U.S. patent application number 13/331459 was filed with the patent office on 2012-04-19 for fluorinated catalyst systems and methods of forming the same.
This patent application is currently assigned to FINA TECHNOLOGY, INC.. Invention is credited to Tim Coffy, Michel Daumerie, Margarito Lopez, Vladimir Marin, Abbas Razavi.
Application Number | 20120095174 13/331459 |
Document ID | / |
Family ID | 40579956 |
Filed Date | 2012-04-19 |
United States Patent
Application |
20120095174 |
Kind Code |
A1 |
Marin; Vladimir ; et
al. |
April 19, 2012 |
Fluorinated Catalyst Systems and Methods of Forming the Same
Abstract
Supported catalyst systems and methods of forming the same are
described herein. In one specific embodiment, the methods generally
include providing an inorganic support material and contacting the
inorganic support material with an aluminum fluoride compound
represented by the formula AlF.sub.pX.sub.3-pB.sub.q to form an
aluminum fluoride impregnated support, wherein X is selected from
Cl, Br and OH.sup.-, B is H.sub.2O, p is selected from 1 to 3 and q
is selected from 0 to 6. The method further includes contacting the
aluminum fluoride impregnated support with a transition metal
compound to form a supported catalyst system, wherein the
transition metal compound is represented by the formula
[L].sub.mM[A].sub.n; wherein L is a bulky ligand, A is a leaving
group, M is a transition metal and m and n are such that a total
ligand valency corresponds to the transition metal valency.
Inventors: |
Marin; Vladimir; (Houston,
TX) ; Lopez; Margarito; (Pasadena, TX) ;
Razavi; Abbas; (Mons, BE) ; Coffy; Tim;
(Houston, TX) ; Daumerie; Michel; (Houston,
TX) |
Assignee: |
FINA TECHNOLOGY, INC.
Houston
TX
|
Family ID: |
40579956 |
Appl. No.: |
13/331459 |
Filed: |
December 20, 2011 |
Related U.S. Patent Documents
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Application
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Filing Date |
Patent Number |
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11978002 |
Oct 26, 2007 |
8110518 |
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13331459 |
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11413791 |
Apr 28, 2006 |
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11978002 |
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11529903 |
Sep 29, 2006 |
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11413791 |
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11413791 |
Apr 28, 2006 |
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11529903 |
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11493090 |
Jul 26, 2006 |
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11978002 |
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11413791 |
Apr 28, 2006 |
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11493090 |
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11540181 |
Sep 29, 2006 |
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11978002 |
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11413791 |
Apr 28, 2006 |
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11540181 |
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11715017 |
Mar 7, 2007 |
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11978002 |
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11471821 |
Jun 21, 2006 |
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11715017 |
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11413791 |
Apr 28, 2006 |
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11471821 |
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11414653 |
Apr 28, 2006 |
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11978002 |
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11414424 |
Apr 28, 2006 |
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11414653 |
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11740478 |
Apr 26, 2007 |
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11414424 |
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11413791 |
Apr 28, 2006 |
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11740478 |
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60848214 |
Sep 29, 2006 |
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Current U.S.
Class: |
526/130 ;
502/154; 526/154 |
Current CPC
Class: |
Y10S 526/943 20130101;
C08F 10/06 20130101; C08F 10/00 20130101; C08F 10/00 20130101; C08F
210/06 20130101; C08F 4/65912 20130101; B01J 21/12 20130101; C08F
110/06 20130101; C08F 210/06 20130101; C08F 4/65927 20130101; B01J
37/26 20130101; C08F 2400/02 20130101; C08F 110/06 20130101; C08F
210/06 20130101; C08F 2/00 20130101; C08F 10/00 20130101; C08F
2500/04 20130101; C08F 2500/12 20130101; C08F 2500/20 20130101;
C08F 2500/12 20130101; C08F 210/16 20130101; C08F 210/14 20130101;
C08F 4/65916 20130101; C08F 210/16 20130101; C08F 2500/12 20130101;
C08F 4/025 20130101; C08F 2500/03 20130101; C08F 2500/20 20130101;
C08F 2500/20 20130101; C08F 2500/20 20130101; C08F 2500/04
20130101; C08F 210/14 20130101; C08F 2500/20 20130101; C08F 2500/12
20130101; C08F 2500/12 20130101; C08F 210/14 20130101; C08F 2500/03
20130101; C08F 2500/04 20130101; C08F 210/16 20130101; C08F 10/06
20130101; C08F 210/06 20130101; C08F 210/06 20130101 |
Class at
Publication: |
526/130 ;
502/154; 526/154 |
International
Class: |
C08F 4/52 20060101
C08F004/52; C08F 10/00 20060101 C08F010/00; C08F 2/00 20060101
C08F002/00 |
Claims
1-7. (canceled)
8. A polymerization process comprising: introducing a supported
catalyst system comprising a fluorinated support composition and
transition metal compound into a polymerization vessel, wherein the
supported catalyst system is formed by a process comprising:
providing a support material comprising silica-alumina prepared by
cogel methods; contacting the support material with a fluorinating
agent selected from ammonium fluoride containing compounds to form
a fluorinated support; contacting the fluorinated support with a
transition metal compound to form a supported catalyst system; and
contacting the supported catalyst system with an olefin monomer
within the polymerization vessel to form a polyolefin.
9-13. (canceled)
14. A method of forming polyolefins comprising: providing an
inorganic support material; contacting the inorganic support
material with an aluminum fluoride compound represented by the
formula AlF.sub.pX.sub.3-pB.sub.q to form an aluminum fluoride
impregnated support, wherein X is selected from Cl, Br and
OH.sup.-, B is H.sub.2O, p is selected from 1 to 3 and q is
selected from 0 to 6; introducing the inorganic support material to
a reaction zone; introducing a transition metal compound to the
reaction zone; contacting the transition metal compound with the
inorganic support material for in situ activation/heterogenization
of the transition metal compound to form a catalyst system;
introducing an olefin monomer to the reaction zone; and contacting
the catalyst system with the olefin monomer to form a
polyolefin.
15. (canceled)
16. A method of forming polyolefins comprising: identifying desired
polymer properties; providing a transition metal compound;
providing an inorganic support material; contacting the inorganic
support material with an aluminum fluoride compound represented by
the formula AlF.sub.pX.sub.3-pB.sub.q to form an aluminum fluoride
impregnated support, wherein X is selected from Cl, Br and
OH.sup.-, B is H.sub.2O, p is selected from 1 to 3 and q is
selected from 0 to 6; contacting the transition metal compound with
the support material to form an active supported catalyst system,
wherein the contact of the transition metal compound with the
support material occurs in proximity to contact with an olefin
monomer; and contacting the active supported catalyst system with
the olefin monomer to form a polyolefin, wherein the polyolefin
comprises the desired polymer properties.
17. (canceled)
18. (canceled)
19. A method of forming copolymers comprising: providing a
transition metal compound represented by the formula
[L].sub.mM[A].sub.n, wherein L is a bis-indenyl, A is a leaving
group, M is a transition metal and m and n are such that the total
ligand valency corresponds to the transition metal valency;
providing an inorganic support material; contacting the inorganic
support material with an aluminum fluoride compound represented by
the formula AlF.sub.pX.sub.3-pB.sub.q to form an aluminum fluoride
impregnated support, wherein X is selected from Cl, Br and
OH.sup.-, B is H.sub.2O, p is selected from 1 to 3 and q is
selected from 0 to 6; contacting the transition metal compound with
the support material to form an active supported catalyst system,
wherein the contact of the transition metal compound with the
support material occurs in proximity to contact with monomer; and
contacting the active supported catalyst system with a plurality of
monomers to form an copolymer.
20-22. (canceled)
23. A method of forming a catalyst system comprising: providing an
inorganic support material, wherein the inorganic support material
has an acid strength (pKa) of less than about 4.8; contacting the
inorganic support material with an aluminum fluoride compound
represented by the formula AlF.sub.pX.sub.3-pB.sub.q to form an
aluminum fluoride impregnated support, wherein X is selected from
Cl, Br and OH.sup.-, B is H.sub.2O, p is selected from 1 to 3 and q
is selected from 0 to 6; introducing an inorganic support material
to a reaction zone; introducing a transition metal compound to the
reaction zone; contacting the transition metal compound with the
inorganic support material for in situ activation/heterogenization
of the transition metal compound to form a catalyst system;
introducing an olefin monomer to the reaction zone; and contacting
the catalyst system with the olefin monomer to form a
polyolefin.
24. (canceled)
25. (canceled)
26. A method of forming a catalyst composition for olefin
polymerization: providing an inorganic support composition, wherein
the inorganic support composition comprises aluminum, fluorine and
silica; contacting the inorganic support composition with a
transition metal compound to form a supported catalyst system,
wherein the transition metal compound is represented by the formula
[L].sub.mM[A].sub.n; wherein L is a ligand, A is a leaving group, M
is a transition metal and m and n are such that a total ligand
valency corresponds to the transition metal valency; and contacting
the inorganic support composition, the transition metal compound,
the supported catalyst system or combinations thereof with a
plurality of compounds, wherein the plurality of compounds comprise
a first compound comprising an organo aluminum compound and a
second compound comprising boron.
27. A polymerization process comprising: providing an inorganic
support composition, wherein the inorganic support composition
comprises aluminum, fluorine and silica; contacting the inorganic
support composition with a transition metal compound to form a
supported catalyst system, wherein the transition metal compound is
represented by the formula [L].sub.mM[A].sub.n; A is a leaving
group, M is a transition metal and m and n are such that a total
ligand valency corresponds to the transition metal valency;
contacting the inorganic support composition, the transition metal
compound, the supported catalyst system or combinations thereof
with at least one compound represented by the formula XR.sub.n,
wherein X is selected from Group 12 to 13 metals, lanthanide series
metals or combinations thereof and each R is independently selected
from alkyls, alkoxys, aryls, aryloxys, halogens, hydrides, Group 1
or 2 metals, organic nitrogen compounds, organic phosphorous
compounds and combinations thereof and n is from 2 to 5; and
contacting the supported catalyst system with an olefin monomer to
form a polyolefin.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation in part of U.S. patent
application Ser. No. 11/413,791, filed Apr. 28, 2006.
[0002] This application is also a continuation of U.S. patent
application Ser. No. 11/529,903, filed Sep. 29, 2006, which is a
continuation in part of U.S. patent application Ser. No.
11/413,791, filed Apr. 28, 2006.
[0003] This application is also a continuation of U.S. patent
application Ser. No. 11/493,090, filed Jul. 26, 2006, which is a
continuation in part of U.S. patent application Ser. No.
11/413,791, filed Apr. 28, 2006.
[0004] This application is also a continuation of U.S. patent
application Ser. No. 11/471,821, filed Jun. 21, 2006, which is a
continuation in part of U.S. patent application Ser. No.
11/413,791, filed Apr. 28, 2006.
[0005] This application is also a continuation of U.S. patent
application Ser. No. 11/540,181, filed Sep. 29, 2006, which is a
continuation in part of U.S. patent application Ser. No.
11/413,791, filed Apr. 28, 2006.
[0006] This application is also a continuation of U.S. patent
application Ser. No. 11/715,017, filed Mar. 7, 2007, which claims
the benefit of U.S. Provisional Patent Application No. 60/848,214,
filed on Sep. 29, 2006 and is a continuation in part of U.S. patent
application Ser. No. 11/471,821, filed Jun. 21, 2006, which is a
continuation in part of U.S. patent application Ser. No.
11/413,791, filed Apr. 28, 2006.
[0007] This application is also a continuation of U.S. patent
application Ser. No. 11/414,653, filed Apr. 28, 2006 and U.S.
patent application Ser. No. 11/414,424, filed Apr. 28, 2006.
[0008] This application is also a continuation of U.S. patent
application Ser. No. 11/740,478, filed Apr. 26, 2007, which is a
continuation in part of U.S. patent application Ser. No.
11/413,791, filed Apr. 28, 2006.
FIELD
[0009] Embodiments of the present invention generally relate to
supported catalyst compositions and methods of forming the
same.
BACKGROUND
[0010] Many methods of forming olefin polymers include contacting
olefin monomers with transition metal catalyst systems, such as
metallocene catalyst systems to form polyolefins. While it is
widely recognized that the transition metal catalyst systems are
capable of producing polymers having desirable properties, the
transition metal catalysts generally do not experience commercially
viable activities.
[0011] Therefore, a need exists to produce transition metal
catalyst systems having enhanced activity.
SUMMARY
[0012] One or more embodiments of the present invention include
methods of forming supported catalyst systems. The methods
generally include providing an inorganic support material and
contacting the inorganic support material with an aluminum fluoride
compound represented by the formula AlF.sub.pX.sub.3-pB.sub.q to
form an aluminum fluoride impregnated support, wherein X is
selected from Cl, Br and OH.sup.-, B is H.sub.2O, p is selected
from 1 to 3 and q is selected from 0 to 6. The method further
includes contacting the aluminum fluoride impregnated support with
a transition metal compound to form a supported catalyst system,
wherein the transition metal compound is represented by the formula
[L].sub.mM[A].sub.n; wherein L is a bulky ligand, A is a leaving
group, M is a transition metal and m and n are such that a total
ligand valency corresponds to the transition metal valency.
[0013] In the one or more embodiments, the method may further
include heating the aluminum fluoride impregnated support at a
temperature of greater than about 200.degree. C.
[0014] In the one or more embodiments, the method may further
include heating the aluminum fluoride impregnated support at a
temperature of greater than about 400.degree. C.
[0015] In the one or more embodiments, the contacting of the
inorganic support material with the aluminum fluoride compound may
occur in the presence of water, an organic medium or in solid
phase.
[0016] In the one or more embodiments, the inorganic support
material may include silica and alumina.
[0017] In the one or more embodiments, the inorganic support
material may consists essentially of silica and alumina.
[0018] In the one or more embodiments, the inorganic support
material may be selected from fluorinated silica, fluorinated
alumina, fluorinated alumina-silica, silica, alumina and
combinations thereof.
[0019] In the one or more embodiments, the aluminum fluoride
impregnated support may include a bonding sequence selected from
Si--O--Al--F and Si--O--Al--O--Al--F.
[0020] In the one or more embodiments, the aluminum fluoride
compound may include AlF.sub.3.
[0021] In the one or more embodiments, the supported catalyst
system may include at least about 1 wt. % alumina.
[0022] In the one or more embodiments, the supported catalyst
system may include at least about 1 wt. % aluminum fluoride.
[0023] In the one or more embodiments, supported metallocene
catalyst compositions may be formed by the method described
herein.
[0024] In the one or more embodiments, the transition metal
compound may include
dimethylsilybis(2-methyl-4-phenyl-indenyl)zirconium dichloride.
[0025] In the one or more embodiments, the method may further
include contacting the supported catalyst system with an olefin
monomer to form a polyolefin.
[0026] In the one or more embodiments, the method may further
include contacting the supported catalyst system with an olefin
monomer to form a polyolefin, wherein the polyolefin includes a
polymer selected from ethylene, a C.sub.3 or greater alpha olefin,
a C.sub.4 or greater conjugated diene, an ethylene-alpha olefin
copolymer or combinations thereof.
[0027] In the one or more embodiments, the method may further
include contacting the supported catalyst system with a propylene
monomer to form isotactic polypropylene.
[0028] One or more embodiments of the invention generally include a
method including providing an inorganic support composition,
wherein the inorganic support composition includes a bonding
sequence selected from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F
and combinations thereof and contacting the inorganic support
composition with a transition metal compound to form a supported
catalyst system, wherein the transition metal compound is
represented by the formula [L].sub.mM[A].sub.n; wherein L is a
bulky ligand, A is a leaving group, M is a transition metal and m
and n are such that a total ligand valency corresponds to the
transition metal valency.
[0029] In the one or more embodiments, the inorganic support
composition may be formed by simultaneously forming SiO.sub.2 and
Al.sub.2O.sub.3 and contacting the SiO.sub.2 and Al.sub.2O.sub.3
with a fluorinating agent.
[0030] In the one or more embodiments, the inorganic support
composition may be formed by contacting a silica containing
compound with a fluorinating agent and then with an organic
aluminum containing compound, wherein the organic aluminum
containing compound is represented by the formula AlR.sub.3 and
wherein each R is independently selected from alkyls, aryls and
combinations thereof.
[0031] In the one or more embodiments, the inorganic support
composition may be formed by contacting a silica containing
compound with an aluminum containing compound and then with a
fluorinating agent, wherein the organic aluminum containing
compound is represented by the formula AlR.sub.3 and where each R
is independently selected from alkyls, aryls and combinations
thereof.
[0032] In the one or more embodiments, the inorganic support
composition may be formed by providing an alumina-silica support
and contacting the alumina-silica support with a fluorinating
agent.
[0033] In the one or more embodiments, the inorganic support
composition may be formed by providing a silica containing support
and contacting the silica support with a fluorinating agent
represented by the formula R.sub.nAlF.sub.3-n, wherein each R is
independently selected from alkyls, aryls and combinations thereof
and n is 1 or 2.
[0034] In the one or more embodiments, the inorganic support
composition may be contacted with the transition metal compound in
the presence of a second aluminum containing compound represented
by the formula AlR.sub.3, wherein each R is independently selected
from alkyls, alkoxys, aryls, aryloxys, halogens or combinations
thereof.
[0035] In the one or more embodiments, the second aluminum
containing compound may be selected from triisobutylaluminum,
trioctylaluminum and combinations thereof.
[0036] In the one or more embodiments, the supported catalyst
composition may include a weight ratio of silica to aluminum
(Al.sup.1) of from about 0.01:1 to about 1000:1 and a weight ratio
of fluorine to silica of from about 0.001:1 to about 0.3:1.
[0037] In the one or more embodiments, the supported catalyst
composition may include a molar ratio of fluorine to aluminum of
about 1:1.
[0038] In the one or more embodiments, the inorganic support
composition may be contacted with the transition metal compound in
the presence of a second aluminum containing compound represented
by the formula AlR.sub.3, wherein each R is independently selected
from alkyls, alkoxys, aryls, aryloxys, halogens or combinations
thereof and in presence of a boron containing organic compound.
[0039] In the one or more embodiments, the supported catalyst
composition may be active for polymerization absent alkylation.
[0040] In the one or more embodiments, the method may further
include storing the supported catalyst system for a period of time
prior to contact with an olefin monomer.
[0041] In the one or more embodiments, the contact of the inorganic
support composition and the transition metal compound may occur in
proximity to contact with an olefin monomer.
[0042] In the one or more embodiments, the inorganic support
composition may be contacted with a plurality of transition metal
compounds.
[0043] In the one or more embodiments, the method may further
include contacting the supported catalyst system with an olefin
monomer to form a polyolefin, wherein the polyolefin has a bimodal
molecular weight distribution.
[0044] In the one or more embodiments, a supported metallocene
catalyst composition may be formed.
[0045] In the one or more embodiments, the method may further
include contacting the supported catalyst system with an olefin
monomer to form a polyolefin in a process selected from gas phase
process, solution phase process, slurry phase processes and
combinations thereof.
[0046] In the one or more embodiments, the method may further
include contacting the supported catalyst system with an olefin
monomer to form a polyolefin, wherein the polyolefin comprises a
polymer selected from ethylene, a C.sub.3 or greater alpha olefin,
a C.sub.4 or greater conjugated diene, an ethylene-alpha olefin
copolymer or combinations thereof.
[0047] In the one or more embodiments, the method may further
include contacting the supported catalyst system with an olefin
monomer to form a polyolefin, wherein the polyolefin is selected
from polyethylene, polypropylene and combinations thereof.
[0048] In the one or more embodiments, the method may further
include contacting the supported catalyst system with a propylene
monomer to form isotactic polypropylene.
[0049] In the one or more embodiments, the method may further
include contacting the supported catalyst system with an olefin
monomer to form a polyolefin comprising a molecular weight
distribution selected from unimodal, bimodal or multimodal.
[0050] In the one or more embodiments, the method may further
include contacting the supported catalyst system with a propylene
monomer to form a syndiotactic polypropylene.
[0051] In the one or more embodiments, the transition metal
compound may be selected from metallocene catalysts comprising a
symmetry selected from C.sub.1, C.sub.s or C.sub.2.
[0052] In the one or more embodiments, the transition metal
compound may be selected from metallocene catalysts, late
transition metal catalysts, post metallocene catalysts and
combinations thereof.
[0053] In the one or more embodiments, the method may further
include calcining the inorganic support composition at a
temperature of from about 200.degree. C. to about 800.degree. C. in
the presence of oxygen.
[0054] One or more embodiments of the invention generally include
catalyst systems. The catalyst systems generally include an
inorganic support composition, wherein the inorganic support
composition includes a bonding sequence selected from Si--O--Al--F,
F--Si--O--Al, F--Si--O--Al--F and combinations thereof and an
organometallic catalyst compound, wherein the transition metal
compound is represented by the formula [L].sub.mM[A].sub.n; wherein
L is a bulky ligand, A is a leaving group, M is a transition metal
and m and n are such that a total ligand valency corresponds to the
transition metal valency.
[0055] In the one or more embodiments, the catalyst system may
further include a second aluminum containing compound represented
by the formula AlR.sub.3, wherein each R is independently selected
from alkyls, aryls, halogens or combinations thereof.
[0056] In the one or more embodiments, the catalyst system may
further include
[0057] In the one or more embodiments, the second aluminum
containing compound may be selected from triisobutylaluminum,
trioctylaluminum or combinations thereof.
[0058] In the one or more embodiments, the catalyst system may
further include a weight ratio of silica to aluminum (Al.sup.1) of
from about 0.01:1 to about 1000:1 and a weight ratio of fluorine to
silica of from about 0.001:1 to about 0.3:1.
[0059] In the one or more embodiments, the catalyst system may
further include from about 0.1 wt. % to about 5 wt. % transition
metal compound.
[0060] In the one or more embodiments, the transition metal
compound may be selected from metallocene catalysts, late
transition metal catalysts, post metallocene catalysts and
combinations thereof.
[0061] One or more embodiments of the invention may further include
methods of forming a supported catalyst system. The methods
generally include providing a support material comprising
silica-alumina prepared by cogel methods, contacting the support
material with a fluorinating agent to form a fluorinated support
and contacting the fluorinated support with a transition metal
compound to form a supported catalyst system.
[0062] In the one or more embodiments, the methods may further
include contacting the fluorinated support with an organoaluminum
compound represented by AlR3, wherein each R is independently
selected from alkyls, aryls and combinations thereof.
