U.S. patent application number 10/357212 was filed with the patent office on 2003-06-26 for polymerization process utilizing an organometal compound, organoaluminum compound and a solid mixed oxide compound.
This patent application is currently assigned to PHILLIPS PETROLEUM COMPANY. Invention is credited to Collins, Kathy S., Johnson, Marvin M., Martin, Shirley J., McDaniel, Max P..
Application Number | 20030120002 10/357212 |
Document ID | / |
Family ID | 22164445 |
Filed Date | 2003-06-26 |
United States Patent
Application |
20030120002 |
Kind Code |
A1 |
McDaniel, Max P. ; et
al. |
June 26, 2003 |
Polymerization process utilizing an organometal compound,
organoaluminum compound and a solid mixed oxide compound
Abstract
This invention provides compositions that are useful for
polymerizing at least one monomer into at least one polymer.
Inventors: |
McDaniel, Max P.;
(Bartlesville, OK) ; Martin, Shirley J.;
(Bartlesville, OK) ; Collins, Kathy S.;
(Bartlesville, OK) ; Johnson, Marvin M.;
(Bartlesville, OK) |
Correspondence
Address: |
McDermott, Will & Emery
600 13th Street, N.W.
Washington
DC
20005-3096
US
|
Assignee: |
PHILLIPS PETROLEUM COMPANY
Bartlesville
OK
|
Family ID: |
22164445 |
Appl. No.: |
10/357212 |
Filed: |
February 4, 2003 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10357212 |
Feb 4, 2003 |
|
|
|
09584438 |
May 31, 2000 |
|
|
|
6531550 |
|
|
|
|
09584438 |
May 31, 2000 |
|
|
|
09081480 |
May 18, 1998 |
|
|
|
6165929 |
|
|
|
|
Current U.S.
Class: |
526/97 ; 502/111;
502/113; 502/120; 502/152; 526/107; 526/114; 526/119; 526/132;
526/160; 526/64 |
Current CPC
Class: |
C08F 4/65912 20130101;
Y10S 526/943 20130101; C08F 10/02 20130101; C08F 4/65925 20130101;
C08F 110/02 20130101; C08F 10/02 20130101; C08F 10/02 20130101;
C08F 4/025 20130101; C08F 4/65916 20130101 |
Class at
Publication: |
526/97 ; 526/64;
526/107; 526/114; 526/119; 526/132; 526/160; 502/113; 502/111;
502/120; 502/152 |
International
Class: |
C08F 004/64 |
Claims
That which is claimed is:
1. A process to produce a composition of matter, said process
comprising contacting an organometal compound, a solid Lewis acid
compound, and an organoaluminum compound to produce said
composition, wherein said composition consists essentially of a
post-contacted organometal compound, a post-contacted solid Lewis
acid compound, and optionally, a post-contacted organoaluminum
compound, and wherein said composition can polymerize ethylene into
a polymer with an activity greater than a composition that uses the
same organometal compound, and the same organoaluminum compound,
but uses untreated Ketjen grade B alumina instead of said solid
Lewis acid, and wherein said organometal compound has the following
general formula (X.sup.1)(X.sup.2)(X.sup.3)(X.sup.4)M.s- up.1
wherein M.sup.1 is selected from the group consisting of titanium,
zirconium, and hafnium, and wherein (X.sup.1) is independently
selected from the group consisting of cyclopentadienyls, indenyls,
fluorenyls, substituted cyclopentadienyls, substituted indenyls,
and substituted fluorenyls, and wherein said substituents on said
substituted cyclopentadienyls, substituted indenyls, and
substituted fluorenyls, are selected from the group consisting of
aliphatic groups, cyclic groups, combinations of aliphatic and
cyclic groups, and organometallic groups, and hydrogen; and wherein
(X.sup.3) and (X.sup.4) are independently selected from the group
consisting of halides, aliphatic groups, cyclic groups,
combinations of aliphatic and cyclic groups, and organometallic
groups, and wherein (X.sup.2) is selected from the group consisting
of Group OMC-I or Group-OMC-II, and wherein said organoaluminun
compound has the following general formula.
A1(X.sup.5).sub.n(X.sup.6).sub.3-n wherein (X.sup.5) is a
hydrocarbyl having from 1-20 carbon atoms, and wherein (X.sup.6) is
a halide, hydride, or alkoxide, and wherein "n" is a number from 1
to 3 inclusive.
