U.S. patent application number 10/348613 was filed with the patent office on 2003-08-28 for organometal catalyst compositions.
Invention is credited to Benham, Elizabeth A., Collins, Kathy S., Eaton, Anthony P., Farmer, Kenneth R., Hawley, Gil R., Jensen, Michael D., Martin, Joel L., McDaniel, Max P., Palackal, Syriac J., Wittner, Christopher E..
Application Number | 20030162651 10/348613 |
Document ID | / |
Family ID | 23867905 |
Filed Date | 2003-08-28 |
United States Patent
Application |
20030162651 |
Kind Code |
A1 |
Collins, Kathy S. ; et
al. |
August 28, 2003 |
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 contacting a organometal
compound/organoaluminum mixture, a treated solid oxide compound,
and, optionally, a second organoaluminum compound.
Inventors: |
Collins, Kathy S.;
(Bartlesville, OK) ; Palackal, Syriac J.;
(Bartlesville, OK) ; McDaniel, Max P.;
(Bartlesville, OK) ; Jensen, Michael D.;
(Bartlesville, OK) ; Hawley, Gil R.; (Dewey,
OK) ; Farmer, Kenneth R.; (Dewey, OK) ;
Wittner, Christopher E.; (Bartlesville, OK) ; Benham,
Elizabeth A.; (Bartlesville, OK) ; Eaton, Anthony
P.; (Dewey, OK) ; Martin, Joel L.;
(Bartlesville, OK) |
Correspondence
Address: |
JOHN S. PRATT, ESQ
KILPATRICK STOCKTON, LLP
1100 PEACHTREE STREET
SUITE 2800
ATLANTA
GA
30309
US
|
Family ID: |
23867905 |
Appl. No.: |
10/348613 |
Filed: |
January 21, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10348613 |
Jan 21, 2003 |
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09470514 |
Dec 22, 1999 |
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6524987 |
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Current U.S.
Class: |
502/114 ;
502/102; 502/103; 502/117; 526/160; 526/64; 526/943 |
Current CPC
Class: |
C08F 4/65927 20130101;
Y10S 526/943 20130101; C08F 4/65912 20130101; C08F 2410/07
20210101; C08F 10/00 20130101; C08F 210/16 20130101; C08F 10/00
20130101; C08F 4/65916 20130101; C08F 210/16 20130101; C08F 210/14
20130101; C08F 2500/12 20130101; C08F 2500/10 20130101 |
Class at
Publication: |
502/114 ;
502/102; 502/103; 502/117; 526/64; 526/160; 526/943 |
International
Class: |
B01J 031/00; B01J
037/00 |
Claims
That which is claimed is:
1. A process to produce a catalyst composition, said process
comprising: 1) contacting at least one organometal compound and at
least one first organoaluminum compound to produce an
organometal/organoaluminum mixture; wherein said organometal
compound has the following general formula:
(X.sup.1)(X.sup.2)(X.sup.3)(X.sup.4)M.sup.1 wherein M.sup.1 is
selected from the group consisting of titanium, zirconium, and
hafnium; wherein (X.sup.1) and (X.sup.2) are cyclopentadienyl
derivatives and at least one is a fluorenyl or substituted
fluorenyl; wherein cyclopentadienyl derivatives are selected from
the group consisting of cyclopentadienyls, indenyls, fluorenyls,
substituted cyclopentadienyls, substituted indenyls, and
substituted fluorenyls; wherein substituents on said substituted
cyclopentadienyls, substituted indenyls, and substituted fluorenyls
of (X.sup.1) and (X.sup.2) 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, oxygen
groups, silicon, phosphorus, boron, germanium, and hydrogen;
wherein (X.sup.1) and (X.sup.2) are connected by a bridge having
one or two atoms between (X.sup.1) and (X.sup.2); and further
wherein said one or two atoms in said bridge can contain
substituents; wherein (X.sup.3) and (X.sup.4) 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; and
wherein said first organoaluminum compound is selected from the
group consisting of triethyl aluminum, tripropyl aluminum and
tri-n-butyl aluminum; 2) contacting said organometal/organoaluminum
mixture with a treated solid oxide compound and optionally, a
second organoaluminum compound; wherein said second organoaluminum
compound has the following general formula:
Al(X.sup.5).sub.n(X.sup.6).sub.3-n wherein (X.sup.5) is a
hydrocarbyl having from 1 to about 20 carbon atoms; wherein
(X.sup.6) is a halide, hydride, or alkoxide; and wherein "n" is a
number from 1 to 3 inclusive; and wherein said treated solid oxide
compound is produced by a process comprising: a) contacting at
least one solid oxide compound with at least one
electron-withdrawing anion source compound; b) optionally, also
contacting said solid oxide compound with at least one metal salt
compound; and c) calcining said solid oxide compound before,
during, or after contacting with said electron-withdrawing anion
source compound or metal salt compound to produce said treated
solid oxide compound.
2. A process according to claim 1 wherein (X.sup.3) and (X.sup.4)
are selected from the group consisting of halides and hydrocarbyls,
where such hydrocarbyls have from 1 to about 10 carbon atoms.
3. A process according to claim 2 wherein M.sup.1 in said
organometal compound is zirconium.
4. A process according to claim 3 wherein (X.sup.1) or (X.sup.2) is
cyclopentadienyl.
5. A process according to claim 4 wherein said bridge in said
organometal compound is a substituted single carbon bridge.
6. A process according to claim 5 wherein (X.sup.3) and (X.sup.4)
are selected from the group consisting of fluoro, chloro, and
methyl.
7. A process according to claim 6 wherein said organometal compound
is selected from the group consisting of [2-
.eta..sup.5-cyclopentadienyl)-2-
-(-.eta..sup.5-fluoren-9-yl)hex-5-ene]zirconium(IV) dichloride;
1,2-ethanediylbis(9-fluorenyl)zirconium dichloride;
diphenylmethanediyl(9-fluorenyl, cyclopentadienyl)zirconium
dichloride; and phenylmethylmethanediyl(9-fluorenyl,
cyclopentadienyl)zirconium dichloride.
8. A process according to claim 7 wherein said organometal compound
is
[2-(.eta..sup.5-cyclopentadienyl)-2-(.eta..sup.5-fluoren-9-yl)hex-5-ene]z-
irconium(IV) dichloride.
9. A process according to claim 1 wherein said first organoaluminum
compound is triethylaluminum.
10. A process according to claim 1 wherein said treated solid oxide
compound comprises oxygen and at least one element selected from
the group consisting of groups IIA-VIIIA and IB-VIIB of the
Periodic Table of Elements, including lanthanides and
actinides.
11. A process according to claim 10 wherein said element is
selected from the group consisting of Al, B, Be, Bi, Cd, Co, Cr,
Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn
and Zr.
12. A process according to claim 10 wherein said solid oxide
compounds are selected from the group consisting of
Al.sub.2O.sub.3, B.sub.2O.sub.3, BeO, Bi.sub.2O.sub.3, CdO,
Co.sub.3O.sub.4, Cr.sub.2O.sub.3, CuO, Fe.sub.2O.sub.3,
Ga.sub.2O.sub.3, La.sub.2O.sub.3, Mn.sub.2O.sub.3, MoO.sub.3, NiO,
P.sub.2O.sub.5, Sb.sub.2O.sub.5, SiO.sub.2, SnO.sub.2, SrO,
ThO.sub.2, TiO.sub.2, V.sub.2O.sub.5, WO.sub.3, Y.sub.2O.sub.3,
ZnO, ZrO.sub.2, and mixtures thereof.
13. A process according to claim 1 wherein the concentration of
said first organoaluminum compound in said
organometal/organoaluminum mixture ranges from about 0.3 to about 5
molar.