[0063] In the one or more embodiments, the fluorinated support may
include semi-spherical particles, a surface area of from about 100
m.sup.2/g to about 300 m.sup.2/g, a pore volume of from about 1.0
ml/g to about 1.5 ml/g and a pore size of from about 15 microns to
about 30 microns.
[0064] In the one or more embodiments, the fluorinated support may
include semi-spherical particles, a surface area of from about 80
m.sup.2/g to about 800 m.sup.2/g, a pore volume of from about 0.1
ml/g to about 5 ml/g and a pore size of from about 10 microns to
about 100 microns.
[0065] In the one or more embodiments, the transition metal
compound may be selected from dichlorides, dimethyls, hydrides and
combinations thereof.
[0066] In the one or more embodiments, the fluorinated support may
include from about 0.1 mmol OH.sup.-/g Si to about 5 mmol
OH.sup.-/g Si.
[0067] In the one or more embodiments, the methods may further
include contacting the fluorinated support and the transition metal
compound in the presence of a solvent.
[0068] In the one or more embodiments, the solvent may include
toluene.
[0069] In the one or more embodiments, the methods may further
include contacting the fluorinated support and the transition metal
compound at a temperature of from about -60.degree. C. to about
120.degree. C.
[0070] In the one or more embodiments, the methods may further
include contacting the fluorinated support and the transition metal
compound at room temperature.
[0071] In the one or more embodiments, the fluorinating agent may
include an ammonium fluoride containing compound.
[0072] In the one or more embodiments, the fluorinating agent may
be selected from (NH.sub.4)F.sub.2NH.sub.4F.HF.sub.2,
(NH.sub.4).sub.2BF.sub.4, (NH.sub.4).sub.2SiF.sub.6 and
combinations thereof.
[0073] One or more embodiments of the invention include supported
metallocene catalysts. The supported metallocene catalysts
generally include a support composition including aluminum,
fluorine and silica, wherein the support composition includes from
about 0.1 wt. % to about 20 wt. % aluminum, an Al:F molar ratio of
from about 1:0.1 to about 1:10, a surface area of from about 80
m.sup.2/g to about 800 m.sup.2/g, a pore volume of from about 0.1
ml/g to about 5 ml/g and a pore size of from about 10 microns to
about 100 microns and a metallocene compound.
[0074] In the one or more embodiments, the metallocene compound may
be selected from cyclopentadienyl compounds, indenyl compounds,
fluorenyl compounds and combinations thereof.
[0075] In the one or more embodiments, the metallocene compound may
include
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride.
[0076] One or more embodiments of the invention include
polymerization processes. The polymerization processes generally
include introducing a supported catalyst system including a
fluorinated support composition and transition metal compound into
a polymerization vessel, wherein the supported catalyst system is
formed by a process. The process generally includes providing a
support material including silica-alumina prepared by cogel
methods, contacting the support material with a fluorinating agent
selected from ammonium fluoride containing compounds to form a
fluorinated support, contacting the fluorinated support with a
transition metal compound to form a supported catalyst system and
contacting the supported catalyst system with an olefin monomer
within the polymerization vessel to form a polyolefin.
[0077] In the one or more embodiments, the polymerization vessel
may include a gas phase vessel and the metallocene compound may
include a cyclopentadienyl fluorenyl catalyst.
[0078] In the one or more embodiments, the supported catalyst
system and the olefin monomer may be contacted in the presence of
an organoaluminum compound represented by AlR.sub.3, wherein each R
is independently selected from alkyls, aryls and combinations
thereof.
[0079] In the one or more embodiments, the polyolefin may include a
molecular weight distribution of from about 2 to about 4.
[0080] In the one or more embodiments, the polyolefin may include a
molecular weight distribution of from about 4 to about 25.
[0081] One or more embodiments include methods of forming catalyst
systems. The methods generally include contacting an alumina-silica
support composition with a fluorination reagent in the presence of
water to form a first fluorinated support composition, heating the
first fluorinated support composition in an oxygen containing
atmosphere to a temperature of from about 200.degree. C. to about
800.degree. C. to form a second fluorinated support composition,
wherein the second fluorinated support composition includes a
bonding sequence selected from Si--O--Al--F, F--Si--O--Al,
F--Si--O--Al--F and combinations thereof and contacting the second
fluorinated support composition with a transition metal compound to
form a supported catalyst system, wherein the transition metal
compound is represented by the formula [L].sub.mM[A].sub.n; wherein
L is a bulky ligand, A is a leaving group, M is a transition metal
and m and n are such that a total ligand valency corresponds to the
transition metal valency.
[0082] One or more embodiments of the present invention include
methods of forming catalyst systems for commercial production. The
methods generally include contacting a commercial quantity of
alumina-silica support composition with an aqueous fluorinating
agent to form a first fluorinated support composition, heating the
first fluorinated support composition in an oxygen containing
atmosphere to a temperature of from about 200.degree. C. to about
800.degree. C. to form a second fluorinated support composition,
wherein the second fluorinated support composition includes a
bonding sequence selected from Si--O--Al--F, F--Si--O--Al,
F--Si--O--Al--F and combinations thereof and contacting the second
fluorinated support composition with a transition metal compound to
form a supported catalyst system, wherein the transition metal
compound is represented by the formula [L].sub.mM[A].sub.n; wherein
L is a bulky ligand, A is a leaving group, M is a transition metal
and m and n are such that a total ligand valency corresponds to the
transition metal valency.
[0083] One or more embodiments of the present invention include
methods of forming catalyst systems comprising contacting an
alumina-silica support composition with a fluorinating agent within
a muffle furnace or fluidized bed to form a first fluorinated
support composition, heating the first fluorinated support
composition in an oxygen containing atmosphere to a temperature of
from about 200.degree. C. to about 800.degree. C. to form a second
fluorinated support composition, wherein the second fluorinated
support composition includes a bonding sequence selected from
Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and combinations
thereof and contacting the second fluorinated support composition
with a transition metal compound to form a supported catalyst
system, wherein the transition metal compound is represented by the
formula [L].sub.mM[A].sub.n; wherein L is a bulky ligand, A is a
leaving group, M is a transition metal and m and n are such that a
total ligand valency corresponds to the transition metal
valency.
[0084] In the one or more embodiments, the contact of the
alumina-silica support composition with the fluorinating agent may
occur in a single batch.
[0085] In the one or more embodiments, the heating of the first
fluorinated support composition may occur in an open dish or
fluidized bed.
[0086] In the one or more embodiments the heating of the first
fluorinated support composition may occur in a container with
partial removal of the volatile product.
[0087] In the one or more embodiments, the fluorinating agent may
include ammonium and a fluorine containing compound.
[0088] In the one or more embodiments, the fluorinating agent may
include ammonium bifluoride.
[0089] In the one or more embodiments, the first fluorinated
support composition may include from about 1 wt. % to about 30 wt.
% fluorinating agent.
[0090] In the one or more embodiments, the alumina-silica may
include from about 1 wt. % to about 30 wt. % alumina.
[0091] In the one or more embodiments, the alumina-silica may
include P10 silica.
[0092] In the one or more embodiments, the second fluorinated
support composition may include from about 0.1 wt. % to about 15
wt. % fluorine.
[0093] In the one or more embodiments, the second fluorinated
support composition may include a molar ratio of aluminum to
fluorine of from about 0.1 to about 10.
[0094] In the one or more embodiments, the second fluorinated
support composition may include a molar ratio of aluminum to
fluorine of from about 1 to about 1.
[0095] In the one or more embodiments, the first fluorinated
support composition may be heated to a first temperature for a
first time of from about 1 hour to about 4 hours and then to a
second temperature for a time of from about 1 hour to about 10
hours, wherein the second temperature is greater than the first
temperature.
[0096] In the one or more embodiments, the first temperature may be
from about 20.degree. C. to about 200.degree. C. and the second
temperature is from about 200.degree. C. to about 450.degree.
C.
[0097] In the one or more embodiments, the temperature may be from
about 300.degree. C. to about 800.degree. C.
[0098] In the one or more embodiments, the methods may further
include from about 1 wt. % to about 20 wt. % alumina and from about
1 wt. % to about 20 wt. % fluorine.
[0099] In the one or more embodiments, from about 2 to about 10
kilograms of alumina-silica support composition may contact the
fluorinating agent.
[0100] In the one or more embodiments, the fluorinating agent may
be represented by the formula R.sub.nAlF.sub.3-n, wherein each R is
independently selected from alkyls, aryls and combinations thereof
and n is 1 or 2.
[0101] In the one or more embodiments, the second fluorinated
support composition may be contacted with the transition metal
compound in the presence of a second aluminum containing compound
represented by the formula AlR.sub.3, wherein each R is
independently selected from alkyls, alkoxys, aryls, aryloxys,
halogens or combinations thereof.
[0102] In the one or more embodiments, the catalyst system may
include from about 0.1 wt. % to about 5 wt. % transition metal
compound.
[0103] In the one or more embodiments, the second fluorinated
support composition may be contacted with a plurality of transition
metal compounds.
[0104] In the one or more embodiments, the second transition metal
compound may be selected from dimethylsilylbis(2-methyl
-4-phenyl-indenyl)zirconium dichloride,
dimethylsilylbis(2-methyl-indenyl)zirconium dichloride,
dimethylsilylbis(2-methyl-4,5-benzo-indenyl)zirconium dichloride,
diphenylmethylene(fluorenyl)(cyclopentadienyl)zirconium dichloride,
dimethylmethylene(2,7-di-tert-butyl-fluorenyl)(cyclopentadienyl)zirconium
dichloride,
diphenylmethylene(3,6-di-tert-butyl-fluorenyl)(cyclopentadienyl)zirconium
dichloride and combinations thereof.
[0105] In the one or more embodiments, the methods may further
include contacting the second fluorinated support composition with
a Ziegler-Natta catalyst.
[0106] One or more embodiments of the invention generally include
polymerization processes. The polymerization processes generally
include contacting an inorganic support composition with a
fluorinating agent to form a fluorinated support, wherein the
fluorinating agent comprises an organofluorine compound having the
formula R.sub.n.sup.4AlF.sub.3-n and wherein each R is
independently selected from alkyls, aryls and combinations thereof
and n is 1 or 2, contacting the fluorinated support with a
transition metal compound to form a supported catalyst system and
contacting an olefin monomer with the supported catalyst
composition to form a polyolefin.
[0107] In the one or more embodiments, the inorganic support
composition may include a hydroxyl containing oxide.
[0108] In the one or more embodiments, the inorganic support
composition may include silica.
[0109] In the one or more embodiments, the silica may include a
surface area of from about 80 m.sup.2/g to about 800 m.sup.2/g, a
pore volume of from about 1.0 ml/g to about 1.5 ml/g and a pore
size of from about 15 microns to about 30 microns.
[0110] In the one or more embodiments, the fluorinating agent may
include diethylaluminum fluoride.
[0111] In the one or more embodiments, the transition metal
compound may include a cyclopentadienyl fluorenyl metallocene
catalyst.
[0112] In the one or more embodiments, the polyolefin may include
syndiotactic polypropylene.
[0113] In the one or more embodiments, the processes may further
include contacting the fluorinated support with a compound selected
from aluminum or boron containing compounds.
[0114] In the one or more embodiments, the processes may further
include calcining the fluorinated support at a temperature of from
about 200.degree. C. to about 800.degree. C. in the presence of
oxygen.
[0115] In the one or more embodiments, the fluorinated support may
include from about 0.1 wt. % to about 50 wt. % aluminum and an Al:F
molar ratio of from about 1:0.1 to about 1:2.
[0116] One or more embodiments of the invention generally include
methods of forming polyolefins. The methods generally include
introducing an inorganic support material to a reaction zone,
wherein the inorganic support material includes a bonding sequence
selected from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and
combinations thereof, introducing a transition metal compound to
the reaction zone, contacting the transition metal compound with
the inorganic support material for in situ
activation/heterogenization of the transition metal compound to
form a catalyst system, introducing an olefin monomer to the
reaction zone and contacting the catalyst system with the olefin
monomer to form a polyolefin.
[0117] In the one or more embodiments, the catalyst system may
contact the olefin monomer in the presence of an alkyl aluminum
compound.
[0118] In the one or more embodiments, the alkyl aluminum compound
may include triisobutyl aluminum.
[0119] One or more embodiments of the invention include methods of
forming supported catalyst systems. The methods generally include
contacting an inorganic support material with a transition metal
compound to form a supported catalyst system, wherein the contact
includes in situ activation/heterogenization and wherein the
inorganic support material includes a bonding sequence selected
from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and combinations
thereof.
[0120] In the one or more embodiments, the inorganic support
composition may be formed by simultaneously forming SiO.sub.2 and
Al.sub.2O.sub.3 and contacting the SiO.sub.2 and Al.sub.2O.sub.3
with a fluorinating agent.
[0121] In the one or more embodiments, the inorganic support
composition may be formed by contacting a silica containing
compound with a fluorinating agent and then with an organic
aluminum containing compound, wherein the organic aluminum
containing compound is represented by the formula AlR.sub.3 and
wherein each R is independently selected from alkyls, aryls and
combinations thereof.
[0122] In the one or more embodiments, the inorganic support
composition may be formed by contacting a silica containing
compound with an aluminum containing compound and then with a
fluorinating agent, wherein the organic aluminum containing
compound is represented by the formula AlR.sub.3 and where each R
is independently selected from alkyls, aryls and combinations
thereof.
[0123] In the one or more embodiments, the inorganic support
composition may be formed by providing an alumina-silica support
and contacting the alumina-silica support with a fluorinating
agent.
[0124] In the one or more embodiments, the inorganic support
composition may be formed by providing a silica containing support
and contacting the silica containing support with a fluorinating
agent represented by the formula R.sub.nAlF.sub.3-n, wherein each R
is independently selected from alkyls, aryls and combinations
thereof and n is 1 or 2.
[0125] In the one or more embodiments, the supported catalyst
composition may include a weight ratio of silica to aluminum
(Al.sup.1) of from about 0.01:1 to about 1000:1 and a weight ratio
of fluorine to silica of from about 0.001:1 to about 0.3:1.
[0126] In the one or more embodiments, the supported catalyst
composition may include a molar ratio of fluorine to aluminum
(Al.sup.1) of about 1:1.
[0127] In the one or more embodiments, the supported catalyst
composition may include from about 0.1 wt. % to about 5 wt. %
transition metal compound.
[0128] One or more embodiments of the invention include methods of
forming polyolefins. The methods generally include identifying
desired polymer properties, providing a transition metal compound,
selecting a support material capable of producing the desired
polymer properties, wherein the support material includes a bonding
sequence selected from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F
and combinations thereof, contacting the transition metal compound
with the support material to form an active supported catalyst
system, wherein the contact of the transition metal compound with
the support material occurs in proximity to contact with an olefin
monomer and contacting the active supported catalyst system with
the olefin monomer to form a polyolefin, wherein the polyolefin
comprises the desired polymer properties.
[0129] In the one or more embodiments, the contact of the
transition metal compound with the support material may include in
situ activation/heterogenization of the transition metal
compound.
[0130] In the one or more embodiments, the transition metal
compound may include a bis-indenyl transition metal compound.
[0131] In the one or more embodiments, the contact of the
transition metal compound with the support material is carried out
in the presence of triisobutyl aluminum to form polypropylene and
the desired polymer properties include a unimodal and narrow
molecular weight distribution.
[0132] In the one or more embodiments, the contact of the
transition metal compound, with the support material may be carried
out in the presence of methyl alumoxane or combinations of methyl
alumoxane and triisobutyl aluminum to form polypropylene and the
desired polymer properties may include a bimodal and broad
molecular weight distribution.
[0133] In the one or more embodiments, the desired polymer
properties may include a high molecular weight polymer.
[0134] In the one or more embodiments, the polyolefin may include
polypropylene or ethylene/propylene copolymers.
[0135] In the one or more embodiments, the desired polymer
properties may include a low molecular weight and the support
material may include a weight ratio of fluorine to aluminum of from
about 1.8:1 to about 7:1.
[0136] In the one or more embodiments, the desired polymer
properties may include a middle molecular weight and the support
material comprises a weight ratio of fluorine to aluminum of from
about 0.9:1 to about 1.8:1.
[0137] In the one or more embodiments, the desired polymer
properties may include a middle molecular weight and the active
supported catalyst system may be contacted with the olefin monomer
in the presence of triethylaluminum or isoprenyl aluminum.
[0138] In the one or more embodiments, the desired polymer
properties may include a high molecular weight and the active
supported catalyst system may be contacted with the olefin monomer
in the presence of triisobutyl aluminum.
[0139] In the one or more embodiments, the methods may further
include contacting the support material with a second aluminum
containing compound.
[0140] In the one or more embodiments, the desired polymer
properties may include a high molecular weight and the second
aluminum containing compound may include methyl alumoxane.
[0141] In the one or more embodiments, the desired polymer
properties may include a middle molecular weight and the second
aluminum containing compound may include triisobutyl aluminum.
[0142] In the one or more embodiments, the desired polymer
properties may include a broad molecular weight distribution.
[0143] In the one or more embodiments, the active supported
catalyst system may include a weight ratio of silica to aluminum
(Al.sup.(1)) of from about 0.01:1 to about 1000:1 and a weight
ratio of fluorine to silica of from about 0.001:1 to about
0.3:1.
[0144] In the one or more embodiments, the active supported
catalyst system may include a molar ratio of fluorine to silica of
about 1:1.
[0145] One or more embodiments of the invention include methods of
forming polyolefins. The methods generally include identifying a
desired polymer molecular weight, providing a transition metal
compound, providing a support material includes a bonding sequence
selected from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and
combinations thereof and wherein a fluorine to aluminum ratio of
the support material is capable of producing the desired polymer
molecular weight, contacting the transition metal compound with the
support material to form an active supported catalyst system,
wherein the contact of the transition metal compound with the
support material occurs in proximity to contact with an olefin
monomer and contacting the active supported catalyst system with
the olefin monomer to form a polyolefin, wherein the polyolefin
includes the desired polymer molecular weight.
[0146] One or more embodiments of the invention include bimodal
propylene polymers. The bimodal propylene polymers are generally
formed by the process including contacting a transition metal
catalyst with a support material to form an active supported
catalyst system, wherein the support material includes a bonding
sequence selected from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F
and combinations thereof and the contact of the transition metal
catalyst with the support material occurs in proximity to contact
with a propylene monomer and contacting the active supported
catalyst system with the olefin monomer to form a polyolefin in the
presence of methyl alumoxane.
[0147] One or more embodiments of the invention include methods of
forming copolymers. The methods generally include providing a
transition metal compound represented by the formula
[L].sub.mM[A].sub.n, wherein L is a bulky ligand including
bis-indenyl, A is a leaving group, M is a transition metal and m
and n are such that the total ligand valency corresponds to the
transition metal valency, providing a support material including a
bonding sequence selected from Si--O--Al--F, F--Si--O--Al,
F--Si--O--Al--F and combinations thereof, contacting the transition
metal compound with the support material to form an active
supported catalyst system, wherein the contact of the transition
metal compound with the support material occurs in proximity to
contact with monomer and contacting the active supported catalyst
system with a plurality of monomers to form an copolymer.
[0148] In the one or more embodiments, the transition metal
compound may be represented by the formula
XCp.sup.ACp.sup.BMA.sub.n, wherein X is a structural bridge,
Cp.sup.A and Cp.sup.B each denote a cyclopentadienyl group, each
being the same or different, at least one comprising a bis-indenyl
and which may be either substituted or unsubstituted, M is a
transition metal and A is an alkyl, hydrocarbyl or halogen group
and n is an integer between 0 and 4.
[0149] In the one or more embodiments, the methods may further
include contacting the plurality of monomers with a second
transition metal compound.
[0150] In the one or more embodiments, the second transition metal
compound may be selected from
dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride,
dimethylsilylbis(2-methyl-indenyl)zirconium dichloride,
dimethylsilylbis(2-methyl-4,5-benzo-indenyl)zirconium dichloride,
diphenylmethylene(fluorenyl)(cyclopentadienyl)zirconium dichloride,
dimethylmethylene(2,7-di-tert-butyl-fluorenyl)(cyclopentadienyl)zirconium
dichloride,
diphenylmethylene(3,6-di-tert-butyl-fluorenyl)(cyclopentadienyl)zirconium
dichloride and combinations thereof.
[0151] In the one or more embodiments, the second transition metal
compound may include a symmetry that is different that the
transition metal compound.
[0152] In the one or more embodiments, the plurality of monomers
may include propylene and at least one monomer represented by the
formula CH.sub.2.dbd.CHR, wherein R is selected from hydrogen,
C.sub.2 to C.sub.20 alkyls, C.sub.6 to C.sub.30 aryls and
combinations thereof.
[0153] In the one or more embodiments, the at least one monomer may
include ethylene.
[0154] In the one or more embodiments, the at least one monomer
includes ethylene and an alpha olefin represented by the formula
CH.sub.2.dbd.CHR, wherein R is selected from C.sub.2 to C.sub.20
alkyls.
[0155] In the one or more embodiments, the plurality of monomers
may include a first olefin monomer comprising propylene, a second
olefin monomer represented by the formula CH.sub.2.dbd.CHR, wherein
R is selected from hydrogen, C.sub.2 to C.sub.20 alkyls, C.sub.6 to
C.sub.30 aryls and combinations thereof and a third olefin monomer
represented by the formula CH.sub.2.dbd.CHR, wherein R is a C.sub.2
to C.sub.20 alkyl.
[0156] In the one or more embodiments, the second olefin monomer
may include ethylene and the third olefin monomer comprises a
C.sub.6 to C.sub.30 styrenic olefin.
[0157] In the one or more embodiments, the copolymer may include
from about 0.5 wt. % to about 70 wt. % polyethylene.
[0158] In the one or more embodiments, the plurality of monomers
may include from about 0.5 wt. % to about 10 wt. % ethylene.
[0159] In the one or more embodiments, the copolymer may include a
melt flow index that increases with an increasing amount of
polyethylene therein.
[0160] In the one or more embodiments, the active supported
catalyst system experiences an increase in activity with an
increasing amount of ethylene monomer.
[0161] In the one or more embodiments, the active supported
catalyst system first contacts bulk propylene and then contacts gas
phase ethylene.
[0162] One or more embodiments of the invention include olefin
copolymers.