2. A process to produce a composition of matter, said process
comprising contacting an organometal compound, a solid mixed oxide
compound, and an organoaluminum compound to produce said
composition, wherein said composition consists essentially of a
post-contacted organometal compound, a post-contacted solid mixed
oxide compound, and optionally, a post-contacted organoaluminum
compound, and wherein said composition can polymerize ethylene into
a polymer with an activity greater than 100 (gP/(gS.multidot.hr)),
and 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, and wherein (X.sup.1) is independently selected from the
group consisting of cyclopentadienyls, indenyls, fluorenyls,
substituted cyclopentadienyls, substituted indenyls, and
substituted fluorenyls, and wherein said substituents on said
substituted cyclopentadienyls, substituted indenyls, and
substituted fluorenyls, are selected from the group consisting of
aliphatic groups, cyclic groups, combinations of aliphatic and
cyclic groups, and organometallic groups, and hydrogen; and wherein
(X.sup.3) and (X.sup.4) are independently selected from the group
consisting of halides, aliphatic groups, cyclic groups,
combinations of aliphatic and cyclic groups, and organometallic
groups, and wherein (X.sup.2) is selected from the group consisting
of Group OMC-I or Group OMC-II, and wherein said organoaluminun
compound has the following general formula.
A1(X.sup.5).sub.n(X.sup.6).sub.3-n wherein (X.sup.5) is a
hydrocarbyl having from 1-20 carbon atoms, and wherein (X.sup.6) is
a halide, hydride, or alkoxide, and wherein "n" is a number from 1
to 3 inclusive, and wherein said solid mixed oxide compounds
comprise oxygen and at least two elements selected from the group
consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
and 15 of the periodic table, including lanthanides and
actinides.
3. A process according to claim 2 wherein said activity is greater
than 150.
4. A process according to claim 3 wherein said activity is greater
than 200.
5. A process according to claim 4 wherein said activity is greater
than 250.
6. A process according to claim 4 wherein said activity is greater
than 300.
7. A composition produced by the process of claim 2.
8. A process of using the composition of claim 7 to polymerize
monomers into polymers.
9. A manufacture that comprises polymers produced according to
claim 8.
10. A machine that comprises manufactures according to claim 9.
11. A process according to claim 8 wherein said polymers are
produced under slurry polymerization conditions.
12. A process according to claim 11 wherein said polymerization is
conducted in a loop reactor.
13. A process according to claim 12 wherein said polymerization is
conducted in the presence of a diluent that comprises, in major
part, isobutane.
14. A manufacture that comprises polymers produced according to
claim 13.
15. A machine that comprises manufactures according to claim
14.
16. A composition produced by the process of claim 6.
17. A process of using the composition of claim 16 to polymerize
monomers into polymers.
18. A manufacture that comprises polymers produced according to
claim 17.
19. A machine that comprises manufactures according to claim
18.
20. A process according to claim 17 wherein said polymers are
produced under slurry polymerization conditions.
21. A process according to claim 20 wherein said polymerization is
conducted in a loop reactor.
22. A process according to claim 21 wherein said polymerization is
conducted in the presence of a diluent that comprises, in major
part, isobutane.
23. A manufacture that comprises polymers produced according to
claim 22.
24. A machine that comprises manufactures according to claim
23.
25. A process to produce a composition of matter, said process
comprising contacting an organometal compound, a solid mixed oxide
compound, and an organoaluminum compound to produce said
composition, wherein said composition consists essentially of a
post-contacted organometal compound, a post-contacted solid mixed
oxide compound, and optionally, a post-contacted organoaluminum,
compound, and wherein said composition can polymerize ethylene into
a polymer with an activity greater than 300 (gP/(gS.multidot.hr)),
and wherein said organometal compound is selected from the group
consisting of bis(cyclopentadienyl) hafnium dichloride;
bis(cyclopentadienyl) zirconium dichloride; [ethyl(indenyl).sub.2]
hafnium dichloride; [ethyl(indenyl).sub.2] zirconium dichloride;
[ethyl(tetrahydroindenyl).sub.2] hafnium dichloride;
[ethyl(tetrahydroindenyl).sub.2] zirconium dichloride;
bis(n-butylcyclopentadienyl) hafnium dichloride;
bis(n-butylcyclopentadie- nyl) zirconium dichloride;
((dimethyl)(diindenyl) silane) zirconium dichloride;
((dimethyl)(diindenyl) silane) hafnium dichloride;
((dimethyl)(ditetrahydroindenyl) silane) zirconium dichloride;
((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride;
bis(fluorenyl) zirconium dichloride, and wherein said
organoaluminum compound is selected from the group consisting of
trimethylaluminum; triethylaluminum; tripropylaluminum;
diethylaluminum ethoxide; tributylaluminum; triisobutylaluminum
hydride; triisobutylaluminum; diethylaluminum chloride, and wherein
said solid mixed oxide compounds are selected from the group
consisting of mixtures of two or more oxides 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 and ZrO.sub.2.
Description
FIELD OF THE INVENTION
[0001] This invention is related to the field of compositions that
can be used to polymerize monomers into at least one polymer.
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 1960,
however, their low productivity did not allow them to be
commercialized. About 1975, it was discovered that contacting one
part water with two parts 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] Borate compounds have been use 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.
[0005] It should also be noted that having a heterogeneous catalyst
is important. This is because heterogeneous catalysts are required
for most modem 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 uniformed 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] Therefore, the inventors provide this invention to solve
these problems.
SUMMARY OF THE INVENTION
[0007] An object of this invention is to provide a process that
produces a composition that can be used to polymerize monomers into
at least one polymer.
