olefins |
US20040089839A1 (en) | 2002-10-25 | 2004-05-13 | Honeywell International, Inc. | Fluorinated alkene refrigerant compositions |
US9085504B2 (en) * | 2002-10-25 | 2015-07-21 | Honeywell International Inc. | Solvent compositions containing fluorine substituted olefins and methods and systems using same |
US9005467B2 (en) * | 2003-10-27 | 2015-04-14 | Honeywell International Inc. | Methods of replacing heat transfer fluids |
US7049262B2 (en) * | 2003-10-20 | 2006-05-23 | Equistar Chemicals, Lp | Cryogenic method for forming a supported catalyst |
US7655610B2 (en) * | 2004-04-29 | 2010-02-02 | Honeywell International Inc. | Blowing agent compositions comprising fluorinated olefins and carbon dioxide |
US9499729B2 (en) | 2006-06-26 | 2016-11-22 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
TWI558685B (en) * | 2005-06-24 | 2016-11-21 | 哈尼威爾國際公司 | Compositions containing fluorine substituted olefins |
US8574451B2 (en) | 2005-06-24 | 2013-11-05 | Honeywell International Inc. | Trans-chloro-3,3,3-trifluoropropene for use in chiller applications |
US8420706B2 (en) * | 2005-06-24 | 2013-04-16 | Honeywell International Inc. | Foaming agents, foamable compositions, foams and articles containing halogen substituted olefins, and methods of making same |
US9000061B2 (en) | 2006-03-21 | 2015-04-07 | Honeywell International Inc. | Foams and articles made from foams containing 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd) |
US8820079B2 (en) * | 2008-12-05 | 2014-09-02 | Honeywell International Inc. | Chloro- and bromo-fluoro olefin compounds useful as organic rankine cycle working fluids |
JP2013504658A (en) | 2009-09-09 | 2013-02-07 | ハネウェル・インターナショナル・インコーポレーテッド | Monochlorotrifluoropropene compound and composition and method using the same |
IT1406472B1 (en) | 2010-12-22 | 2014-02-28 | Nuovo Pignone Spa | TEST FOR SIMILITUDE OF COMPRESSOR PERFORMANCE |
CN109320637B (en) * | 2018-09-03 | 2021-10-22 | 吉化集团吉林市天龙催化剂有限公司 | Supported metallocene catalyst for ethylene polymerization and preparation method thereof |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3518207A (en) * | 1967-10-30 | 1970-06-30 | American Cyanamid Co | Impregnation process for platinum-alumina catalyst and catalyst produced thereby |
US5153157A (en) | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US4871705A (en) * | 1988-06-16 | 1989-10-03 | Exxon Chemical Patents Inc. | Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst |
US4916108A (en) * | 1988-08-25 | 1990-04-10 | Westinghouse Electric Corp. | Catalyst preparation using supercritical solvent |
GB9103527D0 (en) | 1991-02-20 | 1991-04-10 | Exxon Chemical Patents Inc | Hp catalyst killer |
US5625015A (en) | 1994-11-23 | 1997-04-29 | Exxon Chemical Patents Inc. | Method for making supported catalyst systems and catalyst systems therefrom |
US5885924A (en) | 1995-06-07 | 1999-03-23 | W. R. Grace & Co.-Conn. | Halogenated supports and supported activators |
US5744556A (en) | 1995-09-25 | 1998-04-28 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase polymerization employing unsupported catalysts |
US6486089B1 (en) * | 1995-11-09 | 2002-11-26 | Exxonmobil Oil Corporation | Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution |
US5721184A (en) | 1995-11-17 | 1998-02-24 | Hoechst | Method for making supported catalyst systems and catalyst systems therefrom |
US5786291A (en) | 1996-02-23 | 1998-07-28 | Exxon Chemical Patents, Inc. | Engineered catalyst systems and methods for their production and use |
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US6893995B2 (en) | 2005-05-17 |
WO2002005957A3 (en) | 2002-04-25 |
US20050107246A1 (en) | 2005-05-19 |
JP2004513189A (en) | 2004-04-30 |
US6972271B2 (en) | 2005-12-06 |
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