14. A process according to claim 13 wherein the concentration of
said first organoaluminum compound in said
organometal/organoaluminum mixture ranges from about 0.5 to 2.5
molar.
15. A process according to claim 1 wherein the concentration of
organometal compound in said organometal/organoaluminum mixture
ranges from about 0.005 and about 0.5 molar.
16. A process according to claim 15 wherein the concentration of
organometal compound in said organometal/organoaluminum mixture
ranges from 0.01 and 0.1 molar.
17. A process according to claim 1 wherein said catalyst
composition is contacted with monomer in a prepolymerization
step.
18. A process according to claim 17 wherein said catalyst
composition is contacted with ethylene at a temperature of less
than 40.degree. C. and for a period of about 1 to 120 minutes.
19. A process to produce a catalyst composition, said process
comprising: 1) contacting
[2-(.eta..sup.5-cyclopentadienyl)-2-(.eta..sup.5-fluoren-9--
yl)hex-5-ene]zirconium(IV) dichloride with triethyl aluminum to
produce an organometal/triethyl aluminum mixture; wherein the
concentration of triethyl aluminum in said organometal/triethyl
aluminum mixture ranges from 0.5 to 2.5 molar; wherein the
concentration of organometal in said organometal/triethyl aluminum
mixture ranges from 0.01 to 1 molar; 2) combining a chlorided,
zinc-containing alumina and said organometal/triethyl aluminum
mixture to produce said catalyst composition; wherein said
chlorided, zinc-containing alumina is produced by a process
comprising contacting alumina with an aqueous solution of zinc
chloride to produce a zinc-containing alumina, calcining said
zinc-containing alumina at about 600.degree. C. for three hours to
produce a calcined zinc-containing alumina, and while calcining,
contacting said zinc-containing alumina with carbon tetrachloride
to produce said chlorided, zinc-containing alumina.
20. A catalyst composition produced by the process of claim 1.
21. A catalyst composition according to claim 20 wherein said
catalyst composition has an activity greater than 500 under slurry
polymerization conditions, using isobutane as a diluent, with a
polymerization temperature of 90.degree. C., and an ethylene
pressure of 550 psig.
22. A catalyst composition according to claim 21 wherein said
catalyst composition has an activity greater than 1000 under slurry
polymerization conditions, using isobutane as a diluent, with a
polymerization temperature of 90.degree. C., and an ethylene
pressure of 550 psig.
23. A catalyst composition according to claim 22 wherein a weight
ratio of said second organoaluminum compound to said treated solid
oxide compound in said catalyst composition ranges from about 3:1
to about 1:100.
24. A catalyst composition according to claim 23 wherein said
weight ratio of said second organoaluminum compound to said treated
solid oxide compound in said catalyst composition ranges from 1:1
to 1:50.
25. A catalyst composition according to claim 24 wherein a weight
ratio of said treated solid oxide compound to said organometal
compound in said catalyst composition ranges from about 1000:1 to
about 10:1.
26. A catalyst composition according to claim 25 wherein said
weight ratio of said treated solid oxide compound to said
organometal compound in said catalyst composition ranges from 250:1
to 20:1.
27. A catalyst composition according to claim 20 wherein said
composition subsequent to contacting said organometal
compound/organoaluminum compound, treated solid oxide compound, and
second organoaluminum compound consists essentially of organometal
compound and treated solid oxide compound.
28. A catalyst composition according to claim 27 wherein said
composition subsequent to contacting said organometal
compound/organoaluminum compound, treated solid oxide compound, and
second organoaluminum compound consists essentially of organometal
compound, second organoaluminum compound and treated solid oxide
compound.
29. A polymerization process comprising contacting at least one
monomer and said catalyst composition of claim 20 under
polymerization conditions to produce a polymer.
30. A process according to claim 29 wherein said polymerization
conditions comprise slurry polymerization conditions.
31. A process according to claim 30 wherein said contacting is
conducted in a loop reaction zone.
32. A process according to claim 31 wherein said contacting is
conducted in the presence of a diluent that comprises, in major
part, isobutane.
33. A process according to claim 29 wherein at least one monomer is
ethylene.
34. A process according to claim 29 wherein at least one monomer
comprises ethylene and an aliphatic 1-olefin having 3 to 20 carbon
atoms per molecule.
35. A polymer produced in accordance with the process of claim
29.
36. An article that comprises said polymer produced according to
claim 29.
Description
FIELD OF THE INVENTION
[0001] This invention is related to the field of organometal
catalyst compositions.
BACKGROUND OF THE INVENTION
[0002] 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.
[0003] One of these technologies is called metallocene catalyst
technology. Metallocene catalysts have been known since about 1958.
However, their low productivity did not allow them to be
commercialized. About 1974, it was discovered that contacting one
part water with one part trimethylaluminum 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.
[0004] Fluoro-organo borate compounds have been used in place of
large amounts of methyl aluminoxane. However, this is not
satisfactory, since such borate compounds are very sensitive to
poisons and decomposition, and can also be very expensive.
[0005] 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.
[0006] Bridged fluorenyl zirconium metallocenes hold a special
place in the development of loop-slurry polyethylene technology.
Such compounds are known for their excellent ability to incorporate
hexene efficiently, which is important in a loop-slurry process.
They also are capable of producing very high molecular weight
polymer, which is difficult for bis-cyclopentadienyl zirconium
species, or even for bis-indenyl zirconium species. Some, notably
[2-(.eta..sup.5-cyclopentadienyl)-2-(.eta..sup.5-f-
luoren-9-yl)hex-5-ene]zirconium(IV) dichloride, produce
exceptionally transparent and glossy films and other manufactures.
Bridged fluorenyl zirconium metallocenes are activated well enough
by methyl aluminoxanes (MAO), but unfortunately MAO is expensive
and in the liquid state tends to cause fouling in the reactor.
[0007] An object of this invention is to provide a process that
produces a catalyst composition that can be used to polymerize at
least one monomer to produce a polymer.
[0008] Another object of this invention is to provide the catalyst
composition.
[0009] Another object of this invention is to provide a process
comprising contacting at least one monomer and the catalyst
composition under polymerization conditions to produce the
polymer.
[0010] Another object of this invention is to provide an article
that comprises the polymer produced with the catalyst composition
of this invention.
SUMMARY OF THE INVENTION
[0011] 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"):
[0012] 1) contacting at least one organometal compound and at least
one first organoaluminum compound to produce an
organometal/organoaluminum mixture;
[0013] wherein the organometal compound has the following general
formula:
(X.sup.1)(X.sup.2)(X.sup.3)(X.sup.4)M.sup.1
[0014] wherein M.sup.1 is selected from the group consisting of
titanium, zirconium, and hafnium;
[0015] wherein (X.sup.1) and (X.sup.2) are cyclopentadienyl
derivatives and at least one is a fluorenyl or substituted
fluorenyl;
[0016] wherein cyclopentadienyl derivatives are selected from the
group consisting of cyclopentadienyls, indenyls, fluorenyls,
substituted cyclopentadienyls, substituted indenyls, and
substituted fluorenyls;
[0017] wherein substituents on the substituted cyclopentadienyls,
substituted indenyls, and substituted fluorenyls of (X.sup.1) and
(X.sup.2) 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, oxygen groups, silicon,
phosphorus, boron, germanium, and hydrogen;
[0018] wherein (X.sup.1) and (X.sup.2) are connected by a bridge
having one or two atoms between (X.sup.1) and (X.sup.2); and
further wherein the one or two atoms of the bridge can contain
substituents;
[0019] wherein (X.sup.3) and (X.sup.4) 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; and
[0020] wherein the first organoaluminum compound is selected from
the group consisting of triethyl aluminum, tripropyl aluminum, and
tri-n-butyl aluminum;
[0021] 2) contacting the organometal/organoaluminum mixture with a
treated solid oxide compound and optionally, at least one second
organoaluminum compound;
[0022] wherein the second organoaluminum compound is added in a
reactor, and is represented by the following formula:
Al(X.sup.5).sub.n(X.sup.6).sub.3-n
[0023] wherein (X.sup.5) is a hydrocarbyl having from 1 to about 20
carbon atoms;
[0024] wherein (X.sup.6) is a halide, hydride, or alkoxide; and
[0025] wherein "n" is a number from 1 to 3 inclusive; and;
[0026] wherein the treated solid oxide compound is produced by a
process comprising: a) contacting at least one solid oxide compound
with at least one electron-withdrawing anion source compound; b)
optionally, also contacting the solid oxide compound with at least
one metal salt compound; and c) calcining the solid oxide compound
before, during, or after contacting the electron-withdrawing anion
source compound or metal salt compound to produce the treated solid
oxide compound.