[0008] Another object of this invention is to provide said
composition.
[0009] Another object of this invention is to provide a process to
polymerize monomers into at least one polymer using said
composition.
[0010] Another object of this invention is to provide a manufacture
that comprises at least one said polymer.
[0011] Another object of this invention is to provide a machine
that comprises at least one said manufacture.
[0012] In accordance with one embodiment of this invention, a
process to produce a composition of matter is provided. Said
process comprises (or optionally, consists essentially of, or
consists of) contacting an organometal compound, a solid Lewis acid
compound, and an organoaluminum compound to produce said
composition, wherein said composition consists essentially of (or
optionally, consists of) a post-contacted organometal compound, a
post-contacted solid Lewis acid compound, and optionally, a
post-contacted organoaluminum compound.
[0013] In accordance with another embodiment of this invention, a
composition of matter is provided. Said composition consists
essentially of a post-contacted organometal compound, a
post-contacted solid Lewis acid compound, and optionally, a
post-contacted organoaluminum compound.
[0014] In accordance with another embodiment of this invention, a
process to polymerize monomers into at least one polymer using said
composition is provided. Said process comprises contacting said
composition with monomers.
[0015] In accordance with another embodiment of this invention a
manufacture is provided. Said manufacture comprises at least one
said polymer.
[0016] In accordance with another embodiment of this invention a
machine is provided. Said machine comprises at least two said
manufactures.
[0017] These objects, and other objects, will become more apparent
to those with ordinary skill in the art, by reading this
disclosure.
[0018] It should be noted that the phrase "consisting essentially
of" means that the only other items (such as, for example, process
steps, and other compounds) included within the scope of the claims
are those items that do not materially affect the basic and novel
characteristics of the claimed invention.
[0019] It should also be noted that the phrase "consisting of"
means that the no other items (such as, for example, process steps,
and other compounds) are included within the scope of the claims,
except items that are impurities ordinarily associated with a
composition, or items that are process steps ordinarily associated
with a process.
DETAILED DESCRIPTION OF THE INVENTION
[0020] Organometal compounds used in this invention have the
following general formula.
FORMULA ONE: (X.sup.1)(X.sup.2)(X.sup.3)(X.sup.4)M.sup.1
[0021] In this formula, M.sup.1 is selected from the group
consisting of titanium, zirconium, and hafnium. Currently, it is
most preferred when M.sup.1 is zirconium.
[0022] In this formula (X.sup.1) 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.
[0023] The substituents on the substituted cyclopentadienyls,
substituted indenyls, and substituted fluorenyls, can be aliphatic
groups, cyclic groups, combinations of aliphatic and cyclic groups,
and organometallic groups, as long as these groups do not
substantially, and adversely, affect the polymerization activity of
the composition. Additionally, hydrogen can be a substituent.
[0024] 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. Additionally, alkylsilyl groups where each alkyl contains
1-12 carbon atoms, alkyl halide groups where each alkyl contains
1-12 carbon atoms, or halides, can also be used.
[0025] 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, and iodo.
[0026] In this formula (X.sup.3) and (X.sup.4) are independently
selected from the group consisting of (hereafter "Group OMC-II")
halides, aliphatic groups, cyclic groups, combinations of aliphatic
and cyclic groups, and organometallic groups, as long as these
groups do not substantially, and adversely, affect the
polymerization activity of the composition.
[0027] 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 10 carbon atoms.
[0028] However, it is most preferred when (X.sup.3) and (X.sup.4)
are selected from the group consisting of fluoro, chloro, and
methyl.
[0029] In this formula, (X.sup.2) can be selected from either Group
OMC-I or Group OMC-II.
[0030] When (X.sup.2) is selected from Group OMC-I, it should be
noted that (X.sup.1) and (X.sup.2) can be joined with a bridging
group, such as, for example, aliphatic bridging groups, cyclic
bridging groups, combinations of aliphatic and cyclic bridging
groups, and organometallic bridging groups, as long as the bridging
group does not substantially, and adversely, affect the
polymerization activity of the composition.
[0031] Suitable examples of aliphatic bridging groups are
hydrocarbyls, such as, for example, paraffins and olefins. Suitable
examples of cyclic bridging groups are cycloparaffins,
cycloolefins, cycloacetylenes, and arenes. Additionally, it should
be noted that silicon and germanium are also good bridging
units.
[0032] Various processes are known to make these compositions. 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.
[0033] Specific examples of such compositions are as follows:
[0034] bis(cyclopentadienyl) hafnium dichloride;
[0035] bis(cyclopentadienyl) zirconium dichloride;
[0036] [ethyl(indenyl).sub.2] hafnium dichloride;
[0037] [ethyl(indenyl).sub.2] zirconium dichloride;
[0038] [ethyl(tetrahydroindenyl).sub.2] hafnium dichloride;
[0039] [ethyl(tetrahydroindenyl).sub.2] zirconium dichloride;
[0040] bis(n-butylcyclopentadienyl) hafnium dichloride;
[0041] bis(n-butylcyclopentadienyl) zirconium dichloride;
[0042] ((dimethyl)(diindenyl) silane) zirconium dichloride;
[0043] ((dimethyl)(diindenyl) silane) hafnium dichloride:
[0044] ((dimethyl)(ditetrahydroindenyl) silane) zirconium
dichloride;
[0045] ((dimethyl)(di(2-methyl indenyl)) silane) zirconium
dichloride; and
[0046] bis(fluorenyl) zirconium dichloride.