[0163] In the one or more embodiments, the copolymers may be
selected from random copolymers, impact copolymers, block
copolymers, elastomers, rubbers and combinations thereof.
[0164] In the one or more embodiments, the copolymers may include
from about 0.5 wt. % to about 60 wt. % polyethylene and a melt flow
index of from about 1 g/10 min. to about 1000 g/10 min.
[0165] In the one or more embodiments, the copolymers may be
include a melting temperature of from about 90.degree. C. to about
160.degree. C.
[0166] In the one or more embodiments, the copolymer exhibits no
melting temperature peak.
[0167] In the one or more embodiments, the contact of the
transition metal compound with the support material may include in
situ activation/heterogenization of the transition metal
compound.
[0168] In the one or more embodiments, the contact of the
transition metal compound with the support material may be carried
out in the presence of triisobutyl aluminum.
[0169] One or more embodiments of the invention include catalyst
systems. The catalyst systems generally include an inorganic
support material including a bonding sequence selected from
Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and combinations
thereof, wherein the inorganic support material includes an acid
strength (pKa) of less than about 4.8 and a transition metal
compound, wherein the transition metal compound is represented by
the formula [L].sub.mM[A].sub.n; wherein L is a bulky ligand, A is
a leaving group, M is a transition metal and m and n are such that
a total ligand valency corresponds to a transition metal
valency.
[0170] In the one or more embodiments, the inorganic support
material may include a surface acidity of at least 0.3 mmol/g.
[0171] In the one or more embodiments, the catalyst system may
include a weight ratio of silica to aluminum of from about 0.01:1
to about 1000:1 and a weight ratio of fluorine to silica of from
about 0.001:1 to about 0.3:1.
[0172] In the one or more embodiments, the catalyst system may
include a molar ratio of fluorine to aluminum (Al.sup.1) of about
1:1.
[0173] In the one or more embodiments, the catalyst system may
include from about 0.1 wt. % to about 5 wt. % transition metal
compound.
[0174] In the one or more embodiments, the inorganic support
material may include a pH of less than about 7.5.
[0175] One or more embodiments include methods of forming catalyst
systems. The methods generally include providing an inorganic
support material including a bonding sequence selected from
Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and combinations
thereof, wherein the inorganic support material includes an acid
strength (pKa) of less than about 4.8 and contacting the inorganic
support material with a transition metal compound to form the
catalyst system, wherein the transition metal compound is
represented by the formula [L].sub.mM[A].sub.n; wherein L is a
bulky ligand, A is a leaving group, M is a transition metal and m
and n are such that a total ligand valency corresponds to a
transition metal valency.
[0176] In the one or more embodiments, the inorganic support
material may include a surface acidity of at least 0.3 mmol/g.
[0177] One or more embodiments of the invention generally include
methods of forming polyolefins. The methods generally include
introducing an inorganic support material to a reaction zone,
wherein the inorganic support material includes a bonding sequence
selected from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and
combinations thereof and an acid strength (pKa) of less than about
4.8, introducing a transition metal compound to the reaction zone,
contacting the transition metal compound with the inorganic support
material for in situ activation/heterogenization of the transition
metal compound to form a catalyst system, introducing an olefin
monomer to the reaction zone and contacting the catalyst system
with the olefin monomer to form a polyolefin.
[0178] In the one or more embodiments, the inorganic support
material may include a surface acidity of at least 0.3 mmol/g.
[0179] In the one or more embodiments, the catalyst system contacts
the olefin monomer in the presence of an alkyl aluminum
compound.
[0180] In the one or more embodiments, the alkyl aluminum compound
may include triisobutyl aluminum.
[0181] One or more embodiments include methods of forming catalyst
compositions for olefin polymerization. The methods generally
include providing an inorganic support composition, wherein the
inorganic support includes aluminum, fluorine and silica,
contacting the inorganic support composition with a transition
metal compound to form a supported catalyst system, wherein the
transition metal compound is represented by the formula
[L].sub.mM[A].sub.n; wherein L is a bulky ligand, A is a leaving
group, M is a transition metal and m and n are such that a total
ligand valency corresponds to the transition metal valency and
contacting the inorganic support composition, the transition metal
compound, the supported catalyst system or combinations thereof
with at least one compound represented by the formula XR.sub.n,
wherein X is selected from Group 12 to 13 metals, lanthanide series
metals or combinations thereof and each R is independently selected
from alkyls, alkoxys, aryls, aryloxys, halogens, hydrides, Group 1
or 2 metals, organic nitrogen compounds, organic phosphorous
compounds and combinations thereof and n is from 2 to 5.
[0182] In the one or more embodiments, each R is selected from
C.sub.4 to C.sub.30 alkyls.
[0183] In the one or more embodiments, each R is selected from
C.sub.4 to C.sub.8 alkyls.
[0184] In the one or more embodiments, X includes aluminum.
[0185] In the one or more embodiments, X includes boron.
[0186] In the one or more embodiments, the at least one compound
includes a plurality of compounds.
[0187] In the one or more embodiments, the at least one compound
may include a trialkyl aluminum and a trialkyl boron.
[0188] In the one or more embodiments, the inorganic support
composition may include a bonding sequence selected from
Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and combinations
thereof.
[0189] In the one or more embodiments, the aluminum and fluorine of
the inorganic support composition are chemically bonded.
[0190] In the one or more embodiments, the inorganic support
composition may include from about 1 to about 70 wt. %
fluorine.
[0191] In the one or more embodiments, the inorganic support
composition may include from about 1 to about 30 wt. %
fluorine.
[0192] In the one or more embodiments, the inorganic support
composition may include from about 2 to about 15 wt. %
fluorine.
[0193] In the one or more embodiments, the inorganic support
composition may include from about 2 to about 10 wt. %
fluorine.
[0194] In the one or more embodiments, the inorganic support
composition may include from about 5 to about 7 wt. % fluorine.
[0195] In the one or more embodiments, the inorganic support
composition may include from about 1 to about 60 wt. %
aluminum.
[0196] In the one or more embodiments, the inorganic support
composition may include from about 13 to about 17 wt. %
aluminum.
[0197] In the one or more embodiments, the L may include a C.sub.4
to C.sub.30 hydrocarbon, oxygen, nitrogen, phosphorus or
combinations thereof, M is selected from Group 3 to 14 metals,
lanthanides, actinides and combinations thereof and A is selected
from halogens and C.sub.4 to C.sub.30 hydrocarbons.
[0198] In the one or more embodiments, the transition metal
compound may include a Cp-Flu metallocene.
[0199] In the one or more embodiments, the transition metal
compound may include a bis-indenyl metallocene.
[0200] In the one or more embodiments, the transition metal
compound may include a bis-indenyl metallocene and a Cp-Flu
metallocene.
[0201] In the one or more embodiments, the transition metal
compound may include
dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium
dichloride.
[0202] In the one or more embodiments, the at least one compound
contacts the transition metal compound in an amount that is
insufficient to alkylate the transition metal compound.
[0203] In the one or more embodiments, the method may further
include isolating the supported catalyst system.
[0204] In the one or more embodiments, the supported catalyst
system contacts the olefin monomer without isolation.
[0205] In the one or more embodiments, the method may further
include contacting the inorganic support composition, the
transition metal compound or the supported catalyst system with an
anti-fouling agent.
[0206] In the one or more embodiments, at least one compound may be
represented by the formula XR.sub.3, wherein X is selected from
Group 12 to 13 metals, lanthanide series metals or combinations
thereof and each R is independently selected from alkyls, alkoxys,
aryls, aryloxys, halogens, hydrides and combinations thereof.
[0207] One or more embodiments of the invention include methods of
forming a catalyst composition for olefin polymerization. The
methods generally include providing an inorganic support
composition, wherein the inorganic support composition includes
aluminum, fluorine and silica, contacting the inorganic support
composition with a transition metal compound to form a supported
catalyst system, wherein the transition metal compound is
represented by the formula [L].sub.mM[A].sub.n; wherein L is a
bulky ligand, A is a leaving group, M is a transition metal and m
and n are such that a total ligand valency corresponds to the
transition metal valency and contacting the inorganic support
composition, the transition metal compound, the supported catalyst
system or combinations thereof with a plurality of compounds,
wherein the plurality of compounds include a first compound
including an organo aluminum compound and a second compound
comprising boron.
[0208] One or more embodiments of the invention include
polymerization processes. The polymerization processes generally
include providing an inorganic support composition, wherein the
inorganic support composition includes aluminum, fluorine and
silica, contacting the inorganic support composition with a
transition metal compound to form a supported catalyst system,
wherein the transition metal compound is represented by the formula
[L].sub.mM[A].sub.n; wherein L is a bulky ligand, A is a leaving
group, M is a transition metal and m and n are such that a total
ligand valency corresponds to the transition metal valency,
contacting the inorganic support composition, the transition metal
compound, the supported catalyst system or combinations thereof
with at least one compound represented by the formula XR.sub.n,
wherein X is selected from Group 12 to 13 metals, lanthanide series
metals or combinations thereof and each R is independently selected
from alkyls, alkoxys, aryls, aryloxys, halogens, hydrides, Group 1
or 2 metals, organic nitrogen compounds, organic phosphorous
compounds and combinations thereof and n is from 2 to 5 and
contacting the supported catalyst system with an olefin monomer to
form a polyolefin.
BRIEF DESCRIPTION OF DRAWINGS
[0209] FIG. 1 illustrates Al.sup.27 NMR spectra of polymer
samples.
[0210] FIG. 2 illustrates the activity of polymer samples.
[0211] FIG. 3 illustrates an optical microscopy of polymer fluff
produced from embodiments of the invention.
[0212] FIG. 4 illustrates an optical microscopy of polymer fluff
produced from MAO based catalyst systems.
[0213] FIG. 5 illustrates a GPC plot of molecular weight
distribution for different second aluminum containing
compounds.
DETAILED DESCRIPTION
Introduction and Definitions
[0214] A detailed description will now be provided. Each of the
appended claims defines a separate invention, which for
infringement purposes is recognized as including equivalents to the
various elements or limitations specified in the claims. Depending
on the context, all references below to the "invention" may in some
cases refer to certain specific embodiments only. In other cases it
will be recognized that references to the "invention" will refer to
subject matter recited in one or more, but not necessarily all, of
the claims. Each of the inventions will now be described in greater
detail below, including specific embodiments, versions and
examples, but the inventions are not limited to these embodiments,
versions or examples, which are included to enable a person having
ordinary skill in the art to make and use the inventions when the
information in this patent is combined with available information
and technology.
[0215] Various terms as used herein are shown below. To the extent
a term used in a claim is not defined below, it should be given the
broadest definition persons in the pertinent art have given that
term as reflected in printed publications and issued patents at the
time of filing. Further, unless otherwise specified, all compounds
described herein may be substituted or unsubstituted and the
listing of compounds includes derivatives thereof.
[0216] As used herein, the term "impregnated" refers to a support
material in which the aluminum fluoride (or derivatives thereof) is
chemically bonded to the surface of the support material.
[0217] As used herein, the term "bonding sequence" refers to an
element's sequence, wherein each element is connected to another by
sigma bonds, dative bonds, ionic bonds or combinations thereof.
[0218] The term "tacticity" refers to the arrangement of pendant
groups in a polymer. For example, a polymer is "atactic" when its
pendant groups are arranged in a random fashion on both sides of
the chain of the polymer. In contrast, a polymer is "isotactic"
when all of its pendant groups are arranged on the same side of the
chain and "syndiotactic" when its pendant groups alternate on
opposite sides of the chain.
[0219] As used herein, the term "aluminum containing support
material" refers to the support material of all embodiments that is
contacted with the transition metal catalyst. For example, the
aluminum containing support material of the first embodiments
refers to the aluminum fluoride impregnated support while the
aluminum containing support material of other embodiments (e.g.,
the second embodiments) refers to the fluorinated support.
[0220] The term "commercial quantity" includes an amount sufficient
to produce from about 1 ton/hr to about 5 tons/hour of a polyolefin
or from about 1 ton to about 50 tons over a period of from about 5
days to about 2 years.
[0221] The term "open dish" refers to fast removal of volatile
product.
[0222] The term "heterogeneous" refers to processes wherein the
catalyst system is in a different phase than one or more reactants
in the process.
[0223] As used herein, "room temperature", which is used
interchangeably with the term "ambient", means that a temperature
difference of a few degrees does not matter to the phenomenon under
investigation, such as a preparation method. In some environments,
room temperature may include a temperature of from about 21.degree.
C. to about 28.degree. C. (68.degree. F. to 72.degree. F.), for
example. However, room temperature measurements generally do not
include close monitoring of the temperature of the process and
therefore such a recitation does not intend to bind the embodiments
described herein to any predetermined temperature range.
[0224] As used herein, the terms "aluminum", "silica", "fluorine"
and "boron" refer to the chemical composition, as well as derivates
thereof, such as borates, for example.
[0225] Various ranges are further recited below. It should be
recognized that unless stated otherwise, it is intended that the
endpoints are to be interchangeable. Further, any point within that
range is contemplated as being disclosed herein.
Catalyst Systems
[0226] Embodiments of the invention generally include supported
catalyst systems. The supported catalyst systems generally include
a support material and a transition metal compound, which are
described in greater detail below. As discussed in further detail
below, the catalyst systems may be formed in a number of ways and
sequences.
[0227] In one or more embodiments (e.g., first embodiment), the
supported catalyst systems generally are formed by contacting a
support material with an aluminum fluoride compound to form an
aluminum fluoride impregnated support and contacting the aluminum
fluoride impregnated support with a transition metal compound to
form a supported catalyst system.
[0228] The "support material" as used in reference to the first
embodiments refers to the support material prior to contact with
the "aluminum fluoride", discussed in further detail below, and, in
one embodiment, includes an inorganic support composition. The
inorganic support compositions as used in all embodiments herein
generally include materials known to one skilled in the art, such
as talc, inorganic oxides, clays and clay minerals, ion-exchanged
layered compounds, diatomaceous earth compounds, zeolites or a
resinous support material, such as a polyolefin, for example.
Specific inorganic oxides include silica, alumina, magnesia,
titania, zirconia and combinations thereof, for example.
[0229] In one or more embodiments, the support material includes
silica. In another embodiment, the support material is an
alumina-silica (which may be used interchangeably herein as
silica-alumina). In yet another embodiment, the support material
includes a fluorinated alumina-silica. In one or more embodiments,
the support material is formed of spherical particles and/or
semi-spherical particles. In one or more embodiments, the support
material is an aluminum containing support material.
[0230] In one or more embodiments, the support materials may have
an average particle size of from about 5 microns to 200 microns, or
from about 15 microns to about 30 microns, or from about 10 microns
to 100 microns or from about 10 microns to about 30 microns, for
example. The support materials may further have a surface area of
from 50 m.sup.2/g to 1,000 m.sup.2/g, or from about 80 m.sup.2/g to
about 800 m.sup.2/g, or from 100 m.sup.2/g to 400 m.sup.2/g, or
from about 200 m.sup.2/g to about 300 m.sup.2/g or from about 150
m.sup.2/g to about 300 m.sup.2/g, for example. In addition, the
support materials may have a pore volume of from about 0.1 cc/g to
about 5 cc/g, or from about 0.5 cc/g to about 3.5 cc/g, or from
about 0.5 cc/g to about 2.0 cc/g or from about 1.0 cc/g to about
1.5 cc/g, for example.
[0231] In one or more embodiments, the support material may have an
effective number of reactive hydroxyl groups, e.g., a number that
is sufficient for binding the aluminum fluoride to the support
material. For example, the number of reactive hydroxyl groups in
excess of the number needed to bind the aluminum fluoride to the
support material may be minimized. In one embodiment, the support
material may include from about 0.1 mmol OH.sup.-/g Si to about 5
mmol OH.sup.-/g Si or from about 0.5 mmol OH.sup.-/g Si to about 4
mmol OH.sup.-/g Si, for example.
[0232] The support materials are generally commercially available
materials, such as P10 alumina silica, commercially available from
Fuji Sylisia Chemical LTD, for example (e.g., silica alumina having
a surface area of 281 m.sup.2/g and a pore volume of 1.4 ml/g).
[0233] First embodiments of the invention further include
contacting the support material with an aluminum fluoride to form
an aluminum fluoride impregnated support.
[0234] Attempts to create highly active (e.g., greater than about
10,000 g/g/hr) metallocene catalysts have recently included
utilizing fluorine salts and ammonium fluorides, for example.
However, when such processes have approached commercial production,
environmental concerns have been raised (e.g., such processes may
result in ammonia releases into the environment).
[0235] Further, analysis of such fluorinated aluminum silica
samples, and in particular NMR analysis, has revealed an
interesting phenomenon. The Al.sup.27 NMR spectra of such samples
exhibited peaks around -15 ppm, which is generally characteristic
of an aluminum trifluoride (AlF.sub.5 moiety) species. In addition,
a broad feature from 50 ppm to -40 ppm was observed, corresponding
to a variety of aluminum containing compounds. See, FIG. 1. The
analysis further revealed that the intensity of the peaks around
-15 ppm increased with an increasing amount of aluminum fluoride
being used in the fluorination process, which also corresponded
with the polymers formed from catalysts exhibiting the highest
activities. Note that the specific species corresponding to each
line is not relevant to this analysis and therefore is not included
herein.
[0236] As briefly discussed, first embodiments of the invention
include contacting the support material with an aluminum fluoride.
The aluminum fluoride includes a compound including aluminum and
fluorine. For example, in one embodiment, the aluminum fluoride is
generally represented by the formula AlF.sub.pX.sub.3-pB.sub.q,
wherein X is selected from Cl, Br and OH.sup.-, B is H.sub.2O, p is
selected from 1 to 3 and q is selected from 0 to 6. In one
embodiment, the aluminum fluoride is aluminum trifluoride. It is to
be noted that in one or more embodiments, primarily the first
embodiments, the aluminum fluoride does not include ammonium, as it
is believed that ammonium may decompose during the fluorinating
process, resulting in environmental concerns for large scale
production.
[0237] The fluorination process of the first embodiments may
include contacting the support material with the aluminum fluoride
at a temperature of from about 100.degree. C. to about 250.degree.
C. or from about 150.degree. C. to about 200.degree. C. for a time
of from about 1 hour to about 10 hours or from about 1 hour to
about 5 hours, for example, to form an aluminum fluoride
impregnated support.
[0238] In the fluorination process of one or more embodiments
(e.g., the second embodiments), the aluminum containing support
materials may be formed by contacting the support material with a
first aluminum containing compound. Such contact may occur at a
reaction temperature of from about room temperature to about
150.degree. C. The formation may further include calcining at a
calcining temperature of from about 150.degree. C. to about
600.degree. C., or from about 200.degree. C. to about 600.degree.
C. or from about 350.degree. C. to about 500.degree. C., for
example. In one embodiment, the calcining occurs in the presence of
an oxygen containing compound, for example.
[0239] The first aluminum containing compound may include an
organic aluminum containing compound. The organic aluminum
containing compound may be represented by the formula AlR.sub.3,
wherein each R is independently selected from alkyls, aryls and
combinations thereof. The organic aluminum compound may include
methyl alumoxane (MAO) or modified methyl alumoxane (MMAO), for
example or, in a specific embodiment, triethyl aluminum (TEAl),
triisobutyl aluminum (TIBAl) or trioctylaluminum (TNOAl), for
example.
[0240] The support composition of the second embodiments is
fluorinated by methods known to one skilled in the art. For
example, the support composition may be contacted with a
fluorinating agent to form the fluorinated support. The
fluorination process may include contacting the support composition
with the fluorine containing compound at a first temperature of
from about 100.degree. C. to about 200.degree. C. for a first time
of from about 1 hour to about 10 hours or from about 1 hour to
about 5 hours, for example and then raising the temperature to a
second temperature of from about 250.degree. C. to about
550.degree. C. or from about 400.degree. C. to about 500.degree. C.
for a second time of from about 1 hour to about 10 hours, for
example.
[0241] As described herein, the "support composition" of the second
embodiments may be impregnated with aluminum prior to contact with
the fluorinating agent, after contact with the fluorinating agent
or simultaneously with contact with the fluorinating agent. In one
of the second embodiments, the fluorinated support composition is
formed by simultaneously forming SiO.sub.2 and Al.sub.2O.sub.3 and
then contacting the with the fluorinating agent. In another of the
second embodiments, the fluorinated support composition is formed
by contacting an aluminum containing silica support material with
the fluorinating agent. In yet another second embodiment, the
fluorinated support composition is formed by contacting a silica
support material with the fluorinating agent and then contacting
the fluorinated support with the first aluminum containing
compound.
[0242] The fluorinating agent of the second embodiments generally
includes any fluorinating agent which can form fluorinated
supports. Suitable fluorinating agents include, but are not limited
to, hydrofluoric acid (HF), ammonium fluoride (NH.sub.4F), ammonium
bifluoride (NH.sub.4HF.sub.2), ammonium fluoroborate
(NH.sub.4BF.sub.4), ammonium silicofluoride
((NH.sub.4).sub.2SiF.sub.6), ammonium fluorophosphates
(NH.sub.4PF.sub.6), (NH.sub.4).sub.2TaF.sub.7, NH.sub.4NbF.sub.4,
(NH.sub.4).sub.2GeF.sub.6, (NH.sub.4).sub.2SmF.sub.6,
(NH.sub.4).sub.2TiF.sub.6, (NH.sub.4)ZrF.sub.6, MoF.sub.6,
ReF.sub.6, SO.sub.2ClF, F.sub.2, SiF.sub.4, SF.sub.6, ClF.sub.3,
ClF.sub.5, BrF.sub.5, IF.sub.7, NF.sub.3, HF, BF.sub.3, NHF.sub.2
and combinations thereof, for example. In one or more embodiments,
the fluorinating agent is an ammonium fluoride including a
metalloid or nonmetal (e.g., (NH.sub.4).sub.2PF.sub.6,
(NH.sub.4).sub.2BF.sub.4, (NH.sub.4).sub.2SiF.sub.6).
[0243] In one or more of the second embodiments, the molar ratio of
fluorine to the first aluminum containing compound (F:Al.sup.1) is
generally from about 0.5:1 to 6:1 or from about 0.5:1 to about 4:1,
for example.
[0244] In one or more embodiments, the aluminum containing support
material has a bonding sequence selected from Si--O--Al--F,
F--Si--O--Al or F--Si--O--Al--F, for example. In one of the first
embodiments, the aluminum fluoride impregnated support exhibits a
bonding sequence of Fl-Al--O--Si or Fl-Al--O--Al--O--Si.