[0027] In accordance with a second 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.
[0028] In accordance with a third embodiment of this invention, an
article is provided. The article comprises the polymer produced in
accordance with this invention.
[0029] These objects, and other objects, will become more apparent
to those with ordinary skill in the art after reading this
disclosure.
DETAILED DESCRIPTION OF THE INVENTION
[0030] A process to produce a catalyst composition is provided. The
process comprises contacting at least one organometal compound and
at least one first organoaluminum compound to produce an
organometal/organoaluminum mixture. Then, contacting the
organometal/organoaluminum mixture with a treated solid oxide
compound and optionally, at least one second organoaluminum
compound to produce the catalyst composition.
[0031] The organometal compound utilized in this invention has the
following general formula:
(X.sup.1 )(X.sup.2)(X.sup.3)(X.sup.4)M.sup.1
[0032] M.sup.1 is selected from the group consisting of titanium,
zirconium, and hafnium. Preferably, M.sup.1 is zirconium.
[0033] (X.sup.1) and (X.sup.2) are cyclopentadienyl derivatives and
at least one is a fluorenyl or substituted fluorenyl.
Cyclopentadienyl derivatives are selected from the group consisting
of cyclopentadienyls, indenyls, fluorenyls, substituted
cyclopentadienyls, substituted indenyls, and substituted
fluorenyls. Preferably, (X.sup.1) or (X.sup.2) is
cyclopentadienyl.
[0034] Substituents on the substituted cyclopentadienyls,
substituted indenyls, and substituted fluorenyls of (X.sup.1) and
(X.sup.2) 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, oxygen groups, silicon,
phosphorus, boron, germanium, and hydrogen.
[0035] 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. Substituted silyl 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 alkyl 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.
[0036] Suitable examples of such substituents are methyl, ethyl,
propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl,
cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl,
pentenyl, butenyl, phenyl, chloro, bromo, iodo, trimethylsilyl, and
phenyloctylsilyl.
[0037] (X.sup.1) or (X.sup.2) are connected by a bridge having one
or two atoms between (X.sup.1) and (X.sup.2). The one or two atoms
in the bridge can contain substituents. Preferably, the bridge has
one atom connecting (X.sup.1) and (X.sup.2). The atoms of the
bridge can be carbon or silicon, optionally substituted with alkyl
or aryl radicals. A substituted single carbon bridge is
preferred.
[0038] (X.sup.3) and (X.sup.4) 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; aryloxide groups,
organometallic groups, and substituted organometallic groups.
[0039] 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 (X.sup.3) and (X.sup.4) 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 (X.sup.3) and (X.sup.4) are
selected from the group consisting of fluoro, chloro, and
methyl.
[0040] 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.
[0041] Various processes are known to make these organometal
compounds. See, for example, U.S. Pat. Nos. 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.
[0042] Bridged fluorenyl zirconium structures of utility in this
invention as organometal compounds include
1,2-ethanediylbis(9-fluorenyl)zirconium dichloride; (organometal
A), diphenylmethanediyl(9-fluorenyl, cyclopentadienyl)zirconium
dichloride (organometal B), and
phenylmethylmethanediyl(9-fluorenyl, cyclopentadienyl)zirconium
dichloride (organometal C),
[2-(.eta..sup.5-cyclopentadienyl)-2-(.eta..su-
p.5-fluoren-9-yl)hex-5-ene]zirconium(IV) dichloride (organometal
D). These structures are shown below. 1
[0043] Preferably, the organometal compound is organometal D.
[0044] The first organoaluminum compound is selected from the group
consisting of triethyl aluminum (TEA), tripropyl aluminum, and
tri-n-butyl aluminum. Preferably, the first organoaluminum compound
is TEA.
[0045] Optionally, at least one second organoaluminum compound also
can be added to a reactor directly as a cocatalyst. The second
organoaluminum compound has the following general formula:
Al(X.sup.5).sub.n(X.sup.6).sub.3-n
[0046] In this formula, (X.sup.5) is a hydrocarbyl having from 1 to
about 20 carbon atoms. Currently, it is preferred when (X.sup.5) is
a linear alkyl having from 1 to about 10 carbon atoms. However, it
is most preferred when (X.sup.5) is selected from the group
consisting of ethyl, propyl, and butyl.
[0047] In this formula, (X.sup.6) is a halide, hydride, or
alkoxide. Currently, it is preferred when (X.sup.6) is
independently selected from the group consisting of fluoro and
chloro. However, it is most preferred when (X.sup.6) is chloro.
[0048] In this formula, "n" is a number from 1 to 3 inclusive.
However, it is preferred when "n" is 3.
[0049] Examples of such compounds are as follows:
[0050] trimethyl aluminum;
[0051] triethyl aluminum (TEA);
[0052] tripropyl aluminum;
[0053] diethylaluminum ethoxide;
[0054] tributylaluminum;
[0055] diisobutylaluminum hydride;
[0056] triisobutylaluminum hydride;
[0057] triisobutylaluminum; and
[0058] diethylaluminum chloride.
[0059] Currently, TEA is preferred.
[0060] Treated solid oxide compounds are compounds that have had
their Lewis acidity increased. The treated solid oxide compound can
be produced by a process comprising contacting at least one solid
oxide compound with at least one electron-withdrawing anion source
to form an anion-containing solid oxide compound. The solid oxide
compound is calcined either prior to, during, or after contacting
with the electron-withdrawing anion source. Calcining is discussed
later in this disclosure.
[0061] Generally, the specific surface area of the solid oxide
compound after calcining at 500.degree. C. is from about 100 to
about 1000 m.sup.2/g, preferably, from about 200 to about 800
m.sup.2/g, and most preferably, from 250 to 600 m.sup.2/g.
[0062] The specific pore volume of the solid oxide compound is
typically greater than about 0.5 cc/g, preferably, greater than
about 0.8 cc/g, and most preferably, greater than 1.0 cc/g.
[0063] It is preferred when the treated solid oxide compound
comprises oxygen and at least one element selected from the group
consisting of groups IIA-VIIIA and IB-VIIB of the Periodic Table of
Elements, including lanthanides and actinides. However, it is
preferred when the element is selected from the group consisting of
Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn,
Sr, Th, Ti, V, W, P, Y, Zn and Zr. It is important that these
treated solid oxide compounds have electron withdrawing ability,
while not wanting to be bound by theory, it is believed that a
treated solid oxide compound should have a higher Lewis acidity
compared to the untreated solid oxide compound. However, it is hard
to accurately measure the Lewis acidity of these treated, and
untreated solid oxide compounds so various methods have been used.
Currently, comparing the activities of treated and untreated solid
oxide compounds under acid catalyzed reactions is preferred.
[0064] Treated solid oxide compounds can be produced in a variety
of ways, such as, for example, by gelling, co-gelling, or
impregnation of one compound onto another.