[0047] Organoaluminum compounds have the following general
formula.
FORMULA TWO: A1(X.sup.5).sub.n(X.sup.6).sub.3-n
[0048] In this formula (X.sup.5) is a hydrocarbyl having from 1-20
carbon atoms. Currently, it is preferred when (X.sup.5) is an alkyl
having from 1 to 10 carbon atoms. However, it is most preferred
when (X.sup.5) is selected from the group consisting of methyl,
ethyl, propyl, butyl, and isobutyl.
[0049] 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.
[0050] In this formula "n" is a number from 1 to 3 inclusive.
However, it is preferred when "n" is 3.
[0051] Examples of such compounds are as follows:
[0052] trimethylaluminum;
[0053] triethylaluminum;
[0054] tripropylaluminum;
[0055] diethylaluminum ethoxide;
[0056] tributylaluminum;
[0057] triisobutylaluminum hydride;
[0058] triisobutylaluminum; and
[0059] diethylaluminum chloride.
[0060] Currently, triethylaluminum is preferred.
[0061] Solid Lewis acid compounds are compounds that have Lewis
acidity. It is preferred when said solid Lewis acid compounds
comprise solid mixed oxides. It is also preferred when said solid
mixed oxide compounds comprise oxygen and at least two elements
selected from the group consisting of groups 2, 3, 4, 5, 6, 7, 8,
9, 10, 11, 12, 13, 14, and 15 of the periodic table, including
lanthanides and actinides (See Hawley's Condense Chemical
Dictionary, 11th Edition). However, it is preferred when the
elements are 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 solid mixed oxide
compounds have electron withdrawing ability, while not wanting to
be bound by theory, it is believed that solid mixed oxide compounds
should have high Lewis acidity. However, it is hard to accurately
measure the Lewis acidity of these solid mixed oxide compounds, or
other solid Lewis acid compounds, so other methods have been used.
Currently, comparing the activities of solid mixed oxide compounds,
or solid Lewis acid compounds, under acid catalyzed reactions is
preferred.
[0062] Suitable examples of solid mixed oxide compounds include,
but are not limited to, mixtures 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.20.sub.3, ZnO, and ZrO.sub.2.
Currently, a solid mixed oxide compound containing three or more
elements is preferred. One preferred solid mixed oxide compound
comprises a mixed oxide that has oxygen bonded to Zr, B, and Al.
Additionally, it should be noted that solid mixed oxide compounds
that comprise Al-O and two other element-oxygen bonds are currently
preferred.
[0063] It is important that the solid mixed oxide compound is
calcined. This calcining can be conducted in an ambient atmosphere,
preferably a dry ambient atmosphere, at a temperature in the range
of about 300.degree. C. to about 900.degree. C., and for a time in
the range of about 1 minute to about 100 hours. Currently,
temperatures from about 500.degree. C. to about 700.degree. C. and
a time in the range of about 1 hour to about 10 hours, are
preferred.
[0064] Solid mixed oxide compounds, should have pore volumes
greater than about 0.01 cc/g, preferably greater than about 0.1
cc/g, and most preferably, greater than about 1 cc/g.
[0065] Solid Lewis acid compounds should have surface areas greater
that about 1 m.sup.2/g, preferably greater than 100 m.sup.2/g, and
most preferably greater than 200 m.sup.2/g.
[0066] Solid mixed oxide compounds should have surface areas
greater that about 1 m.sup.2/g, preferably greater than 100
m.sup.2/g, and most preferably greater than 200 m.sup.2/g.
[0067] Solid mixed oxide compounds can be produced in a variety of
ways, such as, for example, co-gelling, or impregnation of one
compound onto another.
[0068] The compositions of this invention can be produced by
contacting an organometal compound, a solid Lewis acid compound,
preferably a solid mixed oxide compound, and an 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 the reactor separately, or various
combinations 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 the organometal compound
and the solid Lewis acid compound together, for about 1 minute to
about 24 hours, preferably, about 1 minute to about 1 hour, at a
temperature from about 10.degree. C. to about 200.degree. C.,
preferably about 25.degree. C. to about 100.degree. C., to form a
first mixture, and then contact this first mixture with an
organoaluminum compound to form the composition.
[0069] During contacting, or after contacting, the mixtures or the
composition can be calcined. This calcining can be conducted in an
ambient atmosphere, preferably a dry ambient atmosphere, at a
temperature in the range of about 300.degree. C. to about
900.degree. C., and for a time in the range of about 1 minute to
about 100 hours. Currently, temperatures from about 500.degree. C.
to about 700.degree. C. and a time in the range of about 1 hour to
about 10 hours, are preferred.