[0245] In one or more embodiments, the aluminum containing support
materials (e.g., aluminum fluoride impregnated support) may have an
aluminum content of from about 0.5 wt. % to about 95 wt. %, or from
about 0.1 wt. % to about 20 wt. %, or from about 0.1 wt. % to about
50 wt. %, or from about 1 wt. % to about 25 wt. %, or from about 2
wt. % to about 8 wt. %, or from about 7 wt. % to about 15 wt. % or
at least about 10 wt. %, for example.
[0246] In one of the first embodiments, the aluminum fluoride
impregnated support includes at least about 1 wt. % or at least
about 5 wt. % of the aluminum fluoride, for example.
[0247] It has been observed that fluorinated supports having a high
aluminum and fluorine content (as discussed herein) resulted in
increased thermal stability, and therein increased activity.
[0248] In one of the second embodiments, the aluminum containing
support materials may further have a silica to aluminum molar ratio
of from about 0.01:1 to about 1000:1, for example.
[0249] Six well-characterized crystalline phases of aluminum
fluorides are known to one skilled in the art, which exhibit
varying degrees of Lewis acidity. See, T. Krahl, E. Kemnitz, J.
Fluorine Chem., 127 (2006), 663-678, which is incorporated by
reference herein. Analysis of the structures of AlF.sub.3 by
embodiments of the invention has led to the extrapolation that the
acidity of the surface, and therefore the activity of the resulting
catalyst may relate to the coordination number of the aluminum
center. Therefore, the first embodiments of the invention generally
provide for lowering the coordination number of the aluminum
fluoride (e.g., via complex formation, dissolution or
impregnation). In one or more first embodiments, the coordination
number is lowered via impregnation of the aluminum fluoride.
[0250] The first embodiments of the invention further include
heating the aluminum fluoride impregnated support at a temperature
of at least about 400.degree. C., or from about 350.degree. C. to
about 600.degree. C. or from about 400.degree. C. to about
500.degree. C. for a time of at least about 1 hour, or from about 1
hour to about 10 hours or from about 1.5 hours to about 5 hours,
for example, to form a support which may have a modified chemical
structure.
[0251] In one or more embodiments, the aluminum containing support
(e.g., the aluminum fluoride impregnated support) is prepared by a
cogel method (e.g., a gel including both silica and alumina). As
used herein, the term "cogel method" refers to a preparation
process including mixing a solution including the aluminum fluoride
into a gel of the support material (e.g.,
AlF.sub.3+H.sub.2SO.sub.4+Na.sub.2O--SiO.sub.2).
[0252] Embodiments of the invention generally include contacting
the aluminum containing support material (e.g., aluminum fluoride
impregnated support) with a transition metal compound to form a
supported catalyst composition. Such processes are generally known
to ones skilled in the art and may include charging the transition
metal compound in an inert solvent. Although the process is
discussed below in terms of charging the transition metal compound
in an inert solvent, the aluminum containing support material
(either in combination with the transition metal compound or
alternatively) may be mixed with the inert solvent to form a
support slurry prior to contact with the transition metal compound.
Methods for supporting transition metal catalysts are generally
known in the art. (See, U.S. Pat. No. 5,643,847, U.S. Pat. No.
9,184,358 and U.S. Pat. No. 9,184,389, which are incorporated by
reference herein.)
[0253] A variety of solvents may be used as the inert solvent, but
any solvent selected should remain in liquid form at all relevant
reaction temperatures and the ingredients used to form the
supported catalyst composition should be at least partially soluble
in the solvent.
[0254] Suitable solvents include substituted and unsubstituted
aliphatic hydrocarbons and substituted and unsubstituted aromatic
hydrocarbons. For example, the inert solvent may include hexane,
heptane, octane, decane, toluene, xylene, dichloromethane,
chloroform, 1-chlorobutane or combinations thereof. In one specific
embodiment, the inert solvent includes isohexane. In another
embodiment, the inert solvent includes mineral oil including an
amount of toluene.
[0255] The transition metal compound and the aluminum containing
support material may be contacted at a reaction temperature of from
about -60.degree. C. to about 120.degree. C. or from about
-45.degree. C. to about 112.degree. C. or at a reaction temperature
below about 90.degree. C., e.g., from about 0.degree. C. to about
50.degree. C., or from about 20.degree. C. to about 30.degree. C.
or at room temperature, for example, for a time of from about 10
minutes to about 5 hours or from about 30 minutes to about 120
minutes, for example.
[0256] In addition, and depending on the desired degree of
substitution, the weight ratio of fluorine to transition metal
(F:M) may be from about 1:1 to about 20:1 or from about 1:1 to
about 5:1, for example. In one embodiment, the supported catalyst
composition includes from about 0.1 wt. % to about 5 wt. % or from
about 1 wt. % to about 3 wt. % transition metal compound.
[0257] Upon completion of the reaction, the solvent, along with
reaction by-products, may be removed from the mixture in a
conventional manner, such as by evaporation or filtering, to obtain
the dry, supported catalyst composition. For example, the supported
catalyst composition may be dried in the presence of magnesium
sulfate. The filtrate, which contains the supported catalyst
composition in high purity and yield can, without further
processing, be directly used in the polymerization of olefins if
the solvent is a hydrocarbon. In such a process, the aluminum
fluoride impregnated support and the transition metal compound are
contacted prior to subsequent polymerization (e.g., prior to
entering a reaction vessel). Alternatively, the process may include
contacting the aluminum fluoride impregnated support with the
transition metal in proximity to contact with an olefin monomer
(e.g., contact within a reaction vessel).
[0258] In one specific embodiment (e.g., third embodiments) useful
for producing the catalyst systems described herein in commercial
quantities, the catalyst system is formed by contacting an
alumina-silica support composition with ammonium bifluoride in the
presence of water to form a first fluorinated support composition.
The third embodiments then include heating the first fluorinated
support composition in an oxygen containing atmosphere to a
temperature of from about 200.degree. C. to about 600.degree. C. to
form a second fluorinated support composition, wherein the second
fluorinated support composition includes a bonding sequence
selected from Si--O--Al--F, F--Si--O--Al, F--Si--O--Al--F and
combinations thereof and then contacting the second fluorinated
support composition with a transition metal compound to form a
supported catalyst system, wherein the transition metal compound is
represented by the formula [L].sub.mM[A].sub.n; wherein L is a
bulky ligand, A is a leaving group, M is a transition metal and m
and n are such that a total ligand valency corresponds to the
transition metal valency.
[0259] In one specific third embodiment, the method includes
contacting a commercial quantity of alumina-silica support
composition with an aqueous fluorinating agent to form a first
fluorinated support composition, heating the first fluorinated
support composition in an oxygen containing atmosphere to a
temperature of from about 200.degree. C. to about 600.degree. C. to
form a second fluorinated support composition and contacting the
second fluorinated support composition with the transition metal
compound to form a supported catalyst system.
[0260] In another specific third embodiment, the method includes
contacting an alumina-silica support composition with a
fluorinating agent in the presence of water within a muffle furnace
to form a first fluorinated support composition, heating the first
fluorinated support composition in an oxygen containing atmosphere
to a temperature of from about 200.degree. C. to about 600.degree.
C. to form a second fluorinated support composition and contacting
the second fluorinated support composition with the transition
metal compound to form a supported catalyst system.
[0261] The contact of the alumina-silica support composition with
the fluorinating agent in third embodiments may occur in a single
batch, in multiple batches, in an open dish or in a container with
partial removal of the volatile product, for example.
[0262] In one specific third embodiment, the fluorinating agent
includes ammonium and a fluorine containing compound. For example,
the fluorinating agent includes ammonium bifluoride.
[0263] In one or more third embodiments, the first fluorinated
support composition includes from about 1 wt. % to about 30 wt. %
fluorinating agent, or from about 2 wt. % to about 25 wt. % or from
about 5 wt. % to about 20 wt. %, for example.
[0264] In one or more third embodiments, the alumina-silica
includes from about 1 wt. % to about 30 wt. % alumina, or from
about 2 wt. % to about 25 wt. % or from about 5 wt. % to about 20
wt. %, for example.
[0265] In one or more third embodiments, the second fluorinated
support composition includes from about 0.1 wt. % to about 15 wt. %
fluorine or from about 1 wt. % to about 10 wt. %, for example.
[0266] In one or more third embodiments, the second fluorinated
support composition includes a molar ratio of aluminum to fluorine
of from about 0.1 to about 10, or from about 1 to about 8 or of
about 1 to 1, for example.
[0267] In one or more third embodiments, the first fluorinated
support composition is heated to a first temperature for a first
time of from about 1 hour to about 4 hours or from about 2 hours to
about 3 hours, for example, and then to a second temperature for a
time of from about 1 hour to about 10 hours or from about 2 hours
to about 6 hours, for example, wherein the second temperature is
greater than the first temperature. For example, the first
temperature may be from about 20.degree. C. to about 200.degree. C.
or from about 50.degree. C. to about 150.degree. C. and the second
temperature may be from about 200.degree. C. to about 450.degree.
C. or from about 300.degree. C. to about 400.degree. C.
[0268] One or more embodiments (e.g., fourth embodiments) of the
invention generally include contacting the fluorinated support with
a transition metal compound to form a supported catalyst
composition. The contact includes in situ
activation/heterogenization of the transition metal compound. The
term "in situ activation/heterogenization" refers to
activation/formation of the catalyst at the point of contact
between the support material and the transition metal compound.
Such contact may occur in a reaction zone, either prior to,
simultaneous with or after the introduction of one or more olefin
monomers thereto.
[0269] Alternatively, the transition metal compound and the
fluorinated support may be pre-contacted (contacted prior to
entrance to a reaction zone) at a reaction temperature of from
about -60.degree. C. to about 120.degree. C. or from about
-45.degree. C. to about 100.degree. C. or at a reaction temperature
below about 90.degree. C., e.g., from about 0.degree. C. to about
50.degree. C., or from about 20.degree. C. to about 30.degree. C.
or at room temperature, for example, for a time of from about 10
minutes to about 5 hours or from about 30 minutes to about 120
minutes, for example.
[0270] In addition, and depending on the desired degree of
substitution, the weight ratio of fluorine to transition metal
(F:M) is, in the fourth embodiments, from about 1 equivalent to
about 20 equivalents or from about 1 to about 5 equivalents, for
example. In one fourth embodiment, the supported catalyst
composition includes from about 0.1 wt. % to about 5 wt. % or from
about 0.5 wt. % to about 2.5 wt. % transition metal compound.
[0271] In one or more embodiments (e.g., fifth embodiments), the
molar ratio of fluorine to the first aluminum containing compound
(F:Al.sup.1) is generally from about 0.5:1 to 6:1, or from about
0.5:1 to about 4:1 or from about 2.5:1 to about 3.5:1, for
example.
[0272] The fluorinated support of the fifth embodiments may have a
pH that is lower than about 8.0, or less than about 7.8, or less
than about 7.6, or less than about 7.0, or less than about 6.5, or
less than about 6.0 or less than about 5.5, for example.
[0273] The fluorinated support of the fifth embodiments generally
has an acid strength (pKa) that is lower than about 4.8, or less
than about 4.6, or less than about 4.3 or less than about 4.0, for
example.
[0274] The fluorinated support of the fifth embodiments may have a
surface acidity (as defined in the examples) that is greater than
about 0.3 mmol/g, or greater than about 0.35 or greater than about
4.0, for example.
[0275] In one or more embodiments, the transition metal compound
includes a metallocene catalyst, a late transition metal catalyst,
a post metallocene catalyst or combinations thereof. Late
transition metal catalysts may be characterized generally as
transition metal catalysts including late transition metals, such
as nickel, iron or palladium, for example. Post metallocene
catalysts may be characterized generally as transition metal
catalysts including Group IV, V or VI metals, for example. A brief
discussion of such catalyst systems is included below, but is in no
way intended to limit the scope of the invention to such
catalysts.
[0276] Metallocene catalysts may be characterized generally as
coordination compounds incorporating one or more cyclopentadienyl
(Cp) groups (which may be substituted or unsubstituted, each
substitution being the same or different) coordinated with a
transition metal.
[0277] The substituent groups on Cp may be linear, branched or
cyclic hydrocarbyl radicals, for example. The inclusion of cyclic
hydrocarbyl radicals may transform the Cp into other contiguous
ring structures, such as indenyl, azulenyl and fluorenyl groups,
for example. These contiguous ring structures may also be
substituted or unsubstituted by hydrocarbyl radicals, such as
C.sub.1 to C.sub.20 hydrocarbyl radicals, for example.
[0278] A specific, non-limiting, example of a metallocene catalyst
is a bulky ligand metallocene compound generally represented by the
formula:
[L].sub.mM[A].sub.n;
wherein L is a bulky ligand, A is a leaving group, M is a
transition metal and m and n are such that the total ligand valency
corresponds to the transition metal valency. For example m may be
from 1 to 4 and n may be from 0 to 3.
[0279] The metal atom "M" of the metallocene catalyst compound, as
described throughout the specification and claims, may be selected
from Groups 3 through 12 atoms and lanthanide Group atoms, or from
Groups 3 through 10 atoms or from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn,
Re, Fe, Ru, Os, Co, Rh, Ir and Ni. The oxidation state of the metal
atom "M" may range from 0 to +7 or is +1, +2, +3, +4 or +5, for
example.
[0280] The bulky ligand generally includes a cyclopentadienyl group
(Cp) or a derivative thereof. The Cp ligand(s) form at least one
chemical bond with the metal atom M to form the "metallocene
catalyst". The Cp ligands are distinct from the leaving groups
bound to the catalyst compound in that they are not as highly
susceptible to substitution/abstraction reactions as the leaving
groups.
[0281] Cp ligands may include ring(s) or ring system(s) including
atoms selected from group 13 to 16 atoms, such as carbon, nitrogen,
oxygen, silicon, sulfur, phosphorous, germanium, boron, aluminum
and combinations thereof, wherein carbon makes up at least 50% of
the ring members. Non-limiting examples of the ring or ring systems
include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl,
benzindenyl, fluorenyl, tetrahydroindenyl, octahydrofluorenyl,
cyclooctatetraenyl, cyclopentacyclododecene, 3,4-benzofluorenyl,
9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl,
7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl,
thiophenofluorenyl, hydrogenated versions thereof (e.g.,
4,5,6,7-tetrahydroindenyl or "H.sub.4Ind"), substituted versions
thereof and heterocyclic versions thereof, for example.
[0282] Cp substituent groups may include hydrogen radicals, alkyls
(e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, fluoromethyl,
fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, benzyl, phenyl,
methylphenyl, tert-butylphenyl, chlorobenzyl, dimethylphosphine and
methylphenylphosphine), alkenyls (e.g., 3-butenyl, 2-propenyl and
5-hexenyl), alkynyls, cycloalkyls (e.g., cyclopentyl and
cyclohexyl), aryls (e.g., trimethylsilyl, trimethylgermyl,
methyldiethylsilyl, acyls, aroyls, tris(trifluoromethyl)silyl,
methylbis(difluoromethyl)silyl and bromomethyldimethylgermyl),
alkoxys (e.g., methoxy, ethoxy, propoxy and phenoxy), aryloxys,
alkylthiols, dialkylamines (e.g., dimethyl amine and diphenyl
amine), alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbamoyls,
alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos,
organometalloid radicals (e.g., dimethylboron), Group 15 and Group
16 radicals (e.g., methylsulfide and ethylsulfide) and combinations
thereof, for example. In one embodiment, at least two substituent
groups, two adjacent substituent groups in one embodiment, are
joined to form a ring structure.
[0283] Each leaving group "A" is independently selected and may
include any ionic leaving group, such as halogens (e.g., chloride
and fluoride), hydrides, C.sub.1 to C.sub.12 alkyls (e.g., methyl,
ethyl, propyl, phenyl, cyclobutyl, cyclohexyl, heptyl, tolyl,
trifluoromethyl, methylphenyl, dimethylphenyl and trimethylphenyl),
C.sub.2 to C.sub.12 alkenyls (e.g., C.sub.2 to C.sub.6
fluoroalkenyls), C.sub.6 to C.sub.12 aryls (e.g., C.sub.7 to
C.sub.20 alkylaryls), C.sub.1 to C.sub.12 alkoxys (e.g., phenoxy,
methyoxy, ethyoxy, propoxy and benzoxy), C.sub.6 to C.sub.16
aryloxys, C.sub.7 to C.sub.18 alkylaryloxys and C.sub.1 to C.sub.12
heteroatom-containing hydrocarbons and substituted derivatives
thereof, for example.
[0284] Other non-limiting examples of leaving groups include
amines, phosphines, ethers, carboxylates (e.g., C.sub.1 to C.sub.6
alkylcarboxylates, C.sub.6 to C.sub.12 arylcarboxylates and C.sub.7
to C.sub.18 alkylarylcarboxylates), dienes, alkenes (e.g.,
tetramethylene, pentamethylene, methylidene), hydrocarbon radicals
having from 1 to 20 carbon atoms (e.g., pentafluorophenyl) and
combinations thereof, for example. In one embodiment, two or more
leaving groups form a part of a fused ring or ring system.
[0285] In a specific embodiment, L and A may be bridged to one
another to form a bridged metallocene catalyst. A bridged
metallocene catalyst, for example, may be described by the general
formula:
XCp.sup.ACp.sup.BMA.sub.n;
wherein X is a structural bridge, Cp.sup.A and Cp.sup.B each denote
a cyclopentadienyl group or derivatives thereof, each being the
same or different and which may be either substituted or
unsubstituted, M is a transition metal and A is an alkyl,
hydrocarbyl or halogen group and n is an integer between 0 and 4,
and either 1 or 2 in a particular embodiment.
[0286] Non-limiting examples of bridging groups "X" include
divalent hydrocarbon groups containing at least one Group 13 to 16
atom, such as, but not limited to, at least one of a carbon,
oxygen, nitrogen, silicon, aluminum, boron, germanium, tin and
combinations thereof; wherein the heteroatom may also be a C.sub.1
to C.sub.12 alkyl or aryl group substituted to satisfy a neutral
valency. The bridging group may also contain substituent groups as
defined above including halogen radicals and iron. More particular
non-limiting examples of bridging group are represented by C.sub.1
to C.sub.6 alkylenes, substituted C.sub.1 to C.sub.6 alkylenes,
oxygen, sulfur, R.sub.2C.dbd., R.sub.2Si.dbd.,
--Si(R).sub.2Si(R.sub.2)--, R.sub.2Ge.dbd. or RP.dbd.(wherein
".dbd." represents two chemical bonds), where R is independently
selected from hydrides, hydrocarbyls, halocarbyls,
hydrocarbyl-substituted organometalloids, halocarbyl-substituted
organometalloids, disubstituted boron atoms, disubstituted Group 15
atoms, substituted Group 16 atoms and halogen radicals, for
example. In one embodiment, the bridged metallocene catalyst
component has two or more bridging groups.
[0287] Other non-limiting examples of bridging groups include
methylene, ethylene, ethylidene, propylidene, isopropylidene,
diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene,
1,1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl,
methyl-ethylsilyl, trifluoromethylbutylsilyl,
bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl,
di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl,
diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl,
di(t-butylphenyl)silyl, di(p-tolyl)silyl and the corresponding
moieties, wherein the Si atom is replaced by a Ge or a C atom;
dimethylsilyl, diethylsilyl, dimethylgermyl and/or
diethylgermyl.
[0288] In another embodiment, the bridging group may also be cyclic
and include 4 to 10 ring members or 5 to 7 ring members, for
example. The ring members may be selected from the elements
mentioned above and/or from one or more of boron, carbon, silicon,
germanium, nitrogen and oxygen, for example. Non-limiting examples
of ring structures which may be present as or part of the bridging
moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene,
cycloheptylidene, cyclooctylidene, for example. The cyclic bridging
groups may be saturated or unsaturated and/or carry one or more
substituents and/or be fused to one or more other ring structures.
The one or more Cp groups which the above cyclic bridging moieties
may optionally be fused to may be saturated or unsaturated.
Moreover, these ring structures may themselves be fused, such as,
for example, in the case of a naphthyl group.
[0289] In one embodiment, the metallocene catalyst includes CpFlu
Type catalysts (e.g., a metallocene catalyst wherein the ligand
includes a Cp fluorenyl ligand structure) represented by the
following formula:
X(CpR.sup.1.sub.nR.sup.2.sub.m)(FlR.sup.3.sub.p);
wherein Cp is a cyclopentadienyl group or derivatives thereof, Fl
is a fluorenyl group, X is a structural bridge between Cp and Fl,
R.sup.1 is an optional substituent on the Cp, n is 1 or 2, R.sup.2
is an optional substituent on the Cp bound to a carbon immediately
adjacent to the ipso carbon, m is 1 or 2 and each R.sup.3 is
optional, may be the same or different and may be selected from
C.sub.1 to C.sub.20 hydrocarbyls. In one embodiment, at least one
R.sup.3 is substituted in either the 2 or 7 position on the
fluorenyl group and at least one other R.sup.3 being substituted at
an opposed 2 or 7 position on the fluorenyl group and p is 2 or
4.
[0290] In yet another aspect, the metallocene catalyst includes
bridged mono-ligand metallocene compounds (e.g., mono
cyclopentadienyl catalyst components). In this embodiment, the
metallocene catalyst is a bridged "half-sandwich" metallocene
catalyst. In yet another aspect of the invention, the at least one
metallocene catalyst component is an unbridged "half sandwich"
metallocene. (See, U.S. Pat. No. 6,069,213, U.S. Pat. No.
5,026,798, U.S. Pat. No. 5,703,187, U.S. Pat. No. 5,747,406, U.S.
Pat. No. 5,026,798 and U.S. Pat. No. 6,069,213, which are
incorporated by reference herein.)
