Title of Invention

ORGANOMETAL CATALYST COMPOSITIONS

Abstract This invention provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer. This invention also provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer, wherein said catalyst composition comprises a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted fluorided silica-alumina.
Full Text FIELD OF THE INVENTION
This invention is related to the field of organometal catalyst compositions.
BACKGROUND OF THE INVENTION
By "consisting essentially of* herein it is intended to mean that the process
steps, substance or mixture of substances recited after this phrase does not include any
further respective steps or components which would materially affect the functioning of
the process or the properties of the substance or combination of substances produced by
the process or recited after this phrase.
The production of polymers is a multi-billion dollar business. This
business produces billions of pounds of polymers each year. Millions of dollars have been
spent on developing technologies that can add value to this business.
One of these technologies is called metallocene catalyst technology.
Metallocene catalysts have been known since about 1960. However, their low
productivity did not allow them to be commercialized. About 1975, it was discovered that
contacting one part water with one part trirnethylaluminum to form methyl aluminoxane,
and then contacting such methyl aluminoxane with a metallocene compound, formed a
metallocene catalyst that had greater activity. However, it was soon realized that large
amounts of expensive methyl aluminoxane were needed to form an active metallocene
catalyst. This has been a significant impediment to the commercialization of metallocene
catalysts.
Borate compounds have been used in place of large amounts of methyl
aluminoxane. However, this is not satisfactory, since borate compounds are very sensitive
to poisons and decomposition, and can also be very expensive.
It should also be noted that having a heterogeneous catalyst is important.
This is because heterogeneous catalysts are required for most modern commercial
polymerization processes. Furthermore, heterogeneous catalysts can lead to the formation
of substantially uniform polymer particles that have a high bulk density. These types of
substantially uniform particles are desirable because they improve the efficiency of
polymer production and transportation. Efforts have been made to produce heterogeneous
metallocene catalysts; however, these catalysts have not been entirely satisfactory.
Therefore, the inventors provide this invention to help solve these
problems.
SUMMARY OF THE INVENTION
It is desirable to provide a process that produces a catalyst composition
that can be used to polymerize at least one monomer to produce a polymer.
It is also desirable to provide the catalyst composition.
Again it is desirable to provide a process comprising contacting at least
one monomer and the catalyst composition under polymerization conditions to produce
the polymer.
Once again it is desirable to provide an article that comprises the polymer
produced with the catalyst composition of this invention.
In accordance with one embodiment of this invention, a process to produce
a catalyst composition is provided. The process comprises (or optionally, "consists
essentially of, or "consists of) contacting an organometal compound, an
organoaluminum compound, and a fluorided silica-alumina to produce the catalyst
composition,
wherein said organometal compound has the following general formula:
(X1)(X2)(x3)(x4)m1 ?
wherein M1 is selected from the group consisting of titanium, zirconium,
and hafnium;
wherein (X1) is independently selected from the group consisting of
cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted
indenyls, and substituted fluorenyls;
wherein substituents on the substituted cyclopentadienyls, substituted
indenyls, and substituted fluorenyls of (X1) are selected from the group consisting of
aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups,
alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups,
silicon, phosphorus, boron, germanium, and hydrogen;
wherein at least one substituent on (X1) can be a bridging group which
connects (X1) and (X2);
wherein (X3) and (X4) are independently selected from the group
consisting of halides, aliphatic groups, substituted aliphatic groups, cyclic groups,
substituted cyclic groups, combinations of aliphatic groups and cyclic groups,
combinations of substituted aliphatic groups and cyclic groups, combinations of aliphatic
groups and substituted cyclic groups, combinations of substituted aliphatic groups and
substituted cyclic groups, amido groups, substituted amido groups, phosphido groups,
substituted phosphido groups, alkyloxide groups, substituted alkyloxide groups, aryloxide
groups, substituted aryloxide groups, organometallic groups, and substituted
organometallic groups;
wherein (X2) is selected from the group consisting of cyclopentadienyls,
indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, substituted
fluorenyls, halides, aliphatic groups, substituted aliphatic groups, cyclic groups,
substituted cyclic groups, combinations of aliphatic groups and cyclic groups,
combinations of substituted aliphatic groups and cyclic groups, combinations of aliphatic
groups and substituted cyclic groups, combinations of substituted aliphatic groups and
substituted cyclic groups, amido groups, substituted amido groups, phosphido groups,
substituted phosphido groups, alkyloxide groups, substituted alkyloxide groups, aryloxide
groups, substituted aryloxide groups, organometallic groups, and substituted
organometallic groups;
wherein substituents on (X2) are selected from the group consisting of
aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl
groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen
groups, silicon, phosphorus, boron, germanium, and hydrogen;
wherein at least one substituent on (X2) can be a bridging group which
connects (X1) and (X2);
wherein the organoaluminug compound has the following general formula:
Al(X5)n(X6)3-n
wherein (X5) is a hydrocarbyl having from 1 to about 20 carbon atoms;
wherein (X6) is a halide, hydride, or alkoxide; and
wherein "n" is a number from 1 to 3 inclusive;
wherein the fluorided silica-alumina comprises fluoride; silica, and
alumina.
In accordance with another embodiment of this invention, a process is
provided comprising contacting at least one monomer and the catalyst composition under
polymerization conditions to produce a polymer.
In accordance with another embodiment of this invention, an article is
provided. The article comprises the polymer produced in accordance with this invention.
These objects, and other objects, will become more apparent to those with
ordinary skill in the art after reading this disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
hi the drawings, forming a part hereafter, Fig. 1 discloses a graph of the
activity of the catalyst composition at various fluoride loadings and calcining
temperatures.
Fig. 2 discloses a graph of the activity versus percent NH4HF2 added.
DETAILED DESCRIPTION OF THE INVENTION
Organometal compounds used in this invention have the following general
formula:
(X1)(X2)(X3)(X4)M1
In this formula, M1 is selected from the group consisting of titanium, zirconium, and
hafnium. Currently, it is most preferred when M1 is zirconium.
In this formula, (X1) is independently selected from the group consisting
of (hereafter "Group OMC-I") cyclopentadienyls, indenyls, fluorenyls, substituted
cyclopentadienyls, substituted indenyls, such as, for example, tetrahydroindenyls, and
substituted fluorenyls, such as, for example, octahydrofluorenyls.
Substituents on the substituted cyclopentadienyls, substituted indenyls, and
substituted fluorenyls of (X1) can be selected independently from the group, consisting of
aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups,
alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups,
silicon, phosphorus, boron, germanium, and hydrogen, as long as these groups do not
substantially, and adversely, affect the polymerization activity of the catalyst composition.
Suitable examples of aliphatic groups are hydrocarbyls, such as, ibr
example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffins,
cycloolefins, cycloacetylenes, and arenes. Substituted silyi groups include, but are not
limited to, alkylsilyl groups where each alkyl group contains from 1 to about 12 carbon
atoms, arylsilyl groups, and arylalkylsilyl groups. Suitable alkyl halide groups have alkyi
groups with 1 to about 12 carbon atoms. Suitable organometallic groups include, but are
not limited to, substituted silyl derivatives, substituted tin groups, substituted germanium
groups, and substituted boron groups.
Suitable examples of such substituents are methyl, ethyl, propyl, butyl,
tert-buryl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl,
2-ethylhexyl, pentenyi, butenyl, phenyl, chloro, bromo, iodo, trimethylsilyl, and
phenyloctylsilyl.
In this formula, (X3) and (X4) are independently selected from the group
consisting of (hereafter "Group OMC-II") halides, aliphatic groups, substituted aliphatic
groups, cyclic groups, substituted cyclic groups, combinations of aliphatic groups and
cyclic groups, combinations of substituted aliphatic groups and cyclic groups,
combinations of aliphatic groups and substituted cyclic groups, combinations of
substituted aliphatic and substituted cyclic groups, amido groups, substituted amido
groups, phosphide groups, substituted phosphido groups, alkyloxide groups, substituted
alkyloxide groups, aryloxide groups, substituted aryloxide groups, organometallic groups,
and substituted organometallic groups, as long as these groups do not substantially, and
adversely, affect the polymerization activity of the catalyst composition.
Suitable examples of aliphatic groups are hydrocarbyls, such as, for
example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffins,
cycloolefins, cycloacetylenes, and arenes. Currently, it is preferred when (X3) and (X4)
are selected from the group consisting of halides and hydrocarbyls, where such
hydrocarbyls have from 1 to about 10 carbon atoms. However, it is most preferred when
(X3) and (X4) are selected from the group consisting of fluoro, chloro, and methyl.
In this formula, (X2) can be selected from either Group OMC-I or Group
OMC-II.
At least one substituent on (X1) or (X2) can be a bridging group that
connects (X1) and (X2), as long as the bridging group does not substantially, and
adversely, affect the activity of the catalyst composition. Suitable bridging groups
include, but are not limited to, aliphatic groups, cyclic groups, combinations of aliphatic
groups and cyclic groups, phosphorous groups, nitrogen groups, organometallic groups,
silicon, phosphorus, boron, and germanium.
Suitable examples of aliphatic groups are hydrocarbyls, such as, for
example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffins,
cycloolefins, cycloacetylenes, and arenes. Suitable organometallic groups include, but are
not limited to, substituted silyl derivatives, substituted tin groups, substituted germanium
groups, and substituted boron groups.
Various processes are known to make these organometal compounds. See,
for example, U.S. Patents 4,939,217; 5,210,352; 5,436,305; 5,401,817; 5,631,335,
5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592; 5,347,026; 5,594,078; 5,498,581;