[0070] After contacting, the composition consists essentially of,
(or consists of) a post-contacted organometal compound, a
post-contacted solid Lewis acid compound, and optionally, a
post-contacted organoaluminum compound. It should be noted that the
post-contacted solid Lewis acid compound is the majority, by
weight, of the composition. Since the exact order of contacting is
not known, it is believed that this terminology best describes the
composition's components.
[0071] The composition of this invention has an activity greater
than a compound that uses the same organometal compound, and the
same organoaluminum compound, but uses untreated Ketjen grade B
alumina (see comparative examples 4, 5, and 6) instead of the solid
Lewis acid compounds of this invention. This activity is measured
under slurry polymerization conditions, using isobutane as the
diluent, and with a polymerization temperature in the range of 50
to 150.degree. C., and an ethylene pressure of in the range of 400
to 800 psig. However, it is preferred if the activity is greater
than 100 grams polyethylene per gram of solid Lewis acid compound
per hour (hereafter "gP/(gS.cndot.hr)"), more preferably greater
than 150, even more preferably greater than 200, even more
preferably greater than 250, and most preferably greater than 300.
This activity is measured under slurry polymerization conditions,
using isobutane as the diluent, and with a polymerization
temperature in the range of 90.degree. C., and an ethylene pressure
of in the range of 550 psig. The reactor should have substantially
no indication of any wall scale, coating or other forms of
fouling.
[0072] These compositions are often sensitive to hydrogen and
sometimes incorporate comonomers well, and usually produce polymers
with a low HLMI/MI ratio.
[0073] One of the important aspects of this invention is that no
aluminoxane needs to be used in order to form the composition. 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
borate compounds need to be used in order to form the composition.
In summary, this means that the composition, which is heterogenous,
and which can be used for polymerizing monomers, can be easily and
inexpensively produced because of the substantial absence of any
aluminooxane compounds or borate compounds. Additionally, no
organochromium needs to be added, nor any MgCl.sub.2 needs to be
added to form the invention.
[0074] The monomers useful in this invention, are unsaturated
hydrocarbons having from 2 to 20 carbon atoms. Currently, it is
preferred when the monomer is selected from the group consisting of
ethylene, propylene, 1-butene, 3-methyl-l-butene, 1-pentene,
3-methyl-1-pentene, 4-methyl-l-pentene, 1-hexene, 3-ethyl-i-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof.
However, when a homopolymer is desired, it is most preferred to use
ethylene, or propylene, as the monomer. Additionally, when a
copolymer is desired, it is most preferred to use ethylene and
hexene as the monomers.
[0075] Processes that can polymerize monomers into polymers 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 reactor. Furthermore,
it is even more 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.
[0076] It should be noted that under slurry polymerization
conditions these compositions polymerize ethylene alone, or
ethylene with a 1-olefin, or propylene very well. In particular,
the compositions used in this process produce good quality polymer
particles without substantially fouling the reactor. When the
composition is to be used in a loop reactor under slurry
polymerization conditions, it is preferred when the particle size
of the solid mixed oxide compound is in the range of about 10 to
about 1000 microns, preferably 25 to 500 microns, and most
preferably, about 50 to about 200 microns, for best control during
polymerization.
[0077] After the polymers are produced, they can be formed into
various manufactures, such as, for example, household containers
and utensils, drums, fuel tanks, pipes, geomembranes, and liners.
Various processes can form these manufactures. 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, manufactures can be produced at a lower cost, while
maintaining most, if not all, of the unique properties of polymers
produced with metallocene catalysts.
[0078] Additionally, these manufactures can be part of a machine,
such as, for example, a car, so that the weight of the car will be
less, with the attended benefits thereof.
EXAMPLES
[0079] These examples provide additional information to a person
skilled in the art. These examples are not meant to be construed as
limiting the scope of the claims.
DESCRIPTION OF THE POLYMERIZATIONS RUNS
[0080] All polymerization runs were conducted in a steel reactor
that had a volume of 2.2 liters. This reactor was equipped with a
marine stirrer. During the polymerizations this stirrer was set to
run at 400 rpm. This reactor was also surrounded by a steel jacket
that was connected to a steel condenser. The steel jacket contained
methanol that was boiling. The boiling point of the methanol was
controlled by varying the nitrogen pressure that was applied to the
steel condenser and the steel jacket. This control method permitted
precise temperature control (.+-.0.5.degree. C.).
[0081] First, a solid oxide compound (either a solid unmixed oxide
or a solid mixed oxide) was charged, under nitrogen, to the
reactor, which was dry. Second, organometal compound solution was
added to the reactor by syringe. Third, 0.6 liters of isobutane was
charged to the reactor. Fourth, organoaluminum compound was added
to the reactor. Fifth, 0.6 liters of isobutane was charged to the
reactor. Sixth, ethylene was added to the reactor to equal 550 psig
pressure. Seventh, the reactor was heated to 90.degree. C. This
pressure was maintained during the polymerization. During
polymerization, stirring continued for the specified time. Activity
was determined by recording the flow of ethylene into the reactor
to maintain pressure. Seventh, after the specified time, the
ethylene flow was stopped and the reactor slowly depressurized.