[0291] Non-limiting examples of metallocene catalyst components
consistent with the description herein include, for example
cyclopentadienylzirconiumA.sub.n; indenylzirconiumA.sub.n;
(1-methylindenyl)zirconiumA.sub.n;
(2-methylindenyl)zirconiumA.sub.n,
(1-propylindenyl)zirconiumA.sub.n;
(2-propylindenyl)zirconiumA.sub.n;
(1-butylindenyl)zirconiumA.sub.n; (2-butylindenyl)zirconiumA.sub.n;
methylcyclopentadienylzirconiumA.sub.n;
tetrahydroindenylzirconiumA.sub.n;
pentamethylcyclopentadienylzirconiumA.sub.n;
cyclopentadienylzirconiumA.sub.n;
pentamethylcyclopentadienyltitaniumA.sub.n;
tetramethylcyclopentyltitaniumA.sub.n;
(1,2,4-trimethylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(cyclopentadienyl)zirco-
niumA.sub.n;
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2,3-trimethylcyclope-
ntadienyl)zirconiumA.sub.n;
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2-dimethylcyclopenta-
dienyl)zirconiumA.sub.n;
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(2-methylcyclopentadien-
yl)zirconiumA.sub.n;
dimethylsilylcyclopentadienylindenylzirconiumA.sub.n;
dimethylsilyl(2-methylindenyl)(fluorenyl)zirconiumA.sub.n;
diphenylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-propylcyclopentadien-
yl)zirconiumA.sub.n; dimethylsilyl
(1,2,3,4-tetramethylcyclopentadienyl)
(3-t-butylcyclopentadienyl)zirconiumA.sub.n;
dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-isopropylcyclopentadienyl)-
zirconiumA.sub.n;
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-methylcyclopentadien-
yl)zirconiumA.sub.n;
diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconiumA.sub.n;
diphenylmethylidenecyclopentadienylindenylzirconiumA.sub.n;
isopropylidenebiscyclopentadienylzirconiumA.sub.n;
isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconiumA.sub.n;
isopropylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconiumA.sub.n;
ethylenebis(9-fluorenyl)zirconiumA.sub.n;
ethylenebis(1-indenyl)zirconiumA.sub.n;
ethylenebis(1-indenyl)zirconiumA.sub.n;
ethylenebis(2-methyl-1-indenyl)zirconiumA.sub.n;
ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconiumA.sub.n;
dimethylsilylbis(cyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(9-fluorenyl)zirconiumA.sub.n;
dimethylsilylbis(1-indenyl)zirconiumA.sub.n;
dimethylsilylbis(2-methylindenyl)zirconiumA.sub.n;
dimethylsilylbis(2-propylindenyl)zirconiumA.sub.n;
dimethylsilylbis(2-butylindenyl)zirconiumA.sub.n;
diphenylsilylbis(2-methylindenyl)zirconiumA.sub.n;
diphenylsilylbis(2-propylindenyl)zirconiumA.sub.n;
diphenylsilylbis(2-butylindenyl)zirconiumA.sub.n;
dimethylgermylbis(2-methylindenyl)zirconiumA.sub.n;
dimethylsilylbistetrahydroindenylzirconiumA.sub.n;
dimethylsilylbistetramethylcyclopentadienylzirconiumA.sub.n;
dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconiumA.sub.n;
diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconiumA.sub.n;
diphenylsilylbisindenylzirconiumA.sub.n;
cyclotrimethylenesilyltetramethylcyclopentadienylcyclopentadienylzirconiu-
mA.sub.n;
cyclotetramethylenesilyltetramethylcyclopentadienylcyclopentadie-
nylzirconiumA.sub.n;
cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2-methyl
indenyl)zirconiumA.sub.n;
cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(3-methylcyclopentadie-
nyl)zirconiumA.sub.n;
cyclotrimethylenesilylbis(2-methylindenyl)zirconiumA.sub.n;
cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2,3,5-trimethylclopen-
tadienyl)zirconiumA.sub.n;
cyclotrimethylenesilylbis(tetramethylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilyktetramethylcyclopentadieneyl)(N-tertbutylamido)titaniumA.sub-
.n; biscyclopentadienylchromiumA.sub.n;
biscyclopentadienylzirconiumA.sub.n;
bis(n-butylcyclopentadienyl)zirconiumA.sub.n;
bis(n-dodecyclcyclopentadienyl)zirconiumA.sub.n;
bisethylcyclopentadienylzirconiumA.sub.n;
bisisobutylcyclopentadienylzirconiumA.sub.n;
bisisopropylcyclopentadienylzirconiumA.sub.n;
bismethylcyclopentadienylzirconiumA.sub.n;
bisoctylcyclopentadienylzirconiumA.sub.n;
bis(n-pentylcyclopentadienyl)zirconiumA.sub.n;
bis(n-propylcyclopentadienyl)zirconiumA.sub.n;
bistrimethylsilylcyclopentadienylzirconiumA.sub.n;
bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirconiumA.sub.n;
bis(1-ethyl-2-methylcyclopentadienyl)zirconiumA.sub.n;
bis(1-ethyl-3-methylcyclopentadienyl)zirconiumA.sub.n;
bispentamethylcyclopentadienylzirconiumA.sub.n;
bispentamethylcyclopentadienylzirconiumA.sub.n;
bis(1-propyl-3-methylcyclopentadienyl)zirconiumA.sub.n;
bis(1-n-butyl-3-methylcyclopentadienyl)zirconiumA.sub.n;
bis(1-isobutyl-3-methylcyclopentadienyl)zirconiumA.sub.n;
bis(1-propyl-3-butylcyclopentadienyl)zirconiumA.sub.n;
bis(1,3-n-butylcyclopentadienyl)zirconiumA.sub.n;
bis(4,7-dimethylindenyl)zirconiumA.sub.n;
bisindenylzirconiumA.sub.n; bis(2-methylindenyl)zirconiumA.sub.n;
cyclopentadienylindenylzirconiumA.sub.n;
bis(n-propylcyclopentadienyl)hafniumA.sub.n;
bis(n-butylcyclopentadienyl)hafniumA.sub.n;
bis(n-pentylcyclopentadienyl)hafniumA.sub.n;
(n-propylcyclopentadienyl)(n-butylcyclopentadienyl)hafniumA.sub.n;
bis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumA.sub.n;
bis(trimethylsilylcyclopentadienyl)hafniumA.sub.n;
bis(2-n-propylindenyl)hafniumA.sub.n;
bis(2-n-butylindenyl)hafniumA.sub.n;
dimethylsilylbis(n-propylcyclopentadienyl)hafniumA.sub.n;
dimethylsilylbis(n-butylcyclopentadienyl)hafniumA.sub.n;
bis(9-n-propylfluorenyl)hafniumA.sub.n;
bis(9-n-butylfluorenyl)hafniumA.sub.n;
(9-n-propylfluorenyl)(2-n-propylindenyl)hafniumA.sub.n;
bis(1-n-propyl-2-methylcyclopentadienyl)hafniumA.sub.n;
(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafniumA.-
sub.n;
dimethylsilyltetramethylcyclopentadienylcyclopropylamidotitaniumA.s-
ub.n;
dimethylsilyltetramethyleyclopentadienylcyclobutylamidotitaniumA.sub-
.n;
dimethylsilyltetramethyleyclopentadienylcyclopentylamidotitaniumA.sub.-
n;
dimethylsilyltetramethylcyclopentadienylcyclohexylamidotitaniumA.sub.n;
dimethylsilyltetramethylcyclopentadienylcycloheptylamidotitaniumA.sub.n;
dimethylsilyltetramethylcyclopentadienylcyclooctylamidotitaniumA.sub.n;
dimethylsilyltetramethylcyclopentadienylcyclononylamidotitaniumA.sub.n;
dimethylsilyltetramethylcyclopentadienylcyclodecylamidotitaniumA.sub.n;
dimethylsilyltetramethylcyclopentadienylcycloundecylamidotitaniumA.sub.n;
dimethylsilyltetramethylcyclopentadienylcyclododecylamidotitaniumA.sub.n;
dimethylsilyltetramethylcyclopentadienyl(sec-butylamido)titaniumA.sub.n;
dimethylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titaniumA.sub.n;
dimethylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titaniumA.sub.n;
dimethylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titaniumA.sub-
.n; dimethylsilylbis(cyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(tetramethylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(methylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(dimethylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilyl(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadieny-
l)zirconiumA.sub.n;
dimethylsilyl(2,3,5-trimethylcyclopentadienyl)(2',4',5'-dimethylcyclopent-
adienyl)zirconiumA.sub.n;
dimethylsilylbis(t-butylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(trimethylsilylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(2-trimethylsilyl-4-t-butylcyclopentadienyl)zirconiumA.su-
b.n; dimethylsilylbis(4,5,6,7-tetrahydro-indenyl)zirconiumA.sub.n;
dimethylsilylbis(indenyl)zirconiumA.sub.n;
dimethylsilylbis(2-methylindenyl)zirconiumA.sub.n;
dimethylsilylbis(2,4-dimethylindenyl)zirconiumA.sub.n;
dimethylsilylbis(2,4,7-trimethylindenyl)zirconiumA.sub.n;
dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumA.sub.n;
dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconiumA.sub.n;
dimethylsilylbis(benz[e]indenyl)zirconiumA.sub.n;
dimethylsilylbis(2-methylbenz[e]indenyl)zirconiumA.sub.n;
dimethylsilylbis(benz[f]indenyl)zirconiumA.sub.n;
dimethylsilylbis(2-methylbenzindenyl)zirconiumA.sub.n;
dimethylsilylbis(3-methylbenz[f]indenyl)zirconiumA.sub.n;
dimethylsilylbis(cyclopenta[cd]indenyl)zirconiumA.sub.n;
dimethylsilylbis(cyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(tetramethylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(methylcyclopentadienyl)zirconiumA.sub.n;
dimethylsilylbis(dimethylcyclopentadienyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-fluorenyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-indenyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-3-methylfluorenyl)zirconiumA.sub.n;
isoropylidene(cyclopentadienyl-4-methylfluorenyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-octahydrofluorenyl)zirconiumA.sub.n;
isopropylidene(methylcyclopentadienyl-fluorenyl)zirconiumA.sub.n;
isopropylidene(dimethylcyclopentadienylfluorenyl)zirconiumA.sub.n;
isopropylidene(tetramethylcyclopentadienyl-fluorenyl)zirconiumA.sub.n;
diphenylmethylene(cyclopentadienyl-fluorenyl)zirconiumA.sub.n;
diphenylmethylene(cyclopentadienyl-indenyl)zirconiumA.sub.n;
diphenylmethylene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconiumA.sub-
.n;
diphenylmethylene(cyclopentadienyl-3-methylfluorenyl)zirconiumA.sub.n;
diphenylmethylene(cyclopentadienyl-4-methylfluorenyl)zirconiumA.sub.n;
diphenylmethylene(cyclopentadienyloctahydrofluorenyl)zirconiumA.sub.n;
diphenylmethylene(methylcyclopentadienyl-fluorenyl)zirconiumA.sub.n;
diphenylmethylene(dimethylcyclopentadienyl-fluorenyl)zirconiumA.sub.n;
diphenylmethylene(tetramethylcyclopentadienyl-fluorenyl)zirconiumA.sub.n;
cyclohexylidene(cyclopentadienyl-fluorenyl)zirconiumA.sub.n;
cyclohexylidene(cyclopentadienylindenyl)zirconiumA.sub.n;
cyclohexylidene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconiumA.sub.n-
;
cyclohexylidene(cyclopentadienyl-3-methylfluorenyl)zirconiumA.sub.n;
cyclohexylidene(cyclopentadienyl-4-methylfluorenyl)zirconiumA.sub.n;
cyclohexylidene(cyclopentadienyloctahydrofluorenyl)zirconiumA.sub.n;
cyclohexylidene(methylcyclopentadienylfluorenyl)zirconiumA.sub.n;
cyclohexylidene(dimethylcyclopentadienyl-fluorenyl)zirconiumA.sub.n;
cyclohexylidene(tetramethylcyclopentadienylfluorenyl)zirconiumA.sub.n;
dimethylsilyl(cyclopentadienyl-fluorenyl)zirconiumA.sub.n;
dimethylsilyl(cyclopentadienyl-indenyl)zirconiumA.sub.n;
dimethylsilyl(cyclopentdienyl-2,7-di-t-butylfluorenyl)zirconiumA.sub.n;
dimethylsilyl(cyclopentadienyl-3-methylfluorenyl)zirconiumA.sub.n;
dimethylsilyl(cyclopentadienyl-4-methylfluorenyl)zirconiumA.sub.n;
dimethylsilyl(cyclopentadienyl-octahydrofluorenyl)zirconiumA.sub.n;
dimethylsilyl(methylcyclopentanedienyl-fluorenyl)zirconiumA.sub.n;
dimethylsilyl(dimethylcyclopentadienylfluorenyl)zirconiumA.sub.n;
dimethylsilyl(tetramethylcyclopentadienylfluorenyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-fluorenyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-indenyl)zirconiumA.sub.n;
isopropylidene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconiumA.sub.n;
cyclohexylidene(cyclopentadienylfluorenyl)zirconiumA.sub.n;
cyclohexylidene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconiumA.sub.n-
; dimethylsilyl(cyclopentadienylfluorenyl)zirconiumA.sub.n;
methylphenylsilyltetramethylcyclopentadienylcyclopropylamidotitaniumA.sub-
.n;
methylphenylsilyltetramethylcyclopentadienylcyclobutylamidotitaniumA.s-
ub.n;
methylphenylsilyltetramethylcyclopentadienylcyclopentylamidotitanium-
A.sub.n;
methylphenylsilyltetramethylcyclopentadienylcyclohexylamidotitani-
umA.sub.n;
methylphenylsilyltetramethylcyclopentadienylcycloheptylamidotit-
aniumA.sub.n;
methylphenylsilyltetramethylcyclopentadienylcyclooctylamidotitaniumA.sub.-
n;
methylphenylsilyltetramethylcyclopentadienylcyclononylamidotitaniumA.su-
b.n;
methylphenylsilyltetramethylcyclopentadienylcyclodecylamidotitaniumA.-
sub.n;
methylphenylsilyltetramethylcyclopentadienylcycloundecylamidotitani-
umA.sub.n;
methylphenylsilyltetramethylcyclopentadienylcyclododecylamidoti-
taniumA.sub.n;
methylphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titaniumA.s-
ub.n;
methylphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium-
A.sub.n;
methylphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titan-
iumA.sub.n;
methylphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titaniumA-
.sub.n;
diphenylsilyltetramethylcyclopentadienylcyclopropylamidotitaniumA.-
sub.n;
diphenylsilyltetramethylcyclopentadienylcyclobutylamidotitaniumA.su-
b.n;
diphenylsilyltetramethylcyclopentadienylcyclopentylamidotitaniumA.sub-
.n;
diphenylsilyltetramethylcyclopentadienylcyclohexylamidotitaniumA.sub.n-
;
diphenylsilyltetramethylcyclopentadienylcycloheptylamidotitaniumA.sub.n;
diphenylsilyltetramethylcyclopentadienylcyclooctylamidotitaniumA.sub.n;
diphenylsilyltetramethylcyclopentadienylcyclononylamidotitaniumA.sub.n;
diphenylsilyltetramethylcyclopentadienylcyclodecylamidotitaniumA.sub.n;
diphenylsilyltetramethylcyclopentadienylcycloundecylamidotitaniumA.sub.n;
diphenylsilyltetramethylcyclopentadienylcyclododecylamidotitaniumA.sub.n;
diphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titaniumA.sub.n-
;
diphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titaniumA.sub.n;
diphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titaniumA.sub.n;
and
diphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titaniumA-
.sub.n.
[0292] In one or more embodiments, the transition metal compound
includes cyclopentadienyl ligands, indenyl ligands, fluorenyl
ligands, tetrahydroindenyl ligands, CpFlu type catalysts, alkyls,
aryls, amides or combinations thereof. In one or more embodiments,
the transition metal compound includes a transition metal
dichloride, dimethyl or hydride. In one specific embodiment, the
transition metal compound includes
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride.
[0293] In one or more embodiments, L is selected from C.sub.4 to
C.sub.30 hydrocarbons, oxygen, nitrogen, phosphorous and
combinations thereof. In one or more embodiments, M is selected
from Group 3 to Group 14 metals, lanthanides, actinides and
combinations thereof. In one or more embodiments, A is selected
from halogens, C.sub.4 to C.sub.30 hydrocarbons and combinations
thereof. In one specific embodiment, the transition metal compound
includes
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride.
[0294] One or more embodiments may further include contacting the
aluminum fluoride impregnated support with a plurality of catalyst
compounds (e.g., a bimetallic catalyst). As used herein, the term
"bimetallic catalyst" means any composition, mixture or system that
includes at least two different catalyst compounds. Each catalyst
compound may reside on a single support particle so that the
bimetallic catalyst is a supported bimetallic catalyst. However,
the term bimetallic catalyst also broadly includes a system or
mixture in which one of the catalysts resides on one collection of
support particles and another catalyst resides on another
collection of support particles. The plurality of catalyst
components may include any catalyst component known to one skilled
in the art, so long as at least one of those catalyst components
includes a transition metal compound as described herein.
[0295] Optionally, the aluminum fluoride impregnated support, the
transition metal compound, the catalyst system or combinations
thereof, may be contacted with one or more scavenging compounds
prior to or during polymerization. The term "scavenging compounds"
is meant to include those compounds effective for removing
impurities (e.g., polar impurities) from the subsequent
polymerization reaction environment. Impurities may be
inadvertently introduced with any of the polymerization reaction
components, particularly with solvent, monomer and catalyst feed,
and adversely affect catalyst activity and stability. Such
impurities may result in decreasing, or even elimination, of
catalytic activity, for example. The polar impurities or catalyst
poisons may include water, oxygen and metal impurities, for
example.
[0296] The scavenging compound may include an excess of the
aluminum containing compounds described above, or may be additional
known organometallic compounds, such as Group 13 organometallic
compounds. For example, the scavenging compounds may include
triethyl aluminum (TMA), triisobutyl aluminum (TIBAl),
methylalumoxane (MAO), isobutyl aluminoxane and tri-n-octyl
aluminum. In one specific embodiment, the scavenging compound is
TIBAl.
[0297] In one embodiment, the amount of scavenging compound is
minimized during polymerization to that amount effective to enhance
activity and avoided altogether if the feeds and polymerization
medium may be sufficiently free of impurities.
[0298] In one or more embodiments, the fluorinated support and/or
the transition metal compound may be contacted with at least one
compound prior to or after contact with one another. The at least
one compound is generally represented by the formula XR.sub.n,
wherein X is selected from Group 12 to 13 metals, lanthanide series
metals or combinations thereof and each R is independently selected
from alkyls, alkoxys, aryls, aryloxys, halogens, hydrides, Group 1
or 2 metals, organic nitrogen compounds, organic phosphorous
compounds and combinations thereof and n is from 2 to 5.
[0299] In one embodiment, X includes aluminum. For example, the
compound may include an organic aluminum compound. The organic
aluminum compound may include triethyl aluminum (TEAl), triisobutyl
aluminum (TIBAl), tri-n-hexyl aluminum (TNHAl), tri-n-octyl
aluminum (TNOAl) or tri-isoprenyl aluminum (TISPAl), for example.
However, in one specific embodiment, the supported catalyst system
is formed in the absence of TIBAl.
[0300] In one embodiment, X includes boron. For example, the
compound may include an organic boron compound, such as a C.sub.2
to C.sub.30 trialkyl boron. In one specific embodiment, the
compound includes a borate. For example, the borate may include a
borate salt, such as a lithium borate, triethyl borate or trimethyl
borate.
[0301] In one embodiment, the weight ratio of the silica to the
compound (Si:X.sup.2) may be from about 0.01:1 to about 10:1 or
from about 0.1:1 to about 7:1, for example. The compound generally
contacts the fluorinated support (or components thereof) in an
amount that is insufficient to alkylate the fluorinated
support.
[0302] In one or more embodiments, the compound includes a
plurality of compounds. For example, the plurality of compounds may
include a first compound including aluminum and a second compound
including borane. For example, the plurality of compounds may
include a trialkyl aluminum and a trialkyl borane.
[0303] In one specific embodiment, the compound includes more
aluminum than boron. For example, the compound may include only a
minor amount of boron (e.g., less than about 10 wt. %, or less than
about 5 wt. %, or less than about 2.5 wt. % or less than about 1.0
wt. %).
[0304] It is contemplated that the first and second compound may
contact one another prior to, during or after contact with any
portion of the fluorinated support.
[0305] While it has been observed that contacting the fluorinated
support with the compound results in a catalyst having increased
activity, it is contemplated that the compound may contact the
transition metal compound. When the compound contacts the
transition metal compound, the weight ratio of the compound to
transition metal (X.sup.2:M) may be from about 0.1: to about
5000:1, for example.
[0306] Optionally, the aluminum containing support material and/or
the transition metal compound may be contacted with a second
aluminum containing compound prior to contact with one another. In
one embodiment, the aluminum containing support material is
contacted with the second aluminum containing compound prior to
contact with the transition metal compound. Alternatively, the
aluminum containing support material may be contacted with the
transition metal compound in the presence of the second aluminum
containing compound.
[0307] For example, the contact may occur by contacting the
aluminum containing support material with the second aluminum
containing compound at a reaction temperature of from about
0.degree. C. to about 150.degree. C. or from about 20.degree. C. to
about 100.degree. C. for a time of from about 10 minutes hour to
about 5 hours or from about 30 minutes to about 120 minutes, for
example.
[0308] The second aluminum containing compound may include an
organic aluminum compound. The organic aluminum compound may
include TEAl, TIBAl, TNOAl, MAO or MMAO, for example. In one
embodiment, the organic aluminum compound may be represented by the
formula AlR.sub.3, wherein each R is independently selected from
alkyls, aryls or combinations thereof.
[0309] In one embodiment, the weight ratio of the silica of the
aluminum containing support material to the second aluminum
containing compound (Si:Al.sup.2) is generally from about 0.01:1 to
about 10:1, for example
[0310] While it has been observed that contacting the aluminum
containing support material with the second aluminum containing
compound results in a catalyst having increased activity, it is
contemplated that the second aluminum containing compound may
contact the transition metal compound. When the second aluminum
containing compound contacts the transition metal compound, the
weight ratio of the second aluminum containing compound to
transition metal (Al.sup.2:M) may be from about 0.1: to about
5000:1, for example.
[0311] As demonstrated in the examples that follow, contacting the
aluminum containing support materials with the transition metal
compound via the methods described herein unexpectedly results in a
supported catalyst composition that is active without alkylation
processes (e.g., contact of the catalyst component with an
organometallic compound, such as MAO.)
[0312] The absence of substances, such as MAO, generally results in
lower polymer production costs as alumoxanes are expensive
compounds. Further, alumoxanes are generally unstable compounds
that are generally stored in cold storage. However, embodiments of
the present invention unexpectedly result in a catalyst composition
that may be stored at room temperature for periods of time (e.g.,
up to 2 months) and then used directly in polymerization reactions.