5,496,781; 5,563,284; 5,554,795; 5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203;
5,654,454; 5,705,579; and 5,668,230; the entire disclosures of which are hereby
incorporated by reference.
Specific examples of such organometal compounds are as follows:
bis(cyclopentadienyl)hamium dichloride;
In this formula, (X5) is a hydrocarbyl having from 1 to about 20 carbon atoms. Currently,
it is preferred when (X5) is an alkyl having from 1 to about 10 carbon atoms. However, it
is most preferred when (X5) is selected from the group consisting of methyl, ethyl, propyl,
butyl, and isobutyl.
In this formula, (X6) is a halide, hydride, or alkoxide. Currently, it is,
preferred when (X6) is independently selected from the group consisting of fluoro and
chlorp. However, it is most preferred when (X6) is chloro.
In this formula, "n" is a number from 1 to 3 inclusive. However, it is
preferred when "n" is 3.
Examples of such compounds are as follows:
trimethylaluminum;
triethylaluminum (TEA);
tripropylaluminum;
diethylaluminum ethoxide;
tributylaluminum;
triisobutylaluminum hydride;
triisobutylaluminum; and
diethylaluminum chloride.
Currently, TEA is preferred.
The fluorided silica-alumina comprises silica, alumina and fluoride. The
fluorided silica-alumina is in the form of a particulate solid. Generally, to produce the
fluorided silica-alumina, a silica-alumina is treated with a fluoriding agent, in order to add
fluoride to the silica-alumina. Generally, the fluoride is added to the silica-alumina by
forming a slurry of the silica-alumina in a solution of the fluoriding agent and a suitable
solvent such as alcohol or water. Particularly suitable are one to three carbon atom
alcohols because of their volatility and low surface tension. A suitable amount of the
solution is utilized to provide the desired concentration of fluoride on the silica-alumina
after drying. Drying can be effected by any method known in the art For example, said
drying can be completed by suction filtration followed by evaporation, drying under
vacuum, or by spray drying.
Any organic or inorganic fluoriding agent which can form a surface
fluoride with a silica-alumina can be used in this invention. Suitable fluoriding agents
include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F),
ammonium bifluoride (NH4HF2), ammonium fluoroborate (NH4BF4), ammonium
silicofiuoride ((NH4)2SiF6), ammonium fluorophosphate (NH4PF5), and mixtures
thereof. The most preferred fluoriding agent is ammonium bifluoride, due to ease of use
and availability. The amount of fluoride present before calcining is generally in the range
of about 2 to about 50% by weight, preferably about 3 to about 25% by weight, and most
preferably, 4 to 20% by weight, where the weight percents are based on the weight of the
fluorided silica-alumina before calcining.
It is important that the fluorided silica-alumina be calcined. The calcining
can be conducted in any suitable ambient. Generally, the calcining is conducted in an
ambient atmosphere, preferably a dry ambient atmosphere, at a temperature in the range
of about 200°C to about 900°C, and for a time in the range of about 1 minute to about 100
hours. Preferably, the fluorided silica-alumina is calcined at temperatures from about
300°C to about 600°C and a time in a range of about 1 hour to about 10 hours, most
preferably, temperatures from 350°C to 550°C and a time in a range of 1 hours to 10
hours.
Optionally, the silica-alumina can be treated with a fluoriding agent during
calcining. Any fluoriding agent capable of contacting the silica-alumina during the
calcining step can be used. In addition to those fluoriding agents described previously,
organic fluoriding agents of high volatility are especially useful. Organic fluoriding
agents of high volatility can be selected from the group consisting of freons,
perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and mixtures
thereof. Gaseous hydrogen fluoride or fluorine itself can be used. One convenient method
of contacting the silica-alumina is to vaporize a fluoriding agent into a gas stream used to
fluidize the silica-alumina during calcination.
The silica-alumina should have a pore volume greater than about 0.5 cc/g,
preferably greater than about 0.8 cc/g, and most preferably, greater than 1.0 cc/g.
The silica-alumina should have a surface area greater than about 100 m2/g,
preferably greater than about 250 m2/g, and most preferably greater than 350 m^/g.
The silica-alumina of this invention can have an alumina content from
about 5 to about 95%, preferably from about 8 to about 50%, and most preferably from
10% to 30% alumina by weight
The catalyst compositions of this invention can be produced by contacting
the organometal compound, the fluorided silica-alumina, and the organoaluminum
compound, together. This contacting can occur in a variety of ways, such as, for example,
blending. Furthermore, each of these compounds can be fed into a reactor separately, or
various combinatjpns of these compounds can be contacted together before being further
contacted in the reactor, or all three compounds can be contacted together before being
introduced into the reactor.
Currently, one method is to first contact an organometal compound and a
fluorided silica-alumina together, for about 1 minute to about 24 hours, preferably, 1
minute to 1 hour, at a temperature from about 10°C to about 200°C, preferably 15°C to
80°C, to form a first mixture, and then contact this first mixture with an organoaluminum
compound to form the catalyst composition.
Preferably, the organometal compound, the organoaluminum compound,
and the fluorided silica-alumina are precontacted before injection into the reactor for