Eighth, the reactor was opened to recover a granular polymer
powder.
[0082] In all inventive runs, the reactor was clean with no
indication of any wall scale, coating or other forms of fouling.
The polymer powder was removed and weighed. Activity was specified
as grams of polymer produced per gram of solid oxide compound
charged per hour.
[0083] In some cases the solid oxide compound and the organometal
compound were first pre-contacted, in the reactor, for about half
an hour at 90.degree. C. in one liter of isobutane before the
organoaluminum compound and ethylene were added to the reactor.
PREPARATION OF SOLID OXIDES
[0084] Silica, grade 952, having a pore volume of 1.6 cc/g and a
surface area of about 300 square meters per gram was obtained from
W. R. Grace. About 10 grams of this material was placed in a 1.75
inch quartz tube, which was fitted at the bottom with a sintered
quartz. 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.degree. C. per hour to a temperature of 600.degree. C. At
that temperature, the silica was allowed to fluidize for three
hours in the dry air. Afterward, the silica was collected and
stored under dry nitrogen.
[0085] Some alumina samples were also prepared by the procedure
described in the silica preparation. A commercial alumina sold as
Ketjen grade B alumina was obtained, having a pore volume of about
1.78 cc/g and a -surface area of around 340 square meters per gram.
The temperatures use in the preparation of these aluminas were
400.degree. C., 600.degree. C., and 800.degree. C.
[0086] A silica-alumina was also obtained from W. R. Grace (MS
13-110 containing 13% alumina and 87% silica). This silica-alumina
had a pore volume of 1.2 cc/g and a surface area of about 300
square meters per gram. This silica-alumina was prepared as
described in the silica preparation. The temperature use in the
preparation of this silica-alumina was 600.degree. C.
[0087] A silica-titania was obtained by co-gellation as described
in U.S. Pat. No. 3,887,494 ("Deitz"). Titanyl sulfate was dissolved
in concentrated sulfuric acid, to form a first mixture. Afterwards,
a sodium silicate solution was slowly added, with vigorous
stirring, to this first mixture, to form a second mixture. When the
pH of the second mixture reached about 6, this second mixture
gelled into a homogenous, substantially-clear first product. This
first product was then aged, at 80.degree. C. and a pH 7, for three
hours, followed by washing it nine times with water, and two times
in 1% ammonium nitrate, to form a second product. This second
product, which was a gel, was then azeotropically dried in ethyl
acetate, to form a third product. This third product contained 8%
titanium. It also had a surface area of 450 square meters per gram
and a pore volume of 2.0 cc/g. This silica-titania was then
prepared as described in the silica preparation. The temperature
use in the preparation of this silica-titania was 600.degree.
C.
[0088] An alumino-phosphate was prepared according to U.S. Pat. No.
4,364,855 (McDaniel). Aluminum nitrate (380 grams) and
mono-ammonium phosphate (94 grams) was dissolved in deionized water
to form a first mixture. About 170 milliliters of ammonium
hydroxide was then added to this first mixture to form a second
mixture. At a pH of about 8 this second mixture gelled to form a
first product. This first product was then washed twice in water,
and once in n-propanol, before drying overnight at 80.degree. C.
under a vacuum, to form a second product. This second product
contained a phosphorus to aluminum molar ratio of 0.8, a pore
volume of 2.1 cc/g, and a surface area of 250 square meters per
gram. This alumino-phosphate was then prepared as described in the
silica preparation. The temperature use in the preparation of this
alumina-phosphate was 600.degree. C.
[0089] Another aluminophosphate support was made according to the
preparation above but the phosphorous to aluminum molar ratio was
adjusted to equal 0.4. This mixed oxide had a pore volume after
calcining of 2.5 cc/g and a surface area of 450 m.sup.2/g. The
mixed oxide was activated by calcination at 750.degree. C.
COMPARATIVE EXAMPLES 1-2
[0090] These examples demonstrate that an organometal compound
contacted with an organoaluminum compound, provides little, if any,
polymerization activity.
[0091] A polymerization run was made as described earlier. First,
an organometal compound was added to the reactor (2 ml of
bis(n-butylcyclopentadienyl) zirconium dichloride solution (0.5
grams per 100 ml of toluene)). Second, half of the isobutane was
then added to the reactor. Third, 2 ml of 15 weight percent
triethyl aluminum for example 1, or 2 ml of 25 weight percent ethyl
aluminum dichloride (EADC) for example 2, were added to the
reactor. Fourth, the other half of the isobutane was added to the
reactor.
[0092] Ethylene was then added to the reactor but no polymerization
activity was observed. After one hour of contacting, the reactor
was depressurized and opened.