[0065] In general, it is preferred to contact at least one solid
oxide compound, such as, for example, alumina, zirconia, titania,
and mixtures thereof, such as, for example, silica-alumina, with at
least one electron-withdrawing anion source compound, to form an
anion-containing solid oxide compound, followed by calcining the
anion-containing solid oxide compound to form a treated solid oxide
compound. In the alternative, a solid oxide compound and an
electron-withdrawing anion source compound can be contacted and
calcined simultaneously.
[0066] The electron-withdrawing anion source compound is any
compound that increases the Lewis acidity of the solid oxide under
the conditions given herein for producing the treated solid oxide
compound. These electron-withdrawing anion source compounds
increase the Lewis acidity of the solid oxide compound by
contributing to the formation of an electron withdrawing anion,
such as, for example, sulfates, halides, and triflates. It should
be noted that one or more different electron withdrawing anion
source compounds can be used.
[0067] The acidity of the solid oxide compound can be further
enhanced by using two, or more, electron-withdrawing anion source
compounds in two, or more, separate contacting steps. An example of
such a process is contacting at least one solid oxide compound with
a first electron-withdrawing anion source compound to form a first
anion-containing solid oxide compound, followed by calcining the
first anion-containing solid oxide compound, followed by contacting
with a second electron-withdrawing anion source compound to form a
second anion-containing solid oxide compound, followed by calcining
the second anion-containing solid oxide compound to form a treated
solid oxide compound. It should be noted that the first and second
electron-withdrawing anion source compounds can be the same, but
are preferably different.
[0068] Suitable examples of solid oxide compounds include, but are
not limited to, Al.sub.2O.sub.3, B.sub.2O.sub.3, BeO,
Bi.sub.2O.sub.3, CdO, Co.sub.3O.sub.4, Cr.sub.2O.sub.3, CuO,
Fe.sub.2O.sub.3, Ga.sub.2O.sub.3, La.sub.2O.sub.3, Mn.sub.2O.sub.3,
MoO.sub.3, NiO, P.sub.2O.sub.5,Sb.sub.2- O.sub.5, SiO.sub.2,
SnO.sub.2, SrO, ThO.sub.2, TiO.sub.2, V.sub.2O.sub.5, WO.sub.3,
Y.sub.2O.sub.3, ZnO, ZrO.sub.2: and mixtures thereof, such as, for
example, silica-alumina and silica-zirconia. It should be noted
that solid oxide compounds that comprise Al--O bonds are currently
preferred.
[0069] Before, during or after calcining, the solid oxide compound
can be contacted with an electron-withdrawing anion source
compound. The electron-withdrawing anion source compound can be
selected from the group consisting of at least one
halogen-containing compound, sulfate-containing compound, or
triflate-containing compound. The halogen-containing compound is
selected from the group consisting of chlorine-containing
compounds, bromine-containing compounds, and fluorine-containing
compounds. The halogen-containing compound can be in a liquid
phase, or preferably, a vapor phase. Optionally, the solid oxide
compound can be calcined at 100 to 900.degree. C. before being
contacted with the halogen-containing compound.
[0070] Any method known in the art of contacting the solid oxide
compound with the fluorine-containing compound can be used in this
invention. A common method is to impregnate the solid oxide
compound with an aqueous solution of a fluoride-containing salt
before calcining, such as ammonium fluoride [NH.sub.4F], ammonium
bifluoride [(NH.sub.4HF.sub.2], hydrofluoric acid [HF], ammonium
silicofluoride [(NH.sub.4).sub.2SiF.sub.- 6], ammonium fluoroborate
[NH.sub.4BF.sub.4], ammonium fluorophosphate [NH.sub.4PF.sub.6],
and mixtures thereof.
[0071] In a second method, the fluorine-containing compound can be
dissolved into an organic compound, such as an alcohol, and added
to the solid oxide compound to minimize shrinkage of pores during
drying. Drying can be accomplished by an method known in the art,
such as, for example, vacuum drying, spray drying, flashing drying,
and the like.
[0072] In a third method, the fluorine-containing compound can be
added during the calcining step. In this technique, the
fluorine-containing compound is vaporized into the gas stream used
to fluidize the solid oxide compound so that it is fluorided from
the gas phase. In addition to some of the fluorine-containing
compounds described previously, volatile organic fluorides can be
used at temperatures above their decomposition points, or at
temperatures high enough to cause reaction. For example,
perfluorohexane, perfluorobenzene, trifluoroacetic acid,
trifluoroacetic anhydride, hexafluoroacetylacetonate, and mixtures
thereof can be vaporized and contacted with the solid oxide
compound at about 300 to about 600.degree. C. in air or nitrogen.
Inorganic fluorine-containing compounds can also be used, such as
hydrogen fluoride or even elemental fluorine.
[0073] Generally, the amount of fluorine present is about 2 to
about 50 weight percent fluorine based on the weight of the treated
solid oxide compound before calcining or the amount added to a
precalcined solid oxide compound. Preferably, it is about 3 to
about 25 weight percent, and most preferably, it is 4 to 20 weight
percent fluorine based on the weight of the treated solid oxide
compound before calcining or the amount added to a precalcined
solid oxide compound.
[0074] Any method known in the art of contacting the solid oxide
compound with the chlorine-containing compound or
bromine-containing compound can be used in this invention.
Generally, the contacting is conducted during or after calcining,
preferably during calcining. Any suitable chlorine-containing
compound or bromine-containing compound that can deposit chlorine
or bromine or both on the solid oxide compound can be used.
Suitable chlorine-containing compounds and bromine-containing
compound include volatile or liquid organic chloride or bromide
compounds and inorganic chloride or bromide compounds. Organic
chloride or bromide compounds can be selected from the group
consisting of carbon tetrachloride, chloroform, dichloroethane,
hexachlorobenzene, trichloroacetic acid, bromoform, dibromomethane,
perbromopropane, phosgene, and mixtures thereof. Inorganic chloride
or bromide compounds can be selected from the group consisting of
gaseous hydrogen chloride, silicon tetrachloride, tin
tetrachloride, titanium tetrachloride, aluminum trichloride, boron
trichloride, thionyl chloride, sulfuryl chloride, hydrogen bromide,
boron tribromide, silicon tetrabromide, and mixtures thereof.
Additionally, chlorine and bromine gas can be used.
[0075] If an inorganic chlorine-containing compound or
bromine-containing compound is used, such as titanium
tetrachloride, aluminum trichloride, or boron trichloride, it also
can be possible to contact the chlorine-containing compound or
bromine-containing compound with the solid oxide compound after
calcining, either by vapor phase deposition or even by using an
anhydrous solvent.
[0076] Generally, the amount of chlorine or bromine used is from
about 0.01 to about 10 times the weight of the treated solid oxide
compound before calcining or the amount added to a precalcined
solid oxide compound, preferably it is from about 0.05 to about 5
times, most preferably from 0.05 to 1 times the weight of the
treated solid oxide compound before calcining or the amount added
to a precalcined solid oxide compound.
[0077] In another embodiment of this invention, the treated solid
oxide compound can be produced by a process comprising contacting
at least one solid oxide compound with at least one
electron-withdrawing anion source and at least one metal salt
compound. In general, it is preferred to contact at least one solid
oxide compound, such as, for example, alumina, zirconia, titania,
and mixtures thereof, or with mixtures of other solid oxide
compounds such as, for example, silica-alumina, with at least one
metal salt compound and at least one electron-withdrawing anion
source compound, to form an anion- and metal-containing solid oxide
compound, followed by calcining the anion- and metal-containing
solid oxide compound to form a treated solid oxide compound. In the
alternative, a solid oxide compound, a metal salt compound, and an
electron-withdrawing anion source compound can be contacted and
calcined simultaneously. In another alternative, the metal salt
compound and the electron-withdrawing anion source compound can be
the same compound.