about 1 minute to about 24 hours, preferably, 1 minute to 1 hour, at a temperature from
about 10°C to about 200°C, preferably 20°C to 80°C, in order to obtain high-activity.
A weight ratio of organoaluminum compound to the fluorided silica-
alumina in the catalyst composition ranges from about 5:1 to about 1:1000, preferably,
from about 3:1 to about 1:100, and most preferably, from 1:1 to 1:50.
A weight ratio of the fluorided silica-alumina to the organometal
compound in the catalyst composition ranges from about 10,000:1 to about 1:1,
preferably, from about 1000:1 to about 10:1, and most preferably, from about 250:1 to
20:1. These ratios are based on the amount of the components combined to give the
catalyst composition.
After contacting, the catalyst composition comprises a post-contacted
organometal compound, a post-contacted organoaluminum compound, and a post-
contacted fluorided silica-alumina. It should be noted that the post-contacted fluorided
silica-alumina is the majority, by weight, of the catalyst composition. Often times,
specific components of a catalyst are not known, therefore, for this invention, the catalyst
composition is described as comprising post-contacted compounds.
The catalyst composition of this invention has an activity greater than a
catalyst composition that uses the same organometal compound, and the same
organoaluminum compound, but uses alumina, silica, or silica-alumina that has not been
impregnated with fluoride as shown in control examples 3-7. Furthermore, the catalyst
composition of this invention has an activity greater than a catalyst composition that uses
the same organometal compound, and the same organoaluminum compound, but uses a
fluorided silica or a fluorided alumina as shown in control examples 9-10. This activity is
measured under slurry polymerization conditions, using isobutane as the diluent, and with
a polymerization temperature of about 50 to about 150ºC, and an ethylene pressure of
about 400 to about 800 psig. When comparing activities, polymerization runs should
occur at the same polymerization conditions. The reactor should have substantially no
indication of any wall scale, coating or other forms of fouling.
However, it is preferred if the activity is greater than about 1000 grams of
polymer per gram of fluorided silica-alumina per hour, more preferably greater than about
2000, even more preferably greater than 5000, and most preferably greater than 8,000.
This activity is measured under slurry polymerization conditions, using isobutane as the
diluent, and with a polymerization temperature of 90°C, and an ethylene pressure of 550
psig. The reactor should have substantially no indication of any wall scale, coating or
other forms of fouling.
One of the important aspects of this invention is that no aluminoxane
needs to be used in order to form the catalyst composition. Aluminoxane is an expensive
compound that greatly increases polymer production costs. This also means that no watei
is needed to help form such aluminoxanes. This is beneficial because water can
sometimes kill a polymerization process. Additionally, it should be noted that no borate
compounds need to be used in order to form the catalyst composition. In summary, this
means that the catalyst composition, which is heterogenous, and which can be used for
polymerizing monomers or monomers and one or more comonomers, can be easily and
inexpensively produced because of the absence of any aluminoxane compounds or borate
compounds. Additionally, no organochromium compound needs to be added, nor any
MgCl2 needs to be added to form the invention. Although aluminoxane, borate
compounds, organochromium compounds, or MgCl2 are not needed in the preferred
embodiments, these compounds can be used in other embodiments of this invention.
In another embodiment of this invention, a process comprising contacting
at least one monomer and the catalyst composition to produce at least one polymer is
provided. The term "polymer" as used in this disclosure includes homopolymers and
copolymers. The catalyst composition can be used to polymerize at least one monomer to
produce a homopolymer or a copolymer. Usually, homopolymers are comprised of
monomer residues, having 2 to about 20 carbon atoms per molecule, preferably 2 to about
10 carbon atoms per molecule. Currently, it is preferred when at least one monomer is
selected from the group consisting of ethylene, propylene, 1-butene, 3-methyl-l-butene, 1-
pentene, 3-methyl-l-pentene, 4-methyl-l-pentene, 1-hexene, 3-ethyl-l-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, and mixtures thereof.
When a homopolymer is desired, it is most preferred to polymerize
ethylene or propylene. When a copolymer is desired, the copolymer comprises monomer
residues and one or more comonomer residues, each having from about 2 to about 20
carbon atoms per molecule. Suitable comonomers include, but are not limited to,
aliphatic 1-olefins having from 3 to 20 carbon atoms per molecule, such as, for example,
propylene, l-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, and other olefins
and conjugated or nonconjugated diolefins such as 1,3-butadiene, isoprene, piperylene,
2,3-dimethyl-l,3-butadiene, 1,4-pentadiene, 1,7-hexadiene, and other such diolefins and
mixtures thereof. When a copolymer is desired, it is preferred to polymerize ethylene and
at least one comonomer selected from the group consisting of 1-butene, 1-pentene, 1-
hexene, 1 -octene, and 1 -decene. The amount of comonomer introduced into a reactor
zone to produce a copolymer is generally from about 0.01 to about 10 weight percent
comonomer based on the total weight of the monomer and comonomer, preferably, about
0.01 to about 5, and most preferably, 0.1 to 4. Alternatively, an amount sufficient to give