Such storage ability further results in improved catalyst
variability as a large batch of support material may be prepared
and contacted with a variety of transition metal compounds (which
may be formed in small amounts optimized based on the polymer to be
formed.)
[0313] In addition, it is contemplated that polymerizations absent
alumoxane activators result in minimal leaching/fouling in
comparison with alumoxane based systems. However, embodiments of
the invention generally provide processes wherein alumoxanes may be
included without detriment.
[0314] Such processes, as described by the first embodiments, are
further expected to reduce the amount of byproducts released into
the environment as a result of the fluorination process as compared
with other fluorination methods.
Polymerization Processes
[0315] As indicated elsewhere herein, catalyst systems are used to
form polyolefin compositions. Once the catalyst system is prepared,
as described above and/or as known to one skilled in the art, a
variety of processes may be carried out using that composition. The
equipment, process conditions, reactants, additives and other
materials used in polymerization processes will vary in a given
process, depending on the desired composition and properties of the
polymer being formed. Such processes may include solution phase,
gas phase, slurry phase, bulk phase, high pressure processes or
combinations thereof, for example. (See, U.S. Pat. No. 5,525,678;
U.S. Pat. No. 6,420,580; U.S. Pat. No. 6,380,328; U.S. Pat. No.
6,359,072; U.S. Pat. No. 6,346,586; U.S. Pat. No. 6,340,730; U.S.
Pat. No. 6,339,134; U.S. Pat. No. 6,300,436; U.S. Pat. No.
6,274,684; U.S. Pat. No. 6,271,323; U.S. Pat. No. 6,248,845; U.S.
Pat. No. 6,245,868; U.S. Pat. No. 6,245,705; U.S. Pat. No.
6,242,545; U.S. Pat. No. 6,211,105; U.S. Pat. No. 6,207,606; U.S.
Pat. No. 6,180,735 and U.S. Pat. No. 6,147,173, which are
incorporated by reference herein.)
[0316] In certain embodiments, the processes described above
generally include polymerizing one or more olefin monomers to form
polymers. The olefin monomers may include C.sub.2 to C.sub.30
olefin monomers, or C.sub.2 to C.sub.12 olefin monomers (e.g.,
ethylene, propylene, butene, pentene, methylpentene, hexene, octene
and decene), for example. The monomers may include ethylenically
unsaturated monomers, C.sub.4 to C.sub.18 diolefins, conjugated or
nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins,
for example. Non-limiting examples of other monomers may include
norbornene, nobornadiene, isobutylene, isoprene,
vinylbenzocyclobutane, sytrene, alkyl substituted styrene,
ethylidene norbornene, dicyclopentadiene and cyclopentene, for
example. The formed polymer may include homopolymers, copolymers or
terpolymers, for example.
[0317] Examples of solution processes are described in U.S. Pat.
No. 4,271,060, U.S. Pat. No. 5,001,205, U.S. Pat. No. 5,236,998 and
U.S. Pat. No. 5,589,555, which are incorporated by reference
herein.
[0318] One example of a gas phase polymerization process includes a
continuous cycle system, wherein a cycling gas stream (otherwise
known as a recycle stream or fluidizing medium) is heated in a
reactor by heat of polymerization. The heat is removed from the
cycling gas stream in another part of the cycle by a cooling system
external to the reactor. The cycling gas stream containing one or
more monomers may be continuously cycled through a fluidized bed in
the presence of a catalyst under reactive conditions. The cycling
gas stream is generally withdrawn from the fluidized bed and
recycled back into the reactor. Simultaneously, polymer product may
be withdrawn from the reactor and fresh monomer may be added to
replace the polymerized monomer. The reactor pressure in a gas
phase process may vary from about 100 psig to about 500 psig, or
from about 200 psig to about 400 psig or from about 250 psig to
about 350 psig, for example. The reactor temperature in a gas phase
process may vary from about 30.degree. C. to about 120.degree. C.,
or from about 60.degree. C. to about 115.degree. C., or from about
70.degree. C. to about 110.degree. C. or from about 70.degree. C.
to about 95.degree. C., for example. (See, for example, U.S. Pat.
No. 4,543,399; U.S. Pat. No. 4,588,790; U.S. Pat. No. 5,028,670;
U.S. Pat. No. 5,317,036; U.S. Pat. No. 5,352,749; U.S. Pat. No.
5,405,922; U.S. Pat. No. 5,436,304; U.S. Pat. No. 5,456,471; U.S.
Pat. No. 5,462,999; U.S. Pat. No. 5,616,661; U.S. Pat. No.
5,627,242; U.S. Pat. No. 5,665,818; U.S. Pat. No. 5,677,375 and
U.S. Pat. No. 5,668,228, which are incorporated by reference
herein.)
[0319] Slurry phase processes generally include forming a
suspension of solid, particulate polymer in a liquid polymerization
medium, to which monomers and optionally hydrogen, along with
catalyst, are added. The suspension (which may include diluents)
may be intermittently or continuously removed from the reactor
where the volatile components can be separated from the polymer and
recycled, optionally after a distillation, to the reactor. The
liquefied diluent employed in the polymerization medium may include
a C.sub.3 to C.sub.7 alkane (e.g., hexane or isobutane), for
example. The medium employed is generally liquid under the
conditions of polymerization and relatively inert. A bulk phase
process is similar to that of a slurry process with the exception
that the liquid medium is also the reactant (e.g., monomer) in a
bulk phase process. However, a process may be a bulk process, a
slurry process or a bulk slurry process, for example.
[0320] In a specific embodiment, a slurry process or a bulk process
may be carried out continuously in one or more loop reactors. The
catalyst, as slurry or as a dry free flowing powder, may be
injected regularly to the reactor loop, which can itself be filled
with circulating slurry of growing polymer particles in a diluent,
for example. Optionally, hydrogen may be added to the process, such
as for molecular weight control of the resultant polymer. The loop
reactor may be maintained at a pressure of from about 27 bar to
about 50 bar or from about 35 bar to about 45 bar and a temperature
of from about 38.degree. C. to about 121.degree. C., for example.
Reaction heat may be removed through the loop wall via any method
known to one skilled in the art, such as via a double jacketed pipe
or heat exchanger, for example.
[0321] Alternatively, other types of polymerization processes may
be used, such as stirred reactors in series, parallel or
combinations thereof, for example. Upon removal from the reactor,
the polymer may be passed to a polymer recovery system for further
processing, such as addition of additives and/or extrusion, for
example.
[0322] In one embodiment, the polymerization process includes
contacting the supported catalyst composition with a bulk olefin
monomer prior to contact with the olefin monomer in the gas
phase.
[0323] In one embodiment, the catalyst preparation is an in-situ
process. Such process may occur with our without isolation of the
fluorinated catalyst. While an increase in catalytic activity has
been observed as a result of contacting the supported catalyst
system (or components thereof) with the compound represented by the
formula XR.sub.3 regardless of isolation, processes utilizing
non-isolated catalysts resulted in catalyst activities different
than that obtained with isolated catalysts.
Polymer Product
[0324] The polymers (and blends thereof) formed via the processes
described herein may include, but are not limited to, linear low
density polyethylene, elastomers, plastomers, high density
polyethylenes, low density polyethylenes, medium density
polyethylenes, polypropylene, polypropylene copolymers, random
ethylene-propylene copolymers and impact copolymers, for
example.
[0325] Unless otherwise designated herein, all testing methods are
the current methods at the time of filing.
[0326] In one embodiment, the polymer includes syndiotactic
polypropylene. The syndiotactic polypropylene may be formed by a
supported catalyst composition including a CpFlu type catalyst.
[0327] In one embodiment, the polymer includes isotactic
polypropylene. The isotactic polypropylene may be formed by a
supported catalyst composition including
dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride as
the transition metal compound.
[0328] In one embodiment, the polymer includes a bimodal molecular
weight distribution. The bimodal molecular weight distribution
polymer may be formed by a supported catalyst composition including
a plurality of transition metal compounds.
[0329] In one embodiment, the polymer includes a unimodal molecular
weight distribution. The unimodal molecular weight distribution
polymer may be formed by contacting the transition metal compound
with the support material in the presence of TIBAl, for
example.
[0330] In one or more embodiments, the polymer has a low molecular
weight (e.g., a molecular weight of less than about 100,000). The
low molecular weight polymer may be formed by a support material
having a weight ratio of fluorine to aluminum of from about 1.8:1
to about 7:1 or from about 2:1 to about 5:1, for example.
[0331] In one or more embodiments, the polymer has a middle
molecular weight (e.g., a molecular weight of from about 100,000 to
about 150,000.) The middle molecular weight polymer may be formed
by a support material having a weight ratio of fluorine to aluminum
of from about 0.9:1 to about 1.8:1 or from about 1:1 to about
1.5:1, for example. Alternatively, the middle molecular weight
polymer may be formed by contacting the active supported catalyst
system with an olefin monomer in the presence of triethyl aluminum
(TEAl) or isoprenyl aluminum (IPA), for example.
[0332] In one or more embodiments, the polymer has a high molecular
weight (e.g., a molecular weight of at least about 150,000). The
high molecular weight polymer may be formed by contacting the
active supported catalyst system with an olefin monomer in the
presence of TIBAl, for example.
[0333] In one or more embodiments, the polymer has a narrow
molecular weight distribution (e.g., a molecular weight
distribution of from about 2 to about 4). In another embodiment,
the polymer has a broad molecular weight distribution (e.g., a
molecular weight distribution of from about 4 to about 25). The
broad molecular weight distribution polymer may be formed by
contacting the transition metal compound with the support material
in the presence of MAO, for example.
[0334] In one embodiment, the polymer includes copolymers. The
copolymers generally include a first polymer and a second polymer.
In one or more embodiments, the copolymers include a third
polymer.
[0335] For example, the first polymer may include polypropylene,
while the second polymer may be represented by the formula
CH.sub.2.dbd.CHR, wherein R is selected from hydrogen, C.sub.2 to
C2.sub.0 alkyls, C.sub.6 to C.sub.30 aryls and combinations
thereof. In one specific embodiment, the second polymer is
polyethylene. The third polymer may include C.sub.2 to C.sub.30
alkyls, such as C.sub.6 to C.sub.30 styrenic olefins, for
example.
[0336] In one embodiment, the copolymer includes from about 0.5 wt.
% to about 70 wt. %, or from about 0.5 wt. % to about 50 wt. %, or
from about 0.5 wt. % to about 10 wt. % or from about 2 wt. % to
about 7 wt. % polyethylene, for example.
[0337] In one or more embodiments, the copolymer has a melt flow
index (MFI) of from about 1 g/10 min to about 1000 g/10 min, or
from about 5 g/10 min. to about 500 g.10 min., or from about 10
g/10 min. to about 250 g/10 min. or from about to about 4 g/10 min.
to about 150 g/10 min., for example. In particular, the copolymers
have an MFI that increases with an increase in the polyethylene
content of the copolymer.
[0338] In one or more embodiments, the copolymer has a melting
point of from about 90.degree. C. to about 160.degree. C., or from
about 110.degree. C. to about 155.degree. C. or from about
130.degree. C. to about 150.degree. C., for example. Further, it
has been observed that in one or more embodiments, the copolymers
described herein do not exhibit a melt temperature peak.
Product Application
[0339] The polymers and blends thereof are useful in applications
known to one skilled in the art, such as forming operations (e.g.,
film, sheet, pipe and fiber extrusion and co-extrusion as well as
blow molding, injection molding and rotary molding). Films include
blown, oriented or cast films formed by extrusion or co-extrusion
or by lamination useful as shrink film, cling film, stretch film,
sealing films, oriented films, snack packaging, heavy duty bags,
grocery sacks, baked and frozen food packaging, medical packaging,
industrial liners, and membranes, for example, in food-contact and
non-food contact application. Fibers include slit-films,
monofilaments, melt spinning, solution spinning and melt blown
fiber operations for use in woven or non-woven form to make sacks,
bags, rope, twine, carpet backing, carpet yarns, filters, diaper
fabrics, medical garments and geotextiles, for example. Extruded
articles include medical tubing, wire and cable coatings, sheet,
thermoformed sheet, geomembranes and pond liners, for example.
Molded articles include single and multi-layered constructions in
the form of bottles, tanks, large hollow articles, rigid food
containers and toys, for example.
EXAMPLES
Example-I
[0340] In the following examples, samples of fluorinated
metallocene catalyst compounds were prepared according to the first
embodiments described herein. Examples 1 and 2 illustrate the
impregnation of AlF.sub.3 into silica in a water medium. Examples
3-9 illustrate the preparation of supported AlF.sub.3 on the
alumina-silica in a water medium. Example 10 illustrates the
preparation of supported AlF.sub.3 on the alumina-silica in a
tetrahydrofuran (THF) medium. Example 13 illustrates the
preparation of supported AlF.sub.3 on the alumina-silica by using
the solid phase reaction of AlF.sub.3 with alumina-silica in a
fluidizing bed at 450.degree. C.
[0341] As used herein, "room temperature" means that a temperature
difference of a few degrees does not matter to the phenomenon under
investigation, such as a preparation method. In some environments,
room temperature may include a temperature of from about 20.degree.
C. to about 28.degree. C. (68.degree. F. to 82.degree. F.), while
in other environments, room temperature may include a temperature
of from about 50.degree. F. to about 90.degree. F., for example.
However, room temperature measurements generally do not include
close monitoring of the temperature of the process and therefore
such a recitation does not intend to bind the embodiments described
herein to any predetermined temperature range.
Example 1
[0342] 10 g of silica from Grace (20 .mu.km) was mixed with 2 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solids were then heated in a muffle
furnace at 200.degree. C. for 1 h and 450.degree. C. for 3 h.
Example 2
[0343] 9.3 g of silica from Fuji Sylisia (40 .mu.km) was mixed with
3.9 g of AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was
stirred at 70.degree. C. for 1 h. The water was removed under
vacuum at 90.degree. C. and the resulting solids were then heated
in a muffle furnace at 200.degree. C. for 1 h and 450.degree. C.
for 3 h.
Example 3
[0344] 10 g of alumina-silica from Fuji Sylisia (5%
Al.sub.2O.sub.3, 20 .mu.km) was mixed with 1 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 1 h and 450.degree. C. for 3 h.
Example 4
[0345] 10.3 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 0.37 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 1 h and 450.degree. C. for 3 h.
Example 5
[0346] 10.1 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 0.54 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed, under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 1 h and 450.degree. C. for 3 h.
Example 6
[0347] 10.1 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 1.1 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 1 h and 450.degree. C. for 3 h.
Example 7
[0348] 20.2 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 2.1 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 5 h and 450.degree. C. for 4 h.
Example 8
[0349] 10.0 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 2.0 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 1 h and 450.degree. C. for 3 h.
Example 9
[0350] 10.0 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 3.0 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 1 h and 450.degree. C. for 3 h.
Example 10
[0351] 5.0 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 0.61 g of AlF.sub.3 and
50 ml of THF. The mixture was stirred at 70.degree. C. for 1 h. The
solvent was removed under vacuum and the resulting solid was then
heated in a muffle furnace at 200.degree. C. for 15 min. and
450.degree. C. for 3 h.
Example 11
[0352] 10.1 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 0.54 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 1 h.
Example 12
[0353] 20.2 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km) was mixed with 2.1 g of
AlF.sub.3.3H.sub.2O and 100 ml of water. The mixture was stirred at
70.degree. C. for 1 h. The water was removed under vacuum at
90.degree. C. and the resulting solid was then heated in a muffle
furnace at 200.degree. C. for 5 h.
Example 13
[0354] 25.1 g of alumina-silica from Grace (MS13/110, 13%
Al.sub.2O.sub.3, 60 .mu.km, heated at 200.degree. C. for 12 h in
tube furnace with 0.4 slpm of N.sub.2) was mixed with 3.8 g of
AlF.sub.3 (heated at 200.degree. C. for 3 h). The mixture was
heated in tube furnace under N.sub.2 flow (0.6 slpm) at room
temperature for 1 h, then at 500.degree. C. at 3 h and room
temperature for another 4 h.
Example 14
[0355] 19.5 g of fluorided alumina-silica from Grace (MS 13/110,
13% Al.sub.2O.sub.3, treated with NH.sub.4FFH at 400.degree. C.)
was mixed with 2.1 g of AlF.sub.3 (heated at 200.degree. C. for 3
h) and placed in tube furnace. The mixture was heated in tube
furnace under N.sub.2 flow (0.6 slpm) at room temperature for 1 h,
then at 500.degree. C. for 3 h and at room temperature for another
4 h.
Example 15
[0356] AlF.sub.3 from Aldrich was heated in a muffle furnace at
200.degree. C. for 2 h.
[0357] Catalyst Preparation: 1.0 gram of each support was slurried
in 4.3 grams of isohexane followed by 1.70 grams of TIBAL solution
(30 wt. % in hexane). 10.0 mg of
dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride was
reacted with 1.70 grams of TIBAL solution (30 wt. % in hexane) at
ambient temperature and then added to the support. After stirring
at ambient temperature for 1 hour, mineral oil was added to make a
solid percent concentration of 5 to 6 wt %.
[0358] Polymerization: The catalysts were tested in bulk propylene
polymerization using 6-x pack and 4 L bench reactor at 67.degree.
C. The process conditions and activity of such polymerizations are
illustrated in Table IA below.
TABLE-US-00001 TABLE IA Activity, Example # % AlF.sub.3 Heating
g/g/h MF % Zr 1 13.6 200.degree. C., 1 h; 480 NR NR 450.degree. C.,
3 h 2 28.3 200.degree. C., 1 h; 620 NR NR 450.degree. C., 3 h 3 6.8
200.degree. C., 1 h; 5,830 18.3 NR 450.degree. C., 3 h 4 2.4
200.degree. C., 1.5 h; 2,740 NR 0.0259 450.degree. C., 3 h 5 3.5
200.degree. C., 1.5 h; 4,650 NR NR 450.degree. C., 3 h 6 6.8
200.degree. C., 1 h; 12,492 9.5 0.0668 450.degree. C., 3 h 7 7.0
450.degree. C., 3 h 8,400 NR NR 8 13.6 200.degree. C., 1 h; 9,676
13.6 NR 450.degree. C., 3 h 9 20.4 200.degree. C., 1 h; 7,505 18.7
NR 450.degree. C., 3 h 10 12 450.degree. C., 3 h 10,795 9.2 NR 11
3.5 200.degree. C., 1.5 h 52 NR NR 12 7 200.degree. C., 5 h; 27 NR
NR 13 12 Tube 6,000 NR NR furnace 14 100 200.degree. C., 2 h trace
NR NR 15 12 Tube 12,040 10.7 NR furnace *NR = not recorded
[0359] It was observed that the temperature of the heat treatment
is a crucial factor in high activity catalysts. The heat treatment
at 200.degree. C. resulted in the catalysts having significantly
lower activity compared to the catalysts heated at 450.degree.
C.
[0360] Further increasing activity was observed when the
concentration of alumina in alumina-silica was increased. While
high activities were observed at about 7-13 wt. % of AlF.sub.3
impregnated on the alumina-silica, the catalysts including 13 wt. %
Al.sub.2O.sub.3 exhibited activities of greater than 12,000 g/g/h.
See, FIG. 2. It was further observed that AlF.sub.3 impregnated on
fluorinated alumina-silica resulted in lower catalyst activity than
AlF.sub.3 impregnated on alumina-silica.
[0361] Additionally, the catalysts prepared by mixing the support
and aluminum fluoride in water or an organic solvent (THF) followed
by heat treatment showed approximately the same activity as one
another. However, the catalysts prepared by impregnating the
aluminum fluoride on the support using a solid-phase reaction in
fluidized bed resulted in slightly higher activity.
[0362] The properties of the polymers formed via such
polymerizations were further analyzed and are illustrated in Table
IB below.
TABLE-US-00002 TABLE IB Example .DELTA.H.sub.m, .DELTA.H.sub.c,
M.sub.n/ M.sub.w/ M.sub.z/ # T.sub.m .degree. C. J/g T.sub.c,
.degree. C. J/g 1000 1000 1000 M.sub.w/M.sub.n 1 149.7 88.4 110.3
-89.9 30.3 142.4 354.8 4.7 2 150.7 88.3 109.8 -89.9 38.0 148.3
286.3 3.9 3 151.1 90.1 109.3 -91.1 39.0 185.3 398.4 4.8 4 149.9
105.1 109.9 -96.8 30.1 178.6 410.5 5.9 5 150.8 106.0 109.4 -96.4
36.8 193.3 429.8 5.3 6 150.3 88.3 106.8 -90.9 52.4 258.7 511.5 4.9
7 150.6 104.9 108.1 96.6 34.0 212.7 473.4 6.3 8 150.7 85.1 105.9
-88.5 40.5 208.3 429.7 5.1 9 149.2 91.2 107.3 -92.5 38.4 200.7
411.7 5.2 10 150.7 89.3 106.9 -90.1 48.2 241.5 518.9 5.0 11 158.2
105.7 116.9 -107.3 35.9 137.5 315.6 3.9 12 156.2 95.8 114.9 -92.3
33.7 154.3 364.5 4.6 13 149.3 92.8 109.7 -86.4 41.6 183.0 376.8 4.4
14 152.5 81.1 106.9 -83.5 42.8 139.4 304.3 3.3 15 150.3 106.6 110.1
-98.5 42.4 229.3 499.8 5.4
[0363] It was observed that the catalysts treated at 450.degree. C.
produced highly isotactic polypropylene (99% mmmm pentads by NMR
analysis, see, Table IC below illustrating the tacticity of the
polymer produced in Example 6) with a melting point of about
150.degree. C. and a molecular weight distribution in range of 4 to
6. However, the catalysts treated at 200.degree. C. produced
polypropylene with a melting point of about 158.degree. C.
TABLE-US-00003 TABLE IC Pentades % mmmm 98.9 mmmr 0.3 rmmr 0.0 mmrr
0.3 xmrx 0.1 mrmr 0.0 rrrr 0.0 rrrm 0.2 mrrm 0.1 % meso 99.5 %
racemic 0.5 % error 0.1
Example-II
[0364] In the following examples, samples of fluorinated
metallocene catalyst compounds were prepared according to the
second embodiments of the invention.