[0093] In each case, no polymer was found. These results are shown
in Table-I.
COMPARATIVE EXAMPLES 3-6,9 AND EXAMPLES 7-8
[0094] These examples demonstrate that contacting a solid oxide
compound, with an organometal compound, and with an organoaluminum
compound, provided little, if any, polymerization activity.
[0095] Each of the solid oxide compounds described earlier was
added to the reactor, followed by an organometal compound (2 ml of
bis(n-butylcyclopentadienyl) zirconium dichloride solution (0.5
grams per 100 ml of toluene), and then the organoaluminum compound
(triethylaluminum). These examples are shown in Table-I.
[0096] The first two examples show that contacting an organometal
compound with an organoaluminum compound provides little, if any,
polymerization activity. The silica example produced almost no
polymer. Alumina, which is regarded as more acidic than silica,
produced more polymer, but still the activity was very low. The
alumino- phosphate, silica-alumina, and silica-titania supports
exhibited only marginal activity. Activity is expressed in Table-I
as gP/(gS.cndot.hr).
COMPARATIVE EXAMPLE 10 & EXAMPLES 11-12
[0097] These examples show how to produce a composition that can be
used to polymerize monomers into polymers. Additionally, these
examples show the importance of the organoaluminum compound.
[0098] A solid mixed oxide compound was prepared by co-gelling
approximately equal mole parts of boria, alumina, and zirconia.
Aluminum nitrate nonahydrate (287 grams), boric acid (35 grams),
and zirconyl nitrate dihydrate (25 grams), were dissolved in
deionized water (500 milliliters) to form a first mixture. This
first mixture was then gelled by contacting this first mixture with
concentrated (28 weight percent NH.sub.3 in water) ammonium
hydroxide (210 milliliters), using a stirrer, to form a second
mixture. This second mixture, which was a gel, was washed once in
four liters of water, followed by filtration, and than another wash
in four liters of n-propanol. After being dried overnight in a
vacuum oven at 100.degree. C., the dry gel was pushed through a 35
mesh screen. A ten gram sample was prepared as described in the
silica preparation to produce a solid mixed oxide compound. The
temperature use in the preparation of this sample was 600.degree.
C.
[0099] In Example 10 the activity for ethylene polymerization was
zero. In Example 11 the reactor filled with polymer, giving a high
activity. This polymer was found to have a melt index of 0 and a
high load melt index of 1.2. In Example 12 high activity was also
obtained. See Table-I
COMPARATIVE EXAMPLE 13
[0100] Another three component solid mixed oxide compound was
prepared by co-gellation of about 47.5 mole percent boria, 47.5
mole percent alumina, and 5 mole percent zirconia. Aluminum nitrate
nonahydrate (187 grams), boric acid (31 grams), and zirconyl
nitrate dihydrate (14 grams), were dissolved in deionized water
(500 milliliters) to form a first mixture. This first mixture was
then gelled by contacting this first mixture with concentrated
ammonium hydroxide (130 milliliters), using a stirrer, to form a
second mixture. This second mixture, which was a gel, was washed
once in four liters of water, followed by filtration, and then wash
in four liters of n-propanol. After being dried overnight in a
vacuum oven at 100.degree. C., the dry gel was pushed through a 35
mesh screen. A ten gram sample was prepared as described in the
silica preparation to produce a solid mixed oxide compound. The
temperature use in the preparation of this sample was 600.degree.
C. After calcination, the surface area was found to be 491 m 2/g
and the pore volume was found to be 0.86 cc/g.
[0101] In this example the compositions activity for ethylene
polymerization was satisfactory. The polymer was found to have a
melt index of 0.1 and a high load melt index of 3.19 giving a shear
response (HLMI/MI) of 31.
COMPARATIVE EXAMPLE 14
[0102] An aqueous cogel was made by a procedure similar to that
above containing about 67 mole percent alumina and 33 mole percent
zirconia. Aluminum nitrate nonahydrate (187 grams) and zirconyl
nitrate dihydrate (67 grams), were dissolved in deionized water
(500 milliliters) to form a first mixture. This first mixture was
then gelled by contacting this first mixture with concentrated
ammonium hydroxide (140 milliliters), using a stirrer, to form a
second mixture. This second mixture, which was a gel, was washed
once in four liters of water, followed by filtration, and then wash
in four liters of n-propanol. After being dried overnight in a
vacuum oven at 100.degree. C., the dry gel was pushed through a 35
mesh screen. A ten gram sample was prepared as described in the
silica preparation to produce a solid acid compound. The
temperature use in the preparation of this sample was 600.degree.
C. After calcination, the surface area was found to be 319
m.sup.2/g and the pore volume was found to be 0.55 cc/g.