the above described concentrations, by weight, in the copolymer produced can be used.
Processes that can polymerize at least one monomer to produce a polymer
are known in the art, such as, for example, slurry polymerization, gas phase
polymerization, and solution polymerization. It is preferred to perform a slurry
polymerization in a loop reaction zone. Suitable diluents used in slurry polymerization
are well known in the art and include hydrocarbons which are liquid under reaction
conditions. The term "diluent" as used in this disclosure does not necessarily mean an
inert material; it is possible that a diluent can contribute to polymerization. Suitable
hydrocarbons include, but are not limited to, cyclohexane, isobutane, n-butane, propane,
n-pentane, isopentane, neopentane, and n-hexane. Furthermore, it is most preferred to use
isobutane as the diluent in a slurry polymerization. Examples of such technology can be
found in U.S. Patents 4,424,341; 4,501,885; 4,613,484; 4,737,280; and 5,597,892; the
entire disclosures of which are hereby incorporated by reference.
The catalyst compositions used in this process produce good quality
polymer particles without substantially fouling the reactor. When the catalyst composition
is to be used in a loop reactor zone under slurry polymerization conditions, it is preferred
when the particle size of the solid oxide compound is in the range of about 10 to about
1000 microns, preferably about 25 to about 506 microns, and most preferably, 50 to 200
microns, for best control during polymerization.
In a more specific embodiment of this invention, a process is provided to
produce a catalyst composition, the process comprising {optionally, "consisting essentially
of, or "consisting of):
(1) contacting a silica-alumina with water containing ammonium
bifluoride to produce a fluorided silica-alumina;
(2) calcining the fluorided silica-alumina at a temperature within a range
of 350 to 550°C to produce a calcined composition having 4 to 20 weight percent fluoride
based on the weight of the fluorided silica-alumina before calcining;
(3) combining said calcined composition and bis(n-butylcyclopenta
dienyl) zirconium dichloride at a temperature within the range of 15°C to 80°C to produce
a mixture; and
(4) after between 1 minute and 1 hour, combining said mixture and
triethylaluminum to produce said catalyst composition.
Hydrogen can be used in this invention in a polymerization process to
control polymer molecular weight
After the polymers are produced, they can be formed into various articles,
such as, for example, household containers and utensils, film products, drums, fuel tanks,
pipes, geomembranes, and liners. Various processes can form these articles. Usually,
additives and modifiers are added to the polymer in order to provide desired effects. It is
believed that by using the invention described herein, articles can be produced at a lower
cost, while maintaining most, if not all, of the unique properties of polymers produced
with metallocene catalysts.
EXAMPLES
TESTING METHODS
A "Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument"
was used to determined surface areas and pore volumes. This instrument was acquired
from the Quantachrome Corporation, Syosset, N.Y.
PREPARATION OF OXIDE COMPOUNDS FOR CONTROL EXAMPLES 3-7
Silica was obtained from W.R.Grace, grade 952, having a pore volume of
1.6 cubic centimeter per gram (cc/g) and a surface area of about 300 square meters per
gram (m2/g).
About 10 grams of the silica were placed in a 1.75 inch quartz tube fitted
with a sintered quartz disk at the bottom. While the silica was supported on the disk, dry
air was blown up through the disk at the linear rate of about 1.6 to 1.8 standard cubic feet
per hour. An electric furnace around the quartz tube was then turned on, and the
temperature was raised at the rate of 400°C per hour to a temperature of 600°C. At this
temperature, the silica was allowed to fluidize for three hours in the dry air. Afterward,
the silica was collected and stored under dry nitrogen. The silica did not have any
exposure to the atmosphere.
Alumina sold as Ketjen grade B alumina from Akzo Nobel was obtained
having a pore volume of about 1.78 cc/g and a surface area of about 340 m2/g. Alumina
samples were prepared by the procedure described previously for the silica except the
alumina samples were calcined at 400°C, 600°C, and 800°C.
A silica-alumina was obtained from W.R.Grace as MS 13-110 containing
13% alumina and 87% silica. The silica-alumina had a pore volume of 1.2 cc/g and a
surface area of about 400 m2/g. Silica-alumina samples were prepared as described
previously for the silica.
GENERAL DESCRIPTION OF POLYMER IZATIONS RUNS
Polymerization runs were made in a 2.2 liter steel reactor equipped with a
marine stirrer running at 400 revolutions per minute (rpm). The reactor was surrounded by
a steel jacket containing boiling methanol with a connection to a steel condenser. The
boiling point of the methanol was controlled by varying nitrogen pressure applied to the
condenser and jacket, which permitted precise temperature control to within ±0.5°C, with
the help of electronic control instruments.
Unless otherwise stated, first, an oxide compound or fluorided silica-
alumina was charged under nitrogen to a dry reactor. Next, two milliliters of a solution
containing 0.5 grams of bis(n-butylcyclopentadienyl) zirconium dichloride per 100
milliliters of toluene were added by syringe. Then, 1.2 liters of isobutane were charged to
the reactor, and the reactor was then heated up to 90°C. One milliliter, or two milliliters,
of TEA or ethyl aluminum dichloride (EADC) was added midway during the isobutane
addition. Finally, ethylene was added to the reactor to equal 550 psig, which was