[0078] The metal salt compound is any compound that increases the
Lewis acidity of the solid oxide compound under the conditions
given herein for producing the treated solid oxide compound. It is
preferred when the metal in the metal salt is selected from the
group consisting of groups IIA-VIIIA and IB-VIIB of the Periodic
Table of Elements, including lanthanides and actinides. However, it
is preferred when the element is selected from the group consisting
of Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si,
Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.
[0079] To produce the treated solid oxide compound, at least one
metal salt compound can be contacted with the solid oxide compound
by any means known in the art to produce a metal-containing solid
oxide compound. The metal salt compound can be added to the solid
oxide compound before calcining, during calcining, or in a separate
step after calcining the solid oxide compound.
[0080] Generally, the solid oxide compound is contacted with an
aqueous or organic solution of the metal salt compound before
calcining. For example, the metal can be added to the solid oxide
compound by forming a slurry of the solid oxide compound in a
solution of the metal salt compound 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 metal after drying. Any water soluble or
organic soluble metal salt compound is suitable that can impregnate
the solid oxide compound with metal. For example, the drying can be
completed by suction filtration followed by evaporation, vacuum
drying, spray drying, or flash drying.
[0081] If the metal is added to the solid oxide compound after
calcination, one preferred method is to impregnate the solid oxide
compound with a hydrocarbon solution of the metal salt
compound.
[0082] Generally, the amount of metal present in the
metal-containing solid oxide compound is in a range of about 0.1 to
about 30 weight percent metal where the weight percent is based on
the weight of the metal-containing solid oxide compound before
calcining or the amount added to a precalcined solid oxide
compound. Preferably, the amount of metal present in the
metal-containing solid oxide compound is in a range of about 0.5 to
about 20 weight percent metal based on the weight of the
metal-containing solid oxide compound before calcining or the
amount added to a precalcined solid oxide compound. Most
preferably, the amount of metal present in the metal-containing
solid oxide compound is in a range of 1 to 10 weight percent metal
based on the weight of the metal-containing solid oxide compound
before calcining or the amount added to a precalcined solid oxide
compound.
[0083] The metal-containing solid oxide compound can then be
contacted with at least one electron-withdrawing anion source
compounds by the methods discussed previously in this
disclosure.
[0084] Before, during, or after the solid oxide compound is
combined with the metal salt compound or the electron-withdrawing
anion source compound to produce the metal-containing solid oxide
compound, it is calcined for about 1 minute to about 100 hours,
preferably from about 1 hour to about 50 hours, and most
preferably, from 3 to 20 hours. Generally, the calcining is
conducted at a temperature in a range of about 200.degree. C. to
about 900.degree. C., preferably from about 300.degree. C. to about
700.degree. C., and most preferably, from 350.degree. C. to
600.degree. C. The calcining can be conducted in any suitable
atmosphere. Generally, the calcining can be completed in an inert
atmosphere. Alternatively, the calcining can be completed in an
oxidizing atmosphere, such as, oxygen or air, or a reducing
atmosphere, such as, hydrogen or carbon monoxide.
[0085] In order to obtain high activity from the organometal
compounds discussed previously, it is necessary to first contact
the organometal compound and the first organoaluminum compound to
produce an organometal/organoaluminum mixture. Then, the
organometal/organoaluminum mixture is injected into a reactor along
with the treated solid oxide compound and optionally, the second
organoaluminum compound can be added as a cocatalyst. The
concentration of the first organoaluminum compound in the
organometal/organoaluminum mixture ranges from about 0.1 to about
10 molar, preferably from about 0.3 to about 5 molar, most
preferably from 0.5 to 2.5 molar. The concentration of the
organometal compound in the organometal/organoaluminum mixture
ranges from about 0.001 and about 1.0 molar, preferably between
about 0.005 and about 0.5 molar, most preferably between 0.01 and
0.1 molar.
[0086] Another embodiment of this invention is to pretreat the
catalyst composition with monomer at low temperature for a short
time to obtain a small amount of polymer on the catalyst
composition before the main polymerization reaction at higher
temperatures. This process is called prepolymerization and can
improve activity still further. Preferably, the catalyst
composition is pretreated with ethylene at a temperature of less
than 40.degree. C., most preferably less than 30.degree. C. for a
period of about 1 to about 120 minutes, preferably from 10 to 70
minutes
[0087] A weight ratio of the second organoaluminum compound to the
treated solid oxide compound 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.
[0088] A weight ratio of the treated solid oxide compound 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 250:1 to 20:1. These ratios are based on
the amount of the components combined to give the catalyst
composition.
[0089] After contacting, the catalyst composition comprises a
post-contacted organometal compound, a post-contacted first
organoaluminum compound, a post-contacted treated solid oxide
compound, and, optionally, a post-contacted second organoaluminum
compound. Preferably, the post-contacted treated solid oxide
compound 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.
[0090] A weight ratio of the post-contacted second organoaluminum
compound to the post-contacted treated solid oxide compound 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.
[0091] A weight ratio of the post-contacted treated solid oxide
compound to the post-contacted 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 250:1 to
20:1. These ratios are based on the amount of the components
combined to give the catalyst composition.
[0092] The catalyst composition of this invention has an activity
greater than 100 grams of polymer per gram of treated solid oxide
compound per hour, preferably greater than 500, and most preferably
greater than about 1,000. This activity is measured under slurry
polymerization conditions, using isobutane as the diluent, and with
a polymerization temperature of 90.degree. 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.
[0093] 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 water
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 fluoro-organo borate
compounds need to be used in order to form the catalyst
composition. It should be noted that organochromium compounds and
MgCl.sub.2 are not needed in order to form the catalyst
composition. Although aluminoxane, fluoro-organo borate compounds,
organochromium compounds, and MgCl.sub.2 are not needed in the
preferred embodiments, these compounds can be used in other
embodiments of this invention.
[0094] In another embodiment of this invention, a process
comprising contacting at least one monomer and the catalyst
composition to produce a 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-1-butene, 1-pentene, 3-methyl-1-pentene,
4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, and mixtures thereof.
[0095] 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, 1-butene, 1-pentene,
4-methyl-1-pentene, 1-hexene, 1-octene, and other olefins and
conjugated or nonconjugated diolefins such as 1,3-butadiene,
isoprene, piperylene, 2,3-dimethyl-1,3-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.
[0096] 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.
Pat. Nos. 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.
[0097] 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 micrometers, preferably about
25 to about 500 micrometers, and most preferably, 50 to 200
micrometers, for best control during polymerization.
[0098] 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"):
[0099] (1) contacting
[2-(.eta..sup.5-cyclopentadienyl)-2-(.eta..sup.5-flu-
oren-9-yl)hex-5-ene]zirconium(IV) dichloride with TEA to produce an
organometal/TEA mixture;
[0100] wherein the concentration of TEA in the organometal/TEA
mixture ranges from 0.5 to 2.5 molar;
[0101] wherein the concentration of organometal in the
organometal/TEA mixture ranges from 0.01 to 1 molar;
[0102] (2) combining a chlorided, zinc-containing alumina and the
organometal/TEA mixture to produce the catalyst composition;
[0103] wherein the chlorided, zinc-containing alumina is produced
by a process comprising contacting alumina with an aqueous solution
of zinc chloride to produce a zinc-containing alumina, calcining
said zinc-containing alumina at about 600.degree. C. for three
hours to produce a calcined zinc-containing alumina, and while
calcining, contacting the zinc-containing alumina with carbon
tetrachloride to produce the chlorided, zinc-containing
alumina.
[0104] Hydrogen can be used with this invention in a polymerization
process to control polymer molecular weight.