[0365] As used below "Silica P-10" refers to silica that was
obtained from Fuji Sylisia Chemical LTD (grade: Cariact P-10, 20
.mu.m), such silica having a surface area of 281 m.sup.2/g, a pore
volume of 1.41 mL/g, an average particle size of 20.5 .mu.m and a
pH of 6.3.
[0366] As used below "SiAl (5%)" refers to silica alumina that was
obtained from Fuji Sylisia Chemical LTD (Silica-Alumina 205 20
.mu.m), such silica having a surface area of 260 m.sup.2/g, a pore
volume of 1.30 mL/g, an aluminum content of 4.8 wt. %, an average
particle size of 20.5 .mu.m, a pH of 6.5 and a 0.2% loss on
drying.
[0367] As used below "(NH.sub.4).sub.2SiF.sub.6" refers to ammonium
hexafluorosilicate that was obtained from Aldrich Chemical
Company.
[0368] As used below "DEAF" refers to diethylaluminum fluoride
(26.9 wt. % in heptane) that was obtained from Akzo Nobel Polymer
Chemicals, L.L.C.
[0369] As used below "MAO" refers to methylaluminoxane (30 wt. % in
toluene) that was obtained from Albemarle Corporation.
[0370] Fluorinated Support A: The preparation of Fluorinated
Support A was achieved by dry mixing 25.0 g of silica P 10 with
0.76 g of (NH.sub.4).sub.2SiF.sub.6 and then transferring the
mixture into a quartz tube having a glass-fritted disc. The quartz
tube was then inserted into a tube furnace and equipped with an
inverted glass fritted funnel on the top opening of the tube. The
mixture was then fluidized with nitrogen (0.4 SLPM). Upon
fluidization, the tube was heated from room temperature to an
average reaction temperature of 116.degree. C. over a period of 5
hours. Upon reaching the average reaction temperature, the tube was
maintained at the average reaction temperature for another 4 hours.
The tube was then heated to an average calcining temperature of
470.degree. C. over 2 hours and then held at the calcining
temperature for 4 hours. The tube was then removed from the heat
and cooled under nitrogen. The fluorinated silica P-10 (1.0 g) was
added to a glass insert that was equipped with the magnetic
stirrer. The fluorinated silica was then slurried in 10 mL of
toluene and stirred at ambient temperature. Slowly, 2.5 mL of MAO
(30 wt. % in toluene) was added to the silica at ambient
temperature. The glass inserts were then loaded to the reactor
vessel. The reactor was then closed, placed on a magnetic stir
plate and connected to the top manifold assembly under nitrogen.
The reaction was then heated to 115.degree. C. for 4 hours. After 4
hours, the solid was filtered through a glass filter funnel and
washed once with 5 mL of toluene followed by washing 3.times. with
5 mL of hexane. The solid was then dried under vacuum at ambient
temperature.
[0371] Fluorinated Support B: The preparation of Fluorinated
Support B (middle F:Al/high Al:Si) was achieved by dry mixing 25.22
g of SiAl (5%) with 1.51 g of (NH.sub.4).sub.2SiF.sub.6 and then
transferring the mixture into a quartz tube having a glass-fritted
disc. The quartz tube was then inserted into a tube furnace and
equipped with an inverted glass flitted funnel on the top opening
of the tube. The mixture was then fluidized with nitrogen (0.4
SLPM). Upon fluidization, the tube was heated from room temperature
to an average reaction temperature of 116.degree. C. over a period
of 5 hours. Upon reaching the average reaction temperature, the
tube was maintained at the average reaction temperature for another
4 hours. The tube was then heated to an average calcining
temperature of 470.degree. C. over 2 hours and then held at the
calcining temperature for 4 hours. The tube was then removed from
the heat and cooled under nitrogen.
[0372] Fluorinated Support C: The preparation of Fluorinated
Support C was achieved by transferring 50 grams of silica P-10 into
a quartz glass tube (1.5''.times.4'') equipped with a fritted glass
disc. A flow of 0.6 SLPM Nitrogen was attached to the bottom of the
tube. The tube was placed in a tube furnace and the silica was
heated at 150.degree. C. for 16 hours. The silica was then
collected in an Erlenmeyer flask that was equipped with a rubber
tube. The rubber tube was "pinched" with a tube clip under
nitrogen. The flask was then transferred into a glove box. The
silica was transferred into a glass bottle and left to stand. The
preparation further included weighing and transferring 20 grams of
the heat treated silica P-10 (0.72 mmole OH/gram silica) into a 250
mL, 1-neck, side arm round bottom flask that was equipped with a
magnetic stirrer. The silica was slurred in approximately 150 mL of
toluene and stirred at room temperature. 2.36 g (0.0240 moles) of
DEAF were slowly added to the slurry at room temperature and
stirred for 5 minutes. The round bottom flask was equipped with a
reflux condenser and heated at 50.degree. C. for 1.0 hours. The
resulting mixture was then filtered though a medium glass fritted
funnel and washed 3 times each with 50 mL of hexane. The resulting
solids were dried under vacuum. The preparation further included
transferring 16.97 grams of the solids into the quartz glass tube
and heating under a nitrogen flow of 0.6 standard liters per minute
(SLPM). Upon fluidization, the tube was heated from room
temperature to an average reaction temperature of 130.degree. C.
over a period of 1.0 hour. Upon reaching the temperature at
130.degree. C., the temperature was increased to 450.degree. C. in
1.0 hour. Once the temperature was reached to 450.degree. C., it
was held at 450.degree. C. for 2 hours. The tube was then removed
from the heat and cooled under nitrogen. The solids were collected
and stored under nitrogen. The solids from part were further heat
treated under the same conditions as described above except that
air was used to fluidize the solids.
[0373] Comparative Support D: The preparation of Support D was
achieved by transferring 25.0 g of silica P10 into a quartz tube
having a glass-fritted disc. The quartz tube was then inserted into
a tube furnace and equipped with an inverted glass fitted funnel on
the top opening of the tube. The silica was then fluidized with
nitrogen (0.4 SLPM). Upon fluidization, the tube was then heated to
an average calcining temperature of 200.degree. C. over 12 hours.
The tube was then removed from the heat and cooled under nitrogen.
1.0 gram of the silica P-10 was added to a glass insert that was
equipped with the magnetic stirrer. The silica was then slurried in
10 mL of toluene and stirred at ambient temperature. Slowly, 2.5 mL
of MAO (30 wt. % in toluene) was added to the silica at ambient
temperature. The glass inserts were then loaded to the reactor
vessel. The reactor was then closed, placed on a magnetic stir
plate and connected to the top manifold assembly under nitrogen.
The reaction was then heated to 115.degree. C. for 4 hours. After 4
hours, the solid was filtered through a glass filter funnel and
washed once with 5 mL of toluene followed by washing 3 times with 5
mL of hexane. The solid was then dried under vacuum at ambient
temperature.
[0374] Catalyst A: The preparation of Catalyst A was achieved by
slurrying 0.5 grams of the support A in 5 mL of toluene at ambient
temperature and stirring with a magnetic stir bar. The preparation
then included adding 5 mg of
rac-diemthylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.0 hour. The resulting
mixture was filtered through a glass filter funnel and washed once
with 2 mL toluene followed by washing 3 times with 3 mL hexane. The
final solids were then dried under vacuum and slurried in mineral
oil.
[0375] Catalyst B: The preparation of Catalyst B was achieved by
slurrying 1.01 g of Fluorinated Support B in 6 mL of toluene and
stirring with a magnetic stir bar. The preparation then included
adding 4.0 g of TIBAl (25.2 wt. % in heptane) to the mixture and
the mixture was then stirred for about 5 minutes at room
temperature. The preparation then included adding 22.7 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed two times with 5 mL of hexane. The final
solids were then dried under vacuum and slurried in 12.3 g of
mineral oil.
[0376] Catalyst C: The preparation of Catalyst C was achieved by
slurrying 1.03 g of Fluorinated Support C in 6 mL of toluene and
stirring with a magnetic stir bar. The preparation then included
adding 4.01 g of TIBAl (25.2 wt. % in heptane) to the mixture and
the mixture was then stirred for about 5 minutes at room
temperature. The preparation then included adding 20.0 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.5 hours at room
temperature. The resulting mixture was then filtered through a
medium glass filter funnel and washed once with 5 mL toluene
followed by washing once with 5 mL hexane. After drying at ambient
temperature for about 1 hour, the solids were slurried in dry
mineral oil. The final solids were then dried under vacuum and
slurried in mineral oil.
[0377] Catalyst D: The preparation of Catalyst D was achieved by
slurrying 0.5 grams of the support D in 5 mL of toluene at ambient
temperature and stirring with a magnetic stir bar. The preparation
then included adding 5 mg of
rac-diemthylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.0 hour. The resulting
mixture was filtered through a glass filter funnel and washed once
with 2 mL toluene followed by washing 3 times with 3 mL hexane. The
final solids were then dried under vacuum and slurried in mineral
oil.
[0378] The resulting catalysts were then exposed to polymerization
with olefin monomer to form the resulting polymer. The results of
such polymerizations follow in Tables IIA and IIB,
respectively.
TABLE-US-00004 TABLE IIA (Polypropylene) Catalyst Co-Catalyst
Activity M T.sub.R T.sub.M2 Mw Mw/Mn Mz/Mw D TEAL 10786 1 107.6
149.0 200199 5.2 3.3 A TEAL 12508 1 107.6 149.4 211691 3.7 2.7 B
TEAL 1334 2 108.0 148.7 105258 5.2 2.3 B TIBAL 5272 2 107.1 149.4
200708 4.8 2.6 C TEAL 405 2 109.5 149.9 119610 5.6 2.3 C TIBAL 5849
2 108.0 149.7 174815 4.7 2.7 *t is polymerization time in minutes,
activity is expressed in gPP/gCat/hour, M is the catalyst loading
in wt. %, T.sub.R is recrystallization temperature in .degree. C.,
T.sub.M2 is the temperature of the second melt peak in .degree.
C.
TABLE-US-00005 TABLE IIB (Polyethylene) Co- Catalyst Catlyst t
Activity M T.sub.R T.sub.M2 Mn Mw Mz HLMI B TIBAL 60 1903 2 94.6
103.7 29730 201841 590085 0.3 E TIBAL 60 5151 2 111.0 128.0 23807
216617 618982 1.7 *t is polymerization time in minutes, activity is
expressed in gPP/gCat/hour, M is the catalyst loading in wt. %,
T.sub.R is recrystallization temperature in .degree. C., T.sub.M2
is the temperature of the second melt peak in .degree. C., HLMI is
explessed in g/10 min., Catalyst E is composed of the metallocene
rac-Ethylenebis(tetrahydroindenyl)ZrCl2 supported on MAO/SiO2
support.
[0379] Unexpectedly, it has been discovered that the productivity
of polyolefin polymerizations can be controlled by the catalyst
preparation methods described herein.
[0380] As demonstrated in the examples above, a higher (5 wt. %)
Al.sup.1:Si ratio results in higher catalyst activity than the
lower (1 wt. %) Al.sup.1:Si molar ratio. (See, Catalysts E and
C.)
[0381] Further, it has been demonstrated that F:Al.sup.1 molar
ratios of about 3:1 result in higher catalyst activities than
ratios of 6:1 or 2:1. (See, Catalysts B, C and D.) It has also been
observed that transition metal loadings of 2 wt. % result in higher
catalyst activities than loadings of 1 wt. %. (See, Catalysts B and
C.)
[0382] In addition, it was unexpectedly observed that when the
scavenger was added to the fluorinated support prior to contact
with the transition metal compound, higher catalyst activities were
observed than when the transition metal compound is contacted with
the scavenging compound. (See, Catalysts A and B.)
Example-III
[0383] In the following examples, samples of fluorinated
metallocene catalyst compounds were prepared.
[0384] As used below "SiAl (5%)" refers to Silica Alumina that was
obtained from Fuji Sylisia Chemical LTD (Silica-Alumina 205 20
.mu.m), such silica having a surface area of 260 m.sup.2/g, a pore
volume of 1.30 mL/g, an aluminum content of 4.8 wt. %, an average
particle size of 20.5 .mu.m, a pH of 6.5 and a 0.2% loss on
drying.
[0385] As used below "SiAl (1%)" refers to Silica Alumina that was
obtained from Fuji Sylisia Chemical LTD (Silica-Alumina 201 20
.mu.m), such silica having a surface area of 264 m.sup.2/g, a pore
volume of 1.30 mL/g, an aluminum content of 1.3 wt. %, an average
particle size of 21.7 .mu.m, a pH of 6.5 and a 0.2% loss on
drying.
[0386] As used below "(NH.sub.4).sub.2SiF.sub.6" refers to ammonium
hexafluorosilicate that was obtained from Aldrich Chemical
Company.
[0387] As used below "NH.sub.4BF.sub.4" refers to ammonium
tetrafluoroborate that was obtained from Aldrich Chemical
Company.
[0388] As used below "NH.sub.4FHF" refers to ammonium bifluoride
that was obtained from Aldrich Chemical Company
[0389] Fluorinated Support A: The preparation of Fluorinated
Support A (low F:Al/high Al:Si) was achieved by dry mixing 20.19 g
of SiAl (5%) with 0.60 g of (NH.sub.4).sub.2SiF.sub.6 and then
transferring the mixture into a quartz tube having a glass-fritted
disc. The quartz tube was then inserted into a tube furnace and
equipped with an inverted glass fritted funnel on the top opening
of the tube. The mixture was then fluidized with nitrogen (0.4
SLPM). Upon fluidization, the tube was heated from room temperature
to an average reaction temperature of 116.degree. C. over a period
of 5 hours. Upon reaching the average reaction temperature, the
tube was maintained at the average reaction temperature for another
4 hours. The tube was then heated to an average calcining
temperature of 470.degree. C. over 2 hours and then held at the
calcining temperature for 4 hours. The tube was then removed from
the heat and cooled under nitrogen.
[0390] Fluorinated Support B: The preparation of Fluorinated.
Support B (middle F:Al/high Al:Si) was achieved by dry mixing 25.22
g of SiAl (5%) with 1.51 g of (NH.sub.4).sub.2SiF.sub.6 and then
transferring the mixture into a quartz tube having a glass-fritted
disc. The quartz tube was then inserted into a tube furnace and
equipped with an inverted glass fritted funnel on the top opening
of the tube. The mixture was then fluidized with nitrogen (0.4
SLPM). Upon fluidization, the tube was heated from room temperature
to an average reaction temperature of 116.degree. C. over a period
of 5 hours. Upon reaching the average reaction temperature, the
tube was maintained at the average reaction temperature for another
4 hours. The tube was then heated to an average calcining
temperature of 470.degree. C. over 2 hours and then held at the
calcining temperature for 4 hours. The tube was then removed from
the heat and cooled under nitrogen.
[0391] Fluorinated Support C: The preparation of Fluorinated
Support C (high F:Al/high Al:Si) was achieved by dry mixing 25.14 g
of SiAl (5%) with 2.56 g of (NH.sub.4).sub.2SiF.sub.6 and then
transferring the mixture into a quartz tube having a glass-fritted
disc. The quartz tube was then inserted into a tube furnace and
equipped with an inverted glass fitted funnel on the top opening of
the tube. The mixture was then fluidized with nitrogen (0.4 SLPM).
Upon fluidization, the tube was heated from room temperature to an
average reaction temperature of 116.degree. C. over a period of 5
hours. Upon reaching the average reaction temperature, the tube was
maintained at the average reaction temperature for another 4 hours.
The tube was then heated to an average calcining temperature of
470.degree. C. over 2 hours and then held at the calcining
temperature for 4 hours. The tube was then removed from the heat
and cooled under nitrogen.
[0392] Fluorinated Support D: The preparation of Fluorinated
Support D (middle F:Al/low Al:Si) was achieved by dry mixing 25.1 g
of SiAl (1%) with 1.52 g of (NH.sub.4).sub.2SiF.sub.6 and then
transferring the mixture into a quartz tube having a glass-fritted
disc. The quartz tube was then inserted into a tube furnace and
equipped with an inverted glass fitted funnel on the top opening of
the tube. The mixture was then fluidized with nitrogen (0.4 SLPM).
Upon fluidization, the tube was heated from room temperature to an
average reaction temperature of 116.degree. C. over a period of 5
hours. Upon reaching the average reaction temperature, the tube was
maintained at the average reaction temperature for another 4 hours.
The tube was then heated to an average calcining temperature of
470.degree. C. over 2 hours and then held at the calcining
temperature for 4 hours. The tube was then removed from the heat
and cooled under nitrogen.
[0393] Fluorinated Support E: The preparation of Fluorinated
Support E was achieved by dry mixing 22.0 g of SiAl (5%) with 1.37
g of NH.sub.4BF.sub.4 and then transferring the mixture into a
quartz tube having a glass-fritted disc. The quartz tube was then
inserted into a tube furnace and equipped with an inverted glass
fritted funnel on the top opening of the tube. The mixture was then
fluidized with nitrogen (0.4 SLPM). Upon fluidization, the tube was
heated from room temperature to an average reaction temperature of
116.degree. C. over a period of 5 hours. Upon reaching the average
reaction temperature, the tube was maintained at the average
reaction temperature for another 4 hours. The tube was then heated
to an average calcining temperature of 470.degree. C. over 2 hours
and then held at the calcining temperature for 4 hours. The tube
was then removed from the heat and cooled under nitrogen.
[0394] Fluorinated Support F: The preparation of Fluorinated
Support F was achieved by dry mixing 20.2 g of SiAl (5%) with 1.6 g
of NH.sub.4.HF and then transferring the mixture into a quartz tube
having a glass-fritted disc. The quartz tube was then inserted into
a tube furnace and equipped with an inverted glass fritted funnel
on the top opening of the tube. The mixture was then fluidized with
nitrogen (0.4 SLPM). Upon fluidization, the tube was heated from
room temperature to an average reaction temperature of 116.degree.
C. over a period of 5 hours. Upon reaching the average reaction
temperature, the tube was maintained at the average reaction
temperature for another 4 hours. The tube was then heated to an
average calcining temperature of 470.degree. C. over 2 hours and
then held at the calcining temperature for 4 hours. The tube was
then removed from the heat and cooled under nitrogen.
[0395] Fluorinated Support G: The preparation of Fluorinated
Support G was achieved by mixing 25.0 g of SiAl (5%) with a 150 mL
aqueous solution that contained 1.50 g of NH.sub.4.HF at ambient
temperature. The water was then removed at 70.degree. C. in a
rotary evaporator. The dry solids were transferred into a quartz
tube having a glass-fitted disc. The quartz tube was then inserted
into a tube furnace and equipped with an inverted glass fitted
funnel on the top opening of the tube. The mixture was then
fluidized with nitrogen (0.4 SLPM). Upon fluidization, the tube was
heated from room temperature to an average reaction temperature of
116.degree. C. over a period of 5 hours. Upon reaching the average
reaction temperature, the tube was maintained at the average
reaction temperature for another 4 hours. The tube was then heated
to an average calcining temperature of 470.degree. C. over 2 hours
and then held at the calcining temperature for 4 hours. The tube
was then removed from the heat and cooled under nitrogen.
[0396] Support H:The preparation of Non-Fluorinated Support H was
achieved by transferring 45.6 g of SiAl (5%) into a quartz tube
having a glass-fritted disc. The quartz tube was then inserted into
a tube furnace and equipped with an inverted glass fritted funnel
on the top opening of the tube. The SiAl (5%) was then fluidized
with nitrogen (0.4 SLPM). Upon fluidization, the tube was heated
from room temperature to an average reaction temperature of
116.degree. C. over a period of 5 hours. Upon reaching the average
reaction temperature, the tube was maintained at the average
reaction temperature for another 4 hours. The tube was then heated
to an average calcining temperature of 470.degree. C. over 2 hours
and then held at the calcining temperature for 4 hours. The tube
was then removed from the heat and cooled under nitrogen.
[0397] Catalyst A: The preparation of Catalyst A (late scavenger)
was achieved by slurrying 0.5 g of Fluorinated Support A in 5 mL or
toluene and stirring with a magnetic stir bar. The preparation then
included adding 5 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
mixture was then stirred for about 2 minutes and 1.0 g of TibAl
(25.2 wt. % in heptane) was added to the mixture. The resulting
mixture was then stirred for 1.5 hours at room temperature. The
resulting mixture was then filtered through a medium glass filter
funnel and washed three times with 5 mL of hexane. The final solids
were then dried under vacuum and slurried in 6.27 g of mineral
oil.
[0398] Catalyst B: The preparation of Catalyst B (early
scavenger/high F:Al) was achieved by slurrying 1.02 g of
Fluorinated Support A in 6 mL of toluene and stirring with a
magnetic stir bar. The preparation then included adding 4.0 g of
TibAl (25.2 wt. % in heptane) to the mixture and the mixture was
then stirred for about 5 minutes at room temperature. The
preparation then included adding 11.3 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed once with 6.5 grams of toluene followed by
washing three times with 5 mL of hexane. The final solids were then
dried under vacuum and 0.48 g of the catalyst were slurried in 7.12
g of mineral oil.
[0399] Catalyst C: The preparation of Catalyst C (early scavenger)
was achieved by slurrying 1.01 g of Fluorinated Support B in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 22.7 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed once with 6 mL of toluene followed by
washing two times with 5 mL of hexane. The final solids were then
dried under vacuum and slurried in 12.3 g of mineral oil.
[0400] Catalyst D: The preparation of Catalyst D (early scavenger)
was achieved by slurrying 1.02 g of Fluorinated Support C in 6 mL
or toluene and stirring with a magnetic stir bar. The preparation
then included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 21.3 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed once with 6 mL of toluene followed by
washing two times with 5 mL of hexane. The final solids were then
dried under vacuum and slurried in 12.77 g of mineral oil.
[0401] Catalyst E: The preparation of Catalyst E (early scavenger)
was achieved by slurrying 1 g of Fluorinated Support D in 6 mL or
toluene and stirring with a magnetic stir bar. The preparation then
included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 21.0 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed once with 6 mL of toluene followed by
washing two times with 5 mL of hexane. The final solids were then
dried under vacuum and slurried in 12.88 g of mineral oil.
[0402] Catalyst F: The preparation of Catalyst F (no scavenger) was
achieved by slurrying 0.52 g of Fluorinated Support B in 4 mL of
toluene and stirring with a magnetic stir bar. The preparation then
included adding 11.7 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours. The resulting
mixture was then filtered through a medium glass filter funnel and
washed once with 6 mL of toluene followed by washing three times
with hexane. The final solids were then dried under vacuum and
slurried in 3.24 g of mineral oil.