maintained during the experiment. The stirring was allowed to continue for the specified
time, and the activity was noted by recording the flow of ethylene into the reactor to
maintain pressure.
After the allotted time, the ethylene flow was stopped, and the reactor
slowly depressurized and opened to recover a granular polymer. In all cases, the reactor
was clean with no indication of any wall scale, coating, or other forms of fouling. The
polymer was then removed, dried, and weighed.
EXAMPLES 1-2 (CONTROLS)
This example demonstrates that an organometal compound added to the
reactor with TEA or EADC does not provide any activity.
A polymerization run was made as described previously except no oxide
compound was added. Ethylene was added, but no activity was seen. After one hour of
stirring, the reactor was depressurized and opened, but in each case no polymer was
found. These results are shown in Table 1.
EXAMPLES 3-7 (CONTROLS)
This experiment demonstrates the use of different oxide compounds, an
organometal compound, and TEA.
Each of the oxide compounds described previously was added to the
reactor, followed by the organometal compound and TEA solutions as used in the
procedure discussed previously. These runs are shown in Table 1.
Silica produced almost no polymer. Alumina, which is regarded as more
acidic than the silica, produced more polymer, but still the activity was very low. This was
true of all three different activation temperatures tested. The silica-alumina also exhibited
only very low activity.
EXAMPLE 8 (CONTROL AND INVENTIVE RUNS)
The following catalyst compositions were produced to demonstrate this
invention at different loadings of ammonium bi fluoride and at different calcination
temperatures.
A small amount of a silica-alumina, sold as MS 13-110 by W.R. Grace
Company having a surface area of 400 m2/g and a pore volume of 1.2 cc/g, was
impregnated with about twice its weight of water containing ammonium bifluoride
dissolved in it to produce a fluorided silica-alumina. For example, fifty grams of the
silica-alumina was impregnated with 100 milliliters of an aqueous solution containing 5
grams of ammonium bifluoride for a 10 weight percent loading of ammonium bifluoride.
This resulted in a wet sand consistency.
The fluorided silica-alumina was then placed in a vacuum oven and dried
overnight at 110°C under half an atmosphere of vacuum. The final step was to calcine 10
grams of the fluorided silica-alumina in dry fluidizing air at the required temperature for
three hours. The fluorided silica-alumina was then stored under nitrogen until a small
quantity was charged to the reactor with an organometal compound and TEA as described
previously in this disclosure.
These runs are shown in Table 2, and they are plotted graphically in Figure
1. Table 3 shows the most active run from each loading, regardless of its calcining
temperature plotted against ammonium bifluoride loading. These results are plotted
graphically in Figure 2.
As can be seen from the data in Table 3, excellent catalyst activity was
observed when the ammonium bifluoride loading was from about 5 to about 35% by
weight with a calcining temperature of from about 300°C to about 600°C.
EXAMPLE 9 (CONTROL)
The procedure of example 8 was repeated, except that instead of a silica-
alumina, a silica was used instead.
A grade 952 silica obtained from W.R. Grace was impregnated with 10%
ammonium bifluoride as described previously in this disclosure to produce a fluorided silica.
The silica has a surface area of about 300 m2/g and a pore volume of about 1.6 cc/g. The
fluorided silica was then calcined at 450°C for three hours in dry air and tested for
polymerization activity. It exhibited no activity at all.
EXAMPLE 10 (CONTROL)
The procedure of example 8 was repeated, except that instead of silica-alumina, an
alumina was used instead.
An alumina called Ketjen grade B obtained from Akzo Nobel was impregnated
with various loadings of ammonium bifluoride to produce a fluorided alumina as described
previously. The alumina has a surface area of about 400 m2/g and a pore volume of about
1.6 cc/g. The fluorided alumina samples were then calcined at 450°C or 500°C for three
hours in dry air and tested for polymerization activity as described previously in this
disclosure. These results are shown in Table 4. The activity of the fluorided alumina
samples is considerably below the activity shown in the inventive runs using a fluorided
silica-alumina.
* Activity is in units of grams of polymer/gram of fluorided alumina charged per hour.
While this invention has been described in detail for the purpose of
illustration, it is not intended to be limited thereby but is intended to cover all changes and
modifications within the spirit and scope thereof.
WE CLAIM
1. A process to produce a catalyst composition, said process comprising
contacting an organometal compound, an organoaluminium compound,
and a fiuorided silica-alumina to produce said catalyst composition,
wherein said organometal compound has the following general formula:
(X1)(X2)(X3)(X4)M1
wherein M1 is selected from titanium, zirconium, or hafnium; wherein
(X1) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted
cyclopentadienyls, substituted indenyls, or substituted fluorenyls;
wherein substituents on said substituted cyclopentadienyls, substituted
indenyls, and substituted fluorenyls of (X1) are selected from aliphatic
groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl
groups, alkyl halide groups, halides, organometallic groups, phosphorus
groups, nitrogen groups, silicon, phosphorus, boron, germanium, or
hydrogen; wherein at least one substituent on (X1) can be a bridging
group which connects (X1) and (X2); wherein (X3) and (X4) are