[0105] 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
[0106] Testing Methods
[0107] Melt index (MI, g/10 min) was determined in accordance with
ASTM D1238 at 190.degree. C. with a 2,160 gram weight.
[0108] High load melt index (HLMI, g/10 min) was determined in
accordance with ASTM D1238 at 190.degree. C. with a 21,600 gram
weight.
[0109] Polymer density was determined in grams per cubic centimeter
(g/cc) on a compression molded sample, cooled at about 15.degree.
C. per hour, and conditioned for about 40 hours at room temperature
in accordance with ASTM D1505 and ASTM D1928, procedure C.
[0110] Molecular weights and molecular weight distributions were
obtained using a Waters 150 CV gel permeation chromatograph with
trichlorobenzene (TCB) as the solvent, with a flow rate of 1
milliliter/minute at a temperature of 140.degree. C.
2,6-di-tert-butyl-4-methylphenol (BHT) at a concentration of 1.0
gram per liter was used as a stabilizer in the TCB. An injection
volume of 220 liters was used with a nominal polymer concentration
of 0.3 gram/liter at room temperature. Dissolution of the sample in
stabilized TCB was carried out by heating at about 160-170.degree.
C. for 20 hours with occasional, gentle agitation. The column was
two Waters HT-6E columns (7.8 mm.times.300 mm). The columns were
calibrated with a broad linear polyethylene standard (Phillips
Marlex.RTM. BHB 5003) for which the molecular weight had been
determined.
[0111] A "Quantachrome Autosorb-6 Nitrogen Pore Size Distribution
Instrument" was used to determined specific surface area ("surface
area") and specific pore volume ("pore volume"). This instrument
was acquired from the Quantachrome Corporation, Syosset, N.Y.
[0112] Description of the solid oxide compound preparation:
[0113] A commercial alumina sold as Ketjen grade B alumina was
obtained from Akzo Nobel Chemical having a pore volume of about
1.78 cc/g and a surface area of about 350 square meters per
gram.
[0114] A silica-alumina was obtained from W. R. Grace as MS 13-110
containing 13% by weight alumina and 87% by weight silica. The
silica-alumina had a pore volume of about 1.2 cc/g and a surface
area of about 450 square meters per gram.
[0115] To calcine these solid oxide compounds, about 10 grams were
placed in a 1.75 inch quartz tube fitted with a sintered quartz
disk at the bottom. While the solid oxide compound was supported on
the disk, dry air was blown up through the disk at a rate of about
1.6 to about 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.degree. C. per hour to the indicated
temperature, such as 600.degree. C. At that temperature, the solid
oxide compound was allowed to fluidize for three hours in the dry
air. Afterward the solid oxide compound was collected and stored
under dry nitrogen, where it was protected from the atmosphere
until ready for testing. It was never allowed to experience any
exposure to the atmosphere.
[0116] To prepare one of the treated solid oxide compounds used in
these examples, referred to as treated solid oxide compound A, the
alumina described previously was impregnated with an aqueous
solution of zinc chloride. Approximately 200 milliliters of an
aqueous solution containing 20 grams of zinc chloride, ZnCl.sub.2,
were added to 100 grams of alumina to reach the point of incipient
wetness to produce a zinc-containing alumina. The zinc-containing
alumina was then dried overnight under half an atmosphere of vacuum
at 110.degree. C.. The zinc-containing alumina was calcined at
600.degree. C. for three hours, then 2.3 milliliters of carbon
tetrachloride were injected into the gas stream ahead of the
zinc-containing alumina, where it evaporated and was carried up
through the fluidizing bed to produce a chlorided, zinc-containing
alumina.
[0117] Another treated solid oxide compound used in these examples,
designated treated solid oxide compound B, was prepared, calcined,
and chlorided by the same procedure as described previously except
that the alumina was impregnated with an aqueous solution
containing only 40 grams of ZnCl.sub.2.
[0118] Another treated solid oxide compound used in these examples,
designated treated solid oxide compound C, was prepared by
calcining alumina at 600.degree. C. for three hours, then injecting
2.3 milliliters of carbon tetrachloride into the gas stream ahead
of the alumina bed, where it evaporated and was carried up through
the bed to produce a chlorided alumina.
[0119] To prepare another treated solid oxide compound used in
these examples, designated treated solid oxide compound D, alumina
was impregnated with an aqueous solution containing 20 grams of
ammonium sulfate, (NH.sub.4).sub.2SO.sub.4. It was then calcined at
600.degree. C. to produce a sulfated alumina.
[0120] To prepare another treated solid oxide compound used in
these examples, designated treated solid oxide compound E,
silica-alumina was impregnated with an aqueous solution containing
10 grams of ammonium bifluoride, NH.sub.4HF.sub.2. It was then
calcined at 450.degree. C. to produce a fluorided
silica-alumina.
[0121] Polymerization Test Procedure: 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 half a degree
Celsius, with the help of electronic control instruments.
[0122] Unless otherwise stated, the usual charging procedure was as
follows. First, a small amount (0.01 to 0.10 gram normally) of the
treated solid oxide compound was charged under nitrogen to a dry
reactor. Next, about 5-10 milligrams of the organometal compound or
organometal/organoaluminum mixture were added, followed by 0.6
liter of isobutane liquid. Then, a second organoaluminum compound
was added, if used, typically 1.0 milliliter of a 1.0 molar
solution of triethylaluminum (TEA) was added, followed by another
0.6 liter of isobutane liquid. Then, the reactor was heated up to
the specified temperature, typically 90.degree. C., and finally
ethylene was added to the reactor to equal a fixed pressure,
generally 550 psig to produce a reaction mixture. The reaction
mixture was allowed to stir for usually around one hour. As
ethylene was consumed, more ethylene flowed in to maintain the
pressure. The activity of the catalyst composition was noted by
recording the flow of ethylene into the reactor to maintain the set
pressure.
[0123] 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 and weighed. Activity was specified as grams of
polymer produced per gram of solid oxide compound charged per hour
((g/g)/hr).
Control Examples 1-4
[0124] Polymerization runs 1-4, shown in Table 1, are comparative
runs using organometal D. In the first example, 5.3 milligrams of
organometal compound were added as a solid directly to the reactor
along with treated solid oxide compound A. The other ingredients
were added as described previously in the polymerization procedure,
including 1 millimole of triethylaluminum (TEA). This is a
procedure that has worked well for many simpler organometal
compounds, such as bis-n-butylcyclopentadienyl zirconium
dichloride. However, in example 1, no polymer was produced from
organometal D.
[0125] In examples 2-4, 2.5 milliliters of a toluene solution
containing 0.5 gram of organometal D per 100 milliliters were added
along with the other ingredients previously discussed. This amounts
to 10 milligrams of organometal compound. Although this procedure
provides good activity with simpler organometal compounds, such as
bis-n-butylcyclopentadienyl zirconium dichloride, this procedure
provided only small activity with organometal D.
Control Examples 5-11
[0126] Expecting that organometal D is only sparingly soluble in
the isobutane reaction diluent, and that this might handicap its
potential activity, another procedure was employed. In example 5,
0.027 gram of treated solid oxide compound A was contacted with the
toluene solution of organometal D described previously in Examples
2-4 to produce an organometal-containing treated solid oxide
compound. The treated solid oxide compound immediately turned
black. It was washed several times in heptane, which caused it to
become a lavender color. Then, the heptane was evaporated off under
nitrogen. The organometal-containing treated solid oxide compound
was charged to the reactor normally along with an amount of
organoaluminum compound as specified in Table 1. In run 5, 1
millimole of TEA was used as the organoaluminum compound, but no
activity resulted.