COMPARATIVE EXAMPLE 15
[0103] A cogel was made anhydrously to contain about 50 mole
percent alumina and 50 mole percent boria. Aluminum isopropoxide
(150 grams of 33 weight percent in butanol) and boric acid (15
grams) were dissolved in n-propanol (750 milliliters) to form a
first mixture. This first mixture slowly thickened. A solution of
7.5 milliliters of water combined with 7.5 milliliters of
concentrated ammonium hydroxide was added to this first mixture to
cause gellation. The gel was then dried in a vacuum oven at
100.degree. C. overnight and then was ground through a 35 mesh
sieve. A sample was calcined in air at 600.degree. C. to yield a
pore volume of 0.84 cc/g and a surface area of 378 square meters
per gram. When tested for polymerization activity it yielded an
activity of 25 g/g/h.
COMPARATIVE EXAMPLE 16 & EXAMPLE 17
[0104] Ketjen grade B alumina (13.8 grams) was impregnated with a
solution of 14 milliliters of zirconium butoxide-butanol complex in
26 ml of isopropanol. This made a damp powder which was then dried
in a vacuum oven overnight at 100.degree. C., and then calcined in
air at 700.degree. C. A polymerization test delivered nine grams of
polymer for an activity of 26 g/g/h.
[0105] The procedure of example 16 was followed except that the
zirconia was gelled in place before calcination. Ketjen B alumina
(27.4 grams) was impregnated with a solution of 27 milliliters of
zirconium butoxide-butanol complex in 23 milliliters of isopropanol
to make a damp powder. Then, 2 milliliters of concentrated ammonium
hydroxide combined with 5 milliliters of water was also added to
the dry powder after the zirconium butoxide had been added so that
a zirconia gel would form within the pores of the alumina. This
material was vacuum dried overnight at 100.degree. C., pushed
through a 35 mesh sieve, and calcined in air at 700.degree. C.
EXAMPLE 18
[0106] Alumina was impregnated with boria in this example. Boric
acid (7.33 grams) was dissolved in 43 milliliters of methanol. This
solution was then added to 21.8 grams of Ketjen grade B alumina.
The mixture was shaken until a uniform state of wetness was
achieved. Then the material was dried in a vacuum oven overnight at
90.degree. C. and pushed through a 35 mesh screen. After being
calcined in air at 600.degree. C. the compound was found to have a
pore volume of 1.02 cc/g and a surface area of 319 square meters
per gram.
EXAMPLE 19
[0107] Alumnio-phosphate with a P/Al of 0.4 was also tested after
calcination at 750.degree. C.
1TABLE I Ex. # A.sup.1 .degree. C..sup.2 S.sup.3 OAC.sup.4 P.sup.5
T.sup.6 A.sup.7 .sup. 1.sup.8 None NA 0.0000 2 TEA 0 61.1 0 2 None
NA 0.0000 2 EADC 0 28.0 0 3 Silica 600 0.5686 2 TEA 0.65 63.0 1 4
Alumina 800 0.6948 1 TEA 2.7 30.7 8 5 Alumina 600 0.2361 2 TEA 6.9
60.9 29 6 Alumina 400 0.8475 1 TEA trace 57.2 0 7 Alumino- 600
0.8242 1 TEA 45 66.0 50 Phosphate 8 Silica- 600 0.3912 1 TEA 8.3
40.0 32 Alumina 9 Silica- 600 0.1392 2 TEA 0 60.0 0 Titania 10
Zr--Al--B 600 0.9462 none 0.4 46.4 0 11 Zr--Al--B 600 1.0805 2 TEA
310.0 60.5 285 12 Zr--Al--B 600 0.3080 2 TEA 76.4 60.0 248 13
Zr--Al--B 600 .8742 2 TEA 262.7 60.0 301 14 Zr--Al 600 1.5694 2 TEA
12.1 25.0 19 15 B--Al 600 1.1408 2 TEA 10.6 22.0 25 16 Zr--Al 700
0.9066 2 TEA 9.0 25.5 26 17 Zr--Al 700 0.1732 2 TEA 9.0 21.2 147 18
B--Al 600 0.8527 2 TEA 11.8 22.5 37 19 Alumino- 750 0.1267 2 TEA
33.1 60.2 260 Phosphate Table I Notes .sup.1This is the solid
unmixed oxide compound used, or the solid mixed oxide compound
used. .sup.2This is the calcining temperature. .sup.3This is the
amount of solid oxide compound, in grams, being contacted with the
other compounds. .sup.4This is the amount, in milliliters of
organoaluminum compound used and the type of organoaluminum used.
The TEA was a 15 weight percent solution of triethylaluminum in
heptane. .sup.5This is the amount of polymer produced in grams.
.sup.6This is the amount of time used in minutes. .sup.7This is the
activity in gP/(gS .multidot. hr). .sup.8The amount of organometal
compound used was 25 micromoles. The type of organometal compound
used was bis(n-butylcyclopentadienyl) zirconium dichloride. This
organometal compound was in a solution that contained 0.5 grams of
bis(n-butylcyclopentadienyl) zirconium dichloride per 100
milliliters of toluene. Additionally, these example were run at
90.degree. C., under 550 psig ethylene, in 1.2 liters of
isobutane.
* * * * *