independently selected from halides, aliphatic groups, substituted
aliphatic groups, cyclic groups, substituted cyclic groups, combinations
of aliphatic groups and cyclic groups, combinations of substituted
aliphatic groups and cyclic groups, combinations of aliphatic groups and
substituted cyclic groups, combinations of substituted aliphatic groups
and substituted cyclic groups, amido groups, substituted amido groups,
phosphido groups, substituted phosphido groups, alkyloxide groups,
substituted alkyloxide groups, aryloxide groups, substituted aryloxide
groups, organometallic groups, or substituted organometallic groups;
wherein (X2) is selected from cyclopentadienyls, indenyls, fluorenyls,
substituted cyclopentadienyls, substituted indenyls, substituted
fluorenyls, halides, aliphatic groups, substituted aliphatic groups, cyclic
groups, substituted cyclic groups, combinations of aliphatic groups and
substituted cyclic groups, combinations of substituted aliphatic groups
and substituted cyclic groups, amido groups substituted amido groups
phosphido groups substituted phosphido group, alkyloxide groups,
substituted alkyloxide groups, aryloxide groups, substituted aryloxide
groups, organonetallic groups or substituted organometallic groups,
wherein substituents on (X2) are selected from alphatic groups, cyclic
groups, combinations of aliphatic groups and cyclic groups, silyl groups,
alkyl halide groups, halides, organometallic groups, phosphorus groups,
nitrogen groups, silicon, phosphorus, boron, germanium, or hydrogen;
wherein at least one substituent on (X2) can be a bridging group which
connects (X1) and (X2); wherein said organoaluminium compound has
the following general formula;
AI(X5)n(X6)3-n
wherein (X5) is a hydrocarbyl having from 1 to 20 carbon atoms;
wherein (X6) is a halide, hydride, or alkoxide; wherein "n" is a number
from 1 to 3 inclusive; wherein said fluorided silica-alumina comprises
fluoride, silica, and alumina; and wherein said process proceeds in the
absence of aluminoxanes and borate compounds.
2. A process according to claim 1, wherein said organometal compound,
said organoaluminium compound, and said fluorided silica-alumina are
precontacted for 1 minute to 24 hours before being charged to a
polymerization reactor.
3. A process according to claim 1, including the steps of:
(1) contacting a silica-alumina with water containing ammonium
bifluoride to produce a fluorided silica-alumina;
(2) calcining said fluorided silica-alumina at a temperature within a
range of 350 to 550° C to produce a calcined composition having
4 to 20 weight percent fluoride based on the weight of said
fluorided silica-alumina before calcining.
(3) combining said calcined composition and bis(n-
butylcyclopentadienyl) zirconium dichloride at a temperature
within the range of 15° C to 80° C to produce a mixture; and
(4) after between 1 minute and 1 hour, combining said mixture and
triethylaluminum to produce said catalyst composition.
4. A process according to claim 3, wherein said process consists essentially
of steps (1), (2), (3), and (4),
5. A catalyst composition in which there is an absence of aiuminoxanes and
borate compounds, said catalyst composition being produced by the
process of claim 1.
6. A catalyst composition according to claim 5, wherein said catalyst
composition has an activity greater than 1000 grams of polymer per
gram of fluorided silica-alumina per hour under slurry polymerization
conditions, using isobutene as a diluent, with a polymerization
temperature 90° C, and an ethylene pressure of 3.893 MPa (550 psig).
7. A catalyst composition according to claim 5, wherein said catalyst
composition has an activity greater than 8000 grams of polymer per
gram of fluorided silica-alumina per hour under slurry polymerization
conditions, using isobutene as a diluent, with a polymerization
temperature of 90° C, and an ethylene pressure of 3.893 MPa (550
psig).
12. A catalyst composition according to claim 5, wherein said fluorided silica-
alumina comprises from 10 to 30% by weight alumina, from 4 to 20%
by weight fluoride based on the weight of the fluorided silica-alumina
before calcining, and is calcined at a temperature from 350 to 550° C.
13. A catalyst composition comprising a post-contacted organometal
compound, a post-contacted organoaluminium compound, and a post-
contacted fluorided silica-alumina; wherein there is an absence of
aluminoxanes and borate compounds.
14. A polymerization process comprising contacting at least one monomer
and said composition of claim 5, under polymerization conditions to
produce a polymer.
15. A process according to claim 14, wherein said polymerization conditions
comprise slurry polymerization conditions.
16. A process according to claim 15, wherein said contacting is conducted in
a loop reaction zone.
17. A process according to claim 16, wherein said contacting is conducted in
the presence of a diluents that comprises, in major part, isobutene.
18. A process according to claim 14, wherein at least one monometer is
ethylene.
19. A process according to claim 14, wherein at least one monomer
comprises ethylene and an aliphatic 1-olefin having 3 to 20 carbon
atoms per molecule.
20. A process according to claim 14, further comprising the step of forming
an article from the polymer.
This invention provides catalyst compositions that are useful for
polymerizing at least one monomer to produce a polymer. This invention also
provides catalyst compositions that are useful for polymerizing at least one
monomer to produce a polymer, wherein said catalyst composition comprises a
post-contacted organometal compound, a post-contacted organoaluminum
compound, and a post-contacted fluorided silica-alumina.