[0127] The procedure was repeated in run 6 except that a
dichloromethane solution of organometal D was used to impregnate
treated solid oxide compound A. This time 0.18 gram of organometal
D were dissolved into 10 milliliters of dichloromethane. This was
added to 2.35 grams of treated solid oxide compound A, and the
excess dichloromethane evaporated off under nitrogen to produce an
organometal-containing treated solid oxide compound. Again, the
final color of the organometal-containing treated solid oxide
compound was lavender. Only minimal activity resulted. Then, the
amount of TEA was varied to 0.5 millimole in run 7, and 3
millimoles in run 8. No polymer or very little polymer were
produced in these runs. Then, different organoaluminum compounds
were utilized, including trimethylaluminum (TMA) in run 9 and
diethyl aluminum chloride (DEAC) in run 10. Again, no polymer was
produced.
[0128] To determine if organometal D had been destroyed during the
impregnation process of the treated solid oxide compound, or if
traces of dichloromethane solvent was poisoning the polymerization
reaction, 5 milliliters of 10% by weight methylaluminoxane (MAO)
were utilized as an activator of the organometal compound in Run
11. This proved, as always, to be a potent combination producing an
activity of 2450 grams of polymer per gram of treated solid oxide
compound A per hour. This proved that the organometal compound that
had been impregnated on the treated solid oxide compound was still
intact.
Inventive Examples 12-14
[0129] The next polymerization runs illustrate this invention. In
Run 12, 0.9 milliliter of the organometal D solution described
previously (0.5 grams of organometal D in 100 milliliters of
toluene) was mixed with 1 milliliter of 1 molar TEA and allowed to
contact overnight at room temperature to produce an organometal/TEA
mixture. The organometal/TEA mixture, treated solid oxide compound,
and other ingredients were added to the reactor as discussed
previously in the polymerization procedure. Twenty five milliliters
of hexene were also added to the reactor to produce a copolymer.
634 grams of copolymer per gram of treated solid oxide compound A
per hour were produced which is the highest activity yet obtained
from organometal D in the absence of MAO It was found to have a
melt index (MI) of 0.38 grams/10 minutes, a high load melt index
(HLMI) of 9.59 grams/10 minutes, a HLMI/MI ratio of 25.5, and a
density of 0.9291 g/cc. The copolymer was found to have a weight
average molecular weight (Mw) of 112,000 g/mol, a number average
molecular weight (Mn) of 34,500, and a Mw/Mn ratio of 3.3. It was
found by c13 NMR to have 0.21 mole % ethyl branching (spontaneously
produced) and 1.42 mole % butyl branching from the hexene. This
reflects the same high hexene incorporation efficiency exhibited by
organometal D activated by MAO.
[0130] In examples 13 and 14, a more concentrated organometal D/TEA
mixture was prepared. To 10 milliliters of 1 molar TEA were added
0.15 gram of organometal D to produce an organometal/TEA mixture.
It gradually dissolved and was allowed to stir overnight. 1
milliliter of the organometal/TEA mixture was added to the reactor
along with treated solid oxide compound A. No additional TEA was
added. 25 milliliters of hexene were added to the reactor in both
examples 13 and 14. An activity of 2489 grams of polymer per gram
of treated solid oxide compound A per hour was observed. A repeat
of this procedure in run 14 produced 2458 grams of polymer per gram
of treated solid oxide compound A per hour. Thus, this procedure
produced an activity equivalent to that produced with MAO.
[0131] Example 13 produced a melt index of 0.7 gram/10 minutes,
HLMI of 15.3 grams/10 minutes, HLMI/MI of 21.9, and density of
0.9296 cc/g. The polymer contained 0.20 mole % ethyl branches and
0.99 mole % butyl branches from the hexene, which again displays
excellent hexene incorporation efficiency. Example 14 yielded a
melt index of 0.29 gram/10 minutes, HLMI of 6.98 grams/10 minutes,
HLMI/MI of 24.1, and a density of 0.9280 cc/g.
Control Examples 15-17
[0132] The polymerization test procedure discussed previously was
attempted with two other organoaluminum compounds. Trimethyl
aluminum (TMA) was used in example 15, and tri-isobutyl aluminum
(TIBA) was used in examples 16 and 17. Examples 15-17 used 2
milliliters of an organometal/TEA mixture obtained by dissolving
0.042 gram of organometal D into 20 milliliters of 25% by weight
TIBA or TMA, which was allowed to stir overnight. However, little
or no activity was obtained from these compounds.
Inventive Examples 18-20
[0133] In another embodiment of this invention, catalyst
compositions were given a "prepolymerization" treatment which can
improve activity. Prepolymerization was previously discussed in
this disclosure. In examples 18-20, the procedure of Examples 13
and 14 was used again. In examples 18 and 20, an organometal/TEA
mixture was made containing 0.1370 gram of organometal D in 20
milliliters of 1 molar TEA. The organometal/TEA mixture was stirred
overnight. Then, 0.5 milliliter of this mixture was charged to the
reactor (3.4 mg of organometal D total). In example 19, 0.0177 gram
of organometal D was dissolved in 10 milliliters of 1 molar TEA,
and allowed to stir overnight to produce an organometal/TEA
mixture. 2.5 milliliters of this mixture were added to the reactor.
Next, a prepolymerization step was completed before the
polymerization run. After the treated solid oxide compound had been
added to the reactor, followed by the organometal/TEA mixture and
isobutane, low pressure ethylene was applied to the reactor while
at room temperature for an hour. In example 18, initially the
reactor was pressurized with ethylene to a pressure of 137 psig and
sealed. After an hour had passed, the pressure had dropped to 131
psig, indicating a very small consumption of ethylene to make
prepolymer. In example 19, only 60 psig of ethylene pressure was
used over half an hour. Very little pressure drop was noticed
during this time indicating little consumption of ethylene. In
example 20, 60 psig of ethylene was used for just 11 minutes.
[0134] Then, in all three runs, the temperature and pressure were
raised, and the polymerization reaction was allowed to continue as
described previously. In three repetitions of this method in
examples 18-20, activities of 2725, 2590, and 3753 grams of polymer
per gram of treated solid oxide A per hour were obtained, which
were actually above that obtained from MAO.
Control Examples 21-22
[0135] The procedure of examples 18-20 was repeated, including
prepolymerization, except other organoaluminum compounds were
utilized. In example 21, 0.0429 gram of organometal D was dissolved
in 20 milliliters of 1 molar tri-isobutyl aluminum (TIBA) and
stirred overnight to produce an organometal/TIBA mixture. Two
milliliters of the organometal/TEA mixture were then added to the
reactor. Prepolymerization occurred at 25.degree. C. and 55 psig
for 25 minutes. In example 22, 0.422 gram of organometal D were
dissolved into 10 milliliters of 2 molar trimethylaluminum (TMA)
and stirred overnight to produce an organometal/TMA mixture. Two
milliliters of the organometal/TMA mixture were added to the
reactor. Prepolymerization occurred at 99 psig for 67 minutes at
25.degree. C. But in both cases, little or no activity was
obtained.
Inventive Examples 23-24 and Control Example 25
[0136] The procedure of Examples 13 and 14 was repeated using TEA
but without prepolymerization and with treated solid oxide compound
D. Treated solid oxide compound D has generally given somewhat
lower activities with other organometal compounds. In both
examples, 0.0770 gram of organometal D was dissolved in 15
milliliters of 1 molar TEA and allowed to stir overnight to produce
an organometal/TEA mixture. Then, 2.5 milliliters of this mixture
were added to the reactor. These runs, examples 23 and 24, yielded
440 and 488 grams of polymer per gram of treated solid oxide
compound D per hour. In example 23, 50 milliliters of hexene also
were added to the reactor, while in Example 24, no hexene was
added. The polymer from Example 23 was found to have a melt index
of 0.52 gram/10 minutes, HLMI of 12.4 grams/10 minutes, and a
HLMI/MI of 23.7. GPC analysis showed a weight average molecular
weight (Mw) of 112,000 g/mol, a number average molecular weight
(Mn) of 40,300, and a Mw/Mn ratio of 2.8. It was also found to
contain 0.19 mole % ethyl branches and 1. 13 mole % butyl branches
from hexene incorporation. Polymer from example 24 had HLMI of 0.80
gram/10 minutes, Mw of 260,000 g/mol, Mn of 69,600, a Mw/Mn ratio
of 3.7, and 0.18 mole % ethyl branching. Since hexene was not added
to the reactor, no butyl branches were detected.
[0137] In Control Example 25, the same procedure was performed with
the same treated solid oxide compound as in Examples 23 and 24, but
using a different organometal compound, a simple zirconocene
dichloride. 0.0167 gram of zirconocene dichloride was dissolved in
10 milliliters of 1 molar TEA which was allowed to stir overnight
to produce a zirconocene dichloride/TEA mixture. Then, 2.5
milliliters of this mixture were added to the reactor. As can be
seen, this combination did not provide good activity.
Inventive Example 26
[0138] Finally, the procedure of examples 13 and 14 was again
followed but with treated solid oxide compound (E). About 0.02 gram
of organometal D was dissolved into 4 milliliters of 1 molar TEA
and stirred overnight to produce an organometal/TEA mixture. 2.0
milliliters of this mixture were added to the reactor. An activity
was obtained of 1121 grams of polymer per gram of treated solid
oxide compound E per hour.
Control Example 27 and Inventive Example 28
[0139] In examples 27 and 28, organometal compound A
(1,2-ethanediylbis(9-fluorenyl)zirconium dichloride) was used with
treated solid oxide compound E. This was not a highly active
combination, but one can still see the improvement in activity
resulting from implementation of the procedures of this invention
(Run 28 versus 27). In Example 27, 0.451 gram of organometal
compound A in 20 milliliters of toluene was added to the reactor
according to the polymerization test procedure discussed
previously. In example 28, a rather dilute
organometal/organoaluminum mixture was used consisting of 0.0451
gram of organometal compound A in 20 milliliters of toluene and 2
milliliters of 1 molar TEA. The activity of the catalyst
composition in run 27 was 120 grams of polymer per gram of treated
solid oxide compound E per hour while the activity in run 28 was
177, thus showing the improvement when the organometal compound is
first contacted with organoaluminum compound.
Inventive Examples 29-32
[0140] In runs 29-32, organometal compound A was combined with
treated solid oxide compound (B) to produce much higher activity.
0.0782 gram of organometal compound A was dissolved into 30
milliliters of 1 molar TEA and allowed to stir overnight at room
temperature to produce a metallocene A/TEA mixture. Two milliliters
of this mixture (5.2 mg of organometal compound A) were added to
the reactor in example 29 and 32, while five milliliters were added
in examples 30 and 31.
[0141] All of these runs had 25 milliliters of hexene added to the
reactor. Both polymers 31 and 32 were analyzed and found to have
extremely high molecular weight as evidenced by a zero HLMI.
Incorporation of hexene in the polymer was again very efficient as
evidenced by densities of 0.9301 cc/g and 0.9191 cc/g respectively,
and by butyl branching of 0.74 and 0.82 mole %. No ethyl branching
was detected.
Control Example 33 and Inventive Example 34
[0142] Finally, in examples 33 and 34, the same procedures as used
in Examples 27 and 28 were utilized. The increase in activity can
be clearly observed when the procedures of this invention are
utilized. When organometal B (diphenylmethanediyl(9-fluorenyl,
cyclopentadienyl) zirconium chloride) was added in a toluene
solution to the reactor in Run 33, an activity of only 95 grams of
polymer per gram of treated solid oxide compound A per hour was
observed. However, when organometal B was combined with TEA to
produce an organometal C/TEA mixture, and this mixture was added to
the reactor along with the other ingredients as discussed
previously in the polymerization test procedure, an activity of
2153 grams of polymer per gram of treated solid oxide compound A
per hour was realized.
1TABLE 1 Polymerization runs with organometal D Method of Treated
Organometal Amount of Solid Oxide Compound Organoaluminum Activity
Classification Compound Addition Compound Prepolymer g/g/hr*
1-Control A Solid 1 mmol TEA No 0 2-Control A Toluene solution 1
mmol TEA No 325 3-Control A Toluene solution 1 mmol TEA No 164
4-Control A Toluene solution 0.5 mmol TEA No 95 5-Control A
Impregnated 1 mmol TEA No 0 On Solid Oxide Compound 6-Control A
Impregnated 1 mmol TEA No 97 On Solid Oxide Compound 7-Control A
Impregnated 0.5 mmol TEA No 0 On Solid Oxide Compound 8-Control C
Impregnated 3 mmol TEA No 117 On Solid Oxide Compound 9-Control A
Impregnated 1 mmol TEA No 0 On Solid Oxide Compound 10-Control A
Impregnated 1 mmol DEAC No 0 On Solid Oxide Compound 11-Control A
Impregnated On Solid Oxide 5 ml 10% MAO No 2450 Compound
12-Invention A Reacted with TEA None more No 634 13-Invention A
Reacted with TEA None more No 2489 14-Invention A Reacted with TEA
None more No 2458 15-Control A Reacted with TMA None more No 223
16-Control A Reacted with TIBA None more No 0 17-Control A Reacted
with TIBA None more No 0 18-Invention A Reacted with TEA 1.5 mmol
TEA Yes 2725 19-Invention A Reacted with TEA 1 mmol TEA Yes 2590
20-Invention A Reacted with TEA 1.5 mmol TEA Yes 3753 21-Control A
Reacted with TIBA 1 mmol TEA Yes 0 22-Control A Reacted with TMA
None more Yes 63 23-Invention D Reacted with TEA None more No 440
24-Invention D Reacted with TEA None more No 488 25-Control D
Cp.sub.2ZrCl.sub.2 None more No 40 in TEA 26-Invention E Reacted
with TEA 1 mmol TEA No 1121 *Treated Solid Oxide Compound
A-chlorided, zinc-containing alumina; *Treated Solid Oxide Compound
B-chlorided, zinc-containing alumina; *Treated Solid Oxide Compound
C-chlorided alumina; *Treated Solid Oxide Compound D-sulfated
alumina; *Treated Solid Oxide Compound E-fluorided silica alumina;
*TEA-triethyl aluminum *TMA-trimethyl aluminum *TIBA-tri-isobutyl
aluminum *DEAC-diethyl aluminum chloride *MAO-methylaluminoxane
*Activity-(grams of polymer/gram of treated solid oxide
compound)/hour
[0143]
2TABLE 2 Examples using other organometal compounds Treated Method
of Amount of Solid Oxide Organometal Organometal Organoaluminum
Activity Classification Compound Compound Compound Addition
Compound g/g/hr* 27-Control E A Toluene solution 1 mmol TEA 120
28-Invention E A Reacted with TEA No more 177 29-Invention B A
Reacted with TEA No more 1387 30-Invention B A Reacted with TEA No
more 1812 31-Invention B A Reacted with TEA No more 1772
32-Invention B A Reacted with TEA No more 2738 33-Control A B
Toluene solution 1 mmol TEA 95 34-Invention A B Reacted with TEA 1
mmol TEA 2153 *Organometal
A-(1,2-ethanediylbis(9-fluorenyl)zirconium dichloride) *Organometal
B-diphenylmethanediyl(9-fluorenyl,cyclopentadienyl) zirconium
dichloride *Treated Solid Oxide Compounds as defined in Table 1
*Activity-grams of polymer per gram of treated solid oxide compound
per hour.
[0144] 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.
* * * * *