Documents:

IN-PCT-2002-373-KOL-FORM-27.pdf

in-pct-2002-373-kol-granted-abstract.pdf

in-pct-2002-373-kol-granted-assignment.pdf

in-pct-2002-373-kol-granted-claims.pdf

in-pct-2002-373-kol-granted-correspondence.pdf

in-pct-2002-373-kol-granted-description (complete).pdf

in-pct-2002-373-kol-granted-drawings.pdf

in-pct-2002-373-kol-granted-examination report.pdf

in-pct-2002-373-kol-granted-form 1.pdf

in-pct-2002-373-kol-granted-form 18.pdf

in-pct-2002-373-kol-granted-form 2.pdf

in-pct-2002-373-kol-granted-form 3.pdf

in-pct-2002-373-kol-granted-form 5.pdf

in-pct-2002-373-kol-granted-reply to examination report.pdf

in-pct-2002-373-kol-granted-specification.pdf

in-pct-2002-373-kol-granted-translated copy of priority document.pdf


Patent Number 222755
Indian Patent Application Number IN/PCT/2002/373/KOL
PG Journal Number 34/2008
Publication Date 22-Aug-2008
Grant Date 21-Aug-2008
Date of Filing 19-Mar-2002
Name of Patentee PHILLIPS PETROLEUM COMPANY
Applicant Address 4TH AND KEELER, BARTLESVILLE, OK
Inventors:
# Inventor's Name Inventor's Address
1 MCDANIEL, MAX, P 1601 MELMART DRIVE, BARTLESVILLE, OK 74006
2 COLLINS, KAZTHY, S 3915 SILVER LAKE DRIVE, BAZRTLESVILLE, OK 74006
3 EATON, ANTHONY, P 450 WILLIAMS LANDING DRIVE, SUGAR LAND, TX 77479
4 BENHAM, ELIZABETH, A 431 SHAZNNON, BAZRTLESVILLE, OK 74006
5 JENSEN, MICHAEL, D 2008 SKYLINE PLACE, BARTLESVILLE, OK 74006
6 MARTIN, JOEL, L 636 KENWOOD DRIVE, BARTLESVILLE, OK 74006
7 HAWLEY, GIL, R 1022 N. WYANDOTTE, DEWEY, OK 74029
PCT International Classification Number C08F 2/04, 2/18
PCT International Application Number PCT/US00/26349
PCT International Filing date 2000-09-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/401,354 1999-09-27 U.S.A.