[0403] Catalyst G: The preparation of Catalyst G was achieved by
slurrying 1.03 g of Non-fluorinated Support H in 6 mL of toluene
and stirring with a magnetic stir bar. The preparation then
included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 21.5 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed once with 6 mL of toluene followed by
washing two times with 5 mL of hexane. The final solids were then
dried under vacuum and slurried in 12.00 g of mineral oil.
[0404] Catalyst H: The preparation of Catalyst H (early scavenger)
was achieved by slurrying 1.04 g of Fluorinated Support E in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 11.8 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.0 hour at room
temperature. The resulting mixture was then filtered through a
medium glass filter funnel and washed two times with 5 mL of
hexane. The final solids were then dried under vacuum and slurried
in mineral oil.
[0405] Catalyst I: The preparation of Catalyst I (early scavenger)
was achieved by slurrying 1.04 g of Fluorinated Support F in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 20.6 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 2 hours at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed once with 6 mL of hexane. The final solids
were then dried under vacuum and slurried in mineral oil.
[0406] Catalyst J: The preparation of Catalyst J (early scavenger)
was achieved by slurrying 1.01 g of Fluorinated Support G in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 11.1 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.0 hour at room
temperature. The resulting mixture was then filtered through a
medium glass filter funnel and dried under vacuum. The final solids
were slurried in mineral oil.
[0407] Catalyst K: The preparation of Catalyst K (early scavenger)
was achieved by slurrying 1.16 g of Fluorinated Support B in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 8.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 21.2 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.0 hour at room
temperature. The resulting mixture was then filtered through a
medium glass filter funnel and washed two times with 5 mL of
hexane. The final solids were then dried under vacuum and slurried
in mineral oil.
[0408] Catalyst L: The preparation of Catalyst L (early scavenger)
was achieved by slurrying 1.05 g of Fluorinated Support B in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 12.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 20.9 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1 hour at room temperature.
The resulting mixture was then filtered through a medium glass
filter funnel and washed two times with 5 mL of hexane. The final
solids were then dried under vacuum and slurried in mineral
oil.
[0409] Catalyst M: The preparation of Catalyst M (early scavenger)
was achieved by slurrying 1.03 g of Fluorinated Support B in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 4.0 g of TibAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 19.8 mg of
iPr(3-tBu-5-Me-Cp)(Flu)zirconium dichloride to the fluorinated
support at room temperature. The resulting mixture was then stirred
for 2 hours at room temperature. The resulting mixture was then
filtered through a medium glass filter funnel and washed once with
6 mL of toluene followed by washing two times with 5 mL of hexane.
The final solids were then dried under vacuum and slurried in
mineral oil.
[0410] Catalyst N: The preparation of Catalyst N (early scavenger)
was achieved by slurrying 1.03 g of Fluorinated Support B in 6 mL
of toluene and stirring with a magnetic stir bar. The preparation
then included adding 4.0 g of TiBAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 22.5 mg of
Ph.sub.2C(Cp)(Flu)zirconium dichloride to the fluorinated support
at room temperature. The resulting mixture was then stirred for 2
hours at room temperature. The resulting mixture was then filtered
through a medium glass filter funnel and washed once with 6 mL of
toluene followed by washing two times with 5 mL of hexane. The
final solids were then dried under vacuum and slurried in mineral
oil.
[0411] The resulting catalysts were then exposed to polymerization
with propylene and ethylene monomer to form polypropylene and
polyethylene. The results of such polymerizations follow in the
tables below.
TABLE-US-00006 TABLE IIIA (Polypropylene) Activity T.sub.rec
.DELTA..sub.Recryst .DELTA.2.sup.nd.sub.melt 2.sup.nd T.sub.m
Reactor Catalyst Co-Cat (g/g/h) (.degree. C.) (J/g) T.sub.melt
(.degree. C.) (J/g) (.degree. C.) M.sub.w M.sub.w/M.sub.n
M.sub.z/M.sub.w mmmm 6X A TEAL 125 105.6 -77.99 142.7 80.59 49236
5.0 3.2 6X B TEAL 537 108.47 92.91 148 101.68 90529 6.6 2.7 6X C
TEAL 1334 107.97 94.24 148.7 104.55 105258 5.2 2.3 98.3 6X C TIBAL
5272 107.13 91.51 149.4 96.09 200708 4.8 2.6 4L C TIBAL 3851 6X D
TEAL 472 108 -87.3 146.7 87.5 76055 5.9 2.6 6X D TIBAL 2247 107.6
-87.6 149.7 81.58 236929 6.3 2.7 6X E TEAL 108 105.3 -76.1 140.4
75.4 147 47833 5.2 3.2 6X E TIBAL 279 6X F TEAL 67 99.3 53.44 137.4
59.72 66213 5.6 2.9 6X G TEAL 0 6X H TIBAL 1253 6X I TIBAL 431 6X J
TIBAL 4043 4L K TIBAL 7280 4L L TIBAL 5022 6X Polymerization
Conditions: 170 g propylene, 14 mmoles H2, 10 mg Co-Catalyst,
67.degree. C., 30 min. 4L Polymerization Conditions: 1350 g
propylene, 24 mmoles H2, 90 mg Co-Catalyst, 67.degree. C., 30
min.
TABLE-US-00007 TABLE IIIB (Polypropylene) Polymerization Activity
T.sub.r .quadrature.H.sub.r T.sub.m .quadrature.H.sub.m Catalyst
Co-Cat Temp (.degree. C.) (g/g/h) (.degree. C.) (J/g) (.degree. C.)
(J/g) M.sub.w M.sub.w/M.sub.n M.sub.z/M.sub.w M TIBAL 67 25 99.3
-58.5 136.0 55.2 107144 4 2.2 N TIBAL 60 220 62.3 0.6 119.4 9.2
152963 3.3 2.3 6X Polymerization Conditions: 170 g propylene, 14
mmoles H2, 10 mg Co-Catalyst, 30 min.
TABLE-US-00008 TABLE IIIC (Polyethylene) Co- Catalyst Catlyst t
Activity M T.sub.R T.sub.M2 Mn Mw Mz HLMI C TIBAL 60 1903 2 94.6
103.7 29730 201841 590085 0.3 *t is polymerization time in minutes,
activity is expressed in gPP/gCat/hour, M is the catalyst loading
in wt. %, T.sub.R is recrystallization temperature in .degree. C.,
T.sub.M2 is the temperature of the second melt peak in .degree. C.,
HLMI is explessed in g/10 min.
Example-IV
[0412] Samples of polymers were formed according to the third
embodiments described herein. As used in these examples,
silica-alumina refers to silica alumina that was obtained from Fuji
Sylisia Chemical LTD (Silica-Alumina 205 20 .mu.m), such silica
having a surface area of 260 m.sup.2/g, a pore volume of 1.30 mL/g,
an aluminum content of 4.8 wt. %, an average particle size of 20.5
.mu.m and a pH of 6.5.
[0413] Unless otherwise specified, the fluorination of the
alumina-silica was accomplished by slurrying 5.0 g of
alumina-silica in 15 mL of water at ambient temperature. 0.30 g of
NHF.HF (in 10 mL of water) was added to the slurry. The resulting
mixture was then placed under partial vacuum at 90.degree. C. in a
rotavap. Heat treatment profile 1 included heating the resulting
dry solids in a muffle furnace at 400.degree. C. for 3 hours. Heat
treatment profile 2 included heating the resulting dry solids in a
muffle furnace at 260.degree. C. for 1 hour and then at 400.degree.
C. for 3 hours. The solids were left to cool to ambient temperature
and placed under vacuum.
[0414] Unless otherwise specified, the first catalyst preparation
method ("isolated method") included mixing 1 g. of the fluorinated
support in 6 mL of toluene with 4 g. of TIBAL (25.2 wt. % in
heptane) at a 1:1 wt. ratio and stirring with a magnetic stir bar
for 5 minutes at ambient temperature. 10 mg. of
dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride was
then added at ambient temperature. The mixture was then stirred for
1 hour and filtered. The resulting solids were washed with 6 mL of
toluene, washed twice with 5 mL of hexane and dried under vacuum.
The dried solids were then slurried in 12.3 g. of mineral oil and
stored at -35.degree. C. until use for polymerizations.
[0415] Unless otherwise specified, the second catalyst preparation
method ("one pot") included mixing 10 mg. of
dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride
with 4.0 g of TIBAL (25.2 wt. % in heptane) and stirring the
mixture for about 15 minutes at ambient temperature. 1.0 g of the
fluorinated support was then added as a dry powder and the mixture
was stirred for another 15 minutes. 6 g. of mineral oil were then
added and the resulting mixture was stirred for 5 minutes.
[0416] Propylene Polymerizations: The catalyst slurry was then
contacted with propylene monomer to form polymer. The
polymerization conditions and results of each polymerization follow
in Tables IVA, IVB and IVC.
TABLE-US-00009 TABLE IVA Heat Wt % Treatment Prep Fl. Supp:TIBAL
Activity Run # Profile Method Fl. Agent Agent wt. ratio (g/g/h) BD
(g/cc) 1 1 1 NH.sub.4F.cndot.HF 1:2 2812 0.45 2 2 1
NH.sub.4F.cndot.HF 1:2 3175 NR .sup. 3 (comp) Tube 1
(NH.sub.4).sub.2SiF.sub.6 1:1 3851 NR furnace (500.degree. C.) 4 2
1 NH.sub.4F.cndot.HF 3.8 1:1 1729 5 2 1 NH.sub.4F.cndot.HF 6.0 1:1
3175 6 2 1 NH.sub.4F.cndot.HF 10.0 1:1 2867 *BD refers to and is
measured via ASTM-D-1238-E, 4L reactor, 1350 g. propylene, 24 mmol
H.sub.2, 90 mg TIBAL, 45 mg. catalyst, 67.degree. C., 30
minutes
TABLE-US-00010 TABLE IVB T.sub.r .DELTA.H.sub.r T.sub.m
.DELTA.H.sub.m Run # (.degree. C.) (J/g) (.degree. C.) (J/g) Mw
Mw/Mn Mz/Mw 1 109.6 92.5 150.7 97.1 140547 4.4 1.9 2 112.6 99.2
151.7 76.8 133716 4.0 2.1 .sup. 3(comp) 107.6 94.6 150.0 99.1
142779 5.2 2.3 4 112.3 86.9 155.0 81.0 149935 3.5 2.0 5 112.6 99.2
151.7 76.8 133716 4.0 2.1 6 109.6 88.4 150.7 83.5 137613 4.2 2.0
*Tr refers to recrystallization temperature, .DELTA.Hr refers to
heat of recrystallization, Tm refers to melting point, .DELTA.Hm
refers to heat of melt, Mw refers to weight average molecular
weight, Mn refers to number average molecular weight and Mz refers
to z average molecular weight, NR means not recorded, NA means not
applicable
TABLE-US-00011 TABLE IVC Wt % Prep Fl. Supp:TIBAL Activity Run #
Method Fl. Agent Agent wt. ratio (g/g/h) .sup. 7(comp) 0.7 NA 0 1:1
6251 MAO/P10 8 2 NH.sub.4F.cndot.HF 5 1:1 4557 9 2
(NH.sub.4).sub.2SiF.sub.6 6 1:1 5986 10 2 NH.sub.4F.cndot.HF 7 1:1
7128 11 2 NH.sub.4F.cndot.HF 8 1:1 10049 6X parallel reactor, 170
g. propylene, 10 mmol H.sub.2, 90 mg TIBAL, 10 mg. catalyst,
67.degree. C., 30 minutes
[0417] Unexpectedly, it was observed that both heat treatment
profiles resulted in approximately the same catalytic activity and
properties. Further, it was observed that the highest catalyst
activity was observed for the catalyst prepared with 6 wt. %
fluorinating agent. It was further observed that one-pot catalyst
preparation resulted in higher catalyst activity than the isolated
method. In addition, the one-pot method produced polymer having a
higher molecular weight.
[0418] Ethylene/Propylene Polymerizations: The catalyst slurry was
then contacted with propylene monomer to form polymer. The
polymerization conditions and results of each polymerization follow
in Tables IVD and IVE.
TABLE-US-00012 TABLE IVD Wt. % MFI Prep Wt % Fl. Supp:TIBAL
ethylene in Activity (g/10 Run # Method Fl. Agent Agent wt. ratio
feed (g/g/h) min) 12 Tube NH.sub.4F.cndot.HF 6 1:1 2 8348 95.0
Furnace 13 Tube NH.sub.4F.cndot.HF 6 1:1 3 16903 17.0 Furnace 14
Tube NH.sub.4F.cndot.HF 6 1:1 5 34378 8.9 Furnace .sup. 15(comp)
0.7 1:1 2 8392 66.9 MAO/P10 .sup. 16(comp) 0.7 1:1 3 8192 61.7
MAO/P10 .sup. 17(comp) 0.7 1:1 5 8025 61.4 MAO/P10 18 Muffle
NH.sub.4F.cndot.HF 0 10396 16.5 Furnace 19 Muffle
NH.sub.4F.cndot.HF 1 15173 7.3 Furnace 20 Muffle NH.sub.4F.cndot.HF
2 17460 6.2 Furnace 6X reactor, 170 g. propylene, 116 ppm H.sub.2,
90 mg TIBAL, 10 mg. catalyst, 67.degree. C., 30 minute, 0.5
TEAL:Cat ratio for comp
TABLE-US-00013 TABLE IVE Run T.sub.r .DELTA.H.sub.r T.sub.m
.DELTA.H.sub.m # (.degree. C.) (J/g) (.degree. C.) (J/g) Mw Mw/Mn
Mz/Mw 12 98.3 81.6 140.0 81.8 125039 4.8 2.3 13 93.3 75.4 135.5
75.3 188053 3.9 2.1 14 83.5 59.6 127.9 58.5 293066 4.1 2.5 15 99.0
78.0 140.2 79.3 127695 3.3 1.9 16 94.3 72.4 135.9 75.5 148156 3.7
2.3 17 83.8 61.1 131.0 59.6 138892 3.2 2.0 *Tr refers to
recrystallization temperature, .DELTA.Hr refers to heat of
recrystallization, Tm refers to melting point, .DELTA.Hm refers to
heat of melt, Mw refers to weight average molecular weight, Mn
refers to number average molecular weight and Mz refers to z
average molecular weight, NR means not recorded, NA means not
applicable
[0419] Unexpectedly, it was observed that the fluorinated
alumina-silica catalyst activity increased with an increase in the
ethylene content of the feed. However, the activity of the
MAO/SiO.sub.2 catalyst remained relatively constant. Further, the
melt flow if the fluorinated alumina-silica decreased with an
increase in ethylene content, while the melt flow of the comparison
system did not change.
[0420] Effect of % fluorine: Several samples of prepared
fluorinated supports were analyzed for the amount of fluoride
content, the results of which follow in Table IVF.
TABLE-US-00014 TABLE IVF Fluo- Heat Run rination Wt % Fl. Treatment
Wt. % Activity # Method Fl. Agent Agent Method Fluorine (g/g/h) 21
Tube (NH.sub.4).sub.2SiF.sub.6 6 Tube 1.56 5734 22 Muffle
NH.sub.4F.cndot.HF 6 Glass Dish 1.23 5986 (small) 23 Muffle
NH.sub.4F.cndot.HF 8 Glass Dish 2.32 10049 (small) 24 Muffle
NH.sub.4F.cndot.HF 10 Glass Dish 1.98 10461 (small) 25 Muffle
NH.sub.4F.cndot.HF 10 Flask 1.38 6886 26 Muffle NH.sub.4F.cndot.HF
10 Glass Dish 2.06 10086 (large) 6X reactor, 170 g. propylene, 116
ppm H.sub.2, 90 mg TIBAL, 10 mg. catalyst, 67.degree. C., 30
minute, 0.5 TEAL:Cat ratio for comp
[0421] It was observed that the highest fluoride content was
obtained when the fluorinating process was carried out under open
glass dish heat treatments at 400.degree. C. for 5 hours, which
also resulted in the highest activity.
[0422] Stability: A 20-gram sample of NH.sub.4F.HF supported AlSiO2
was heat-treated using the small glass dish heat treatment method
(method Al). The resulting F--AlSiO.sub.2 support was used to
prepare catalyst using the insitu catalyst preparation method. The
catalyst system was then tested for stability at 0.degree. C. and
at ambient temperature (25.degree. C.).
TABLE-US-00015 TABLE IVG Storage Wt. % % Item Stadis Temp. C.sub.2
in Storage Activity Activity # (ppm) (.degree. C.) Feed Time
(g/g/h) decrease 1 0 0 0 1 night 13088 -- 2 0 0 0 2 nights 11958 9
3 0 0 0 4 weeks 9103 30 4 0.5 0 0 2 nights 7855 40 5 1.5 0 0 2
nights 6540 50 6 3 0 0 1 night 7079 46 7 0.5 25 0 3 days 9504 27 8
0.5 25 0 4 days 7917 40 9 3 25 0 4 days 4779 63 10 3 25 3 4 days
4709 64 Polymerization conditions: 2L reactor: 700 g propylene, 15
mmoles H2, 67.degree. C., 30 min. All runs produced fluff B.D. in
the range of 0.40 to 0.45 g/cc.
[0423] Effect of Supporting Methods: Method A was achieved by
slurrying 5.04 grams of alumina-silica in 10 mL of water at ambient
temperature. To the silica/water slurry, a solution of 0.52 grams
of NHF.HF in 15 mL of water was added at ambient temperature
(25.degree. C.). The resulting "wet" solids were then placed under
partial vacuum (15 in. Hg) at 90.degree. C. in a rotavap to remove
the water.
[0424] Method B was a achieved adding about 3.15 L of water to a 3
gallon HDPE bucket that was equipped with a mechanical stirrer
(4.5'' L.times.3.5'' W anchor-type). About 1.0 Kg of alumina-silica
were slowly added to the water while maintaining agitation at 60
rpm. To the thick slurry, a solution of 100 grams of NH.sub.4F.HF
in 800 mL of water were slowly added while stirring at ambient
temperature. The mixture was left to stir for 1 hour at ambient
temperature.
[0425] Method 1 was achieved by adding to a 3.0-L, 1-neck (24/40),
round bottom flask, the white slurry until the flask was about 2/3
full. The flask was attached to a rotavap that was equipped with a
mineral oil bath and two-piece cold trap style condenser. The
condenser was charged with ice and the flask was placed under full
vacuum (760 mm mercury; dry vacuum pump). The flask was rotated at
60 rpm while the bath temperature increased from ambient
temperature up to 95.degree. C. The water was removed after 2
hours. The supported NH4F.HF on AlSiO2 was obtained as a semi-wet
solid.
[0426] Method 2 was achieved by charging a vessel to about 1/4 full
with the water slurry of the supported NH4F.HF on AlSiO.sub.2. The
flask was equipped with a stir shaft that contained 4 kneading
propeller-type impellors. The flask was closed with a 3 (24/40)
neck lid and placed in a mineral oil bath. The slurry was heated
from ambient temperature to 115.degree. C. under a slow nitrogen
purge while stirring. After 3 hours, about % of the water
evaporated and stirring was not possible. The stirrer and the oil
bath were turned off and the slurry was left to slowly cool in the
bath with a slow nitrogen flow overnight. The water evaporated
overnight.
[0427] Heat treatment Method A1 was achieved by placing 20 gram of
the supported NH4F.HF on AlSiO.sub.2 solid mixture in a small glass
dish. The dish was placed in a muffle furnace and heated at
400.degree. C. for 3 hours. While still "hot" (about 250.degree.
C.), the solids were transferred into a "hot" (about 110.degree.
C.) schlenk round bottom flask. The flask was capped with a rubber
septa and placed under vacuum while it cooled to ambient
temperature. The solids were then stored under nitrogen.
[0428] Heat treatment Method A2 was achieved by charging a 3 L
round bottom flask (1-neck, 24/40) (2/3 full) with the supported
ammonium bifluoride salt on AlSiO.sub.2. The 3 L flask was then
placed in a muffle furnace and heat-treated for 5 hours at
400.degree. C. The flask was removed from the muffle furnace and
cooled to about 250.degree. C. The flask was then equipped with a
coarse glass filter adapter and placed in a vacuum atmosphere's
antechamber where it was then placed under vacuum and backfilled
with nitrogen three times. The flask was then stored under nitrogen
in a glove box.
[0429] Heat treatment Method A3 was achieved by transferring the
contents from each 3 L Flask into two medium (170 mm O.D..times.90
mm Height) glass dishes and two large (190 mm O.D..times.100 mm
Height) glass dishes. The glass dishes were then placed in a muffle
furnace at 350.degree. C. After 1.0 hour, the temperature reached
to 400.degree. C. and left at this temperature for 5 hours. The
dish was taken out of the muffle furnace and place in a hood to
cool to about 250.degree. C. (thermocouple). The solids were slowly
transferred into a 2 gallon pressure/vacuum vessel (Alloy Products)
that was equipped with a metal funnel. The process was repeated for
the second dish. The vessel was placed under vacuum (-30 in. Hg)
overnight. The vessel was transferred into a glove box and slowly
filled with nitrogen. The catalysts were then exposed to
polymerization, the results of which follow in the tables
below.
TABLE-US-00016 TABLE IVH Heat Pol. Support Treatment Cat. Time
Propyl- Activity B.D. MF Example # Method Method (mg) (min.) ene
(g) H.sub.2 (ppm) (g/g/h) (g/mL) (dg/min.) 1 A A1 20 30 690 43
14642 0.41 16.5 2 A A1 20 60 698 43 10461 0.46 5 3 B A1 20.0 30 690
43 14806 4 B A1 10.2 30 170 118 2392 5 B A1 10.3 30 170 118 4224 6
B A2 10.0 30 170 118 1462 7 B A2 10.1 30 170 118 1308 8 B A2 10.2
30 170 118 512 9 B A1 10.2 30 170 118 8012 10 B A1 10.3 30 170 118
8548 11 B A2 10.0 30 170 118 3715 12 B A2 10.0 30 170 118 4052 13 B
A2 10.3 30 170 118 2619 14 B A1 10.1 30 172 117 10826 15 B A1 10.2
30 175 115 5556 16 B A3 10.0 30 175 115 7328 17 B A3 10.4 30 175
115 9254 18 B A2* 10.2 30 175 115 5274 19 B A2* 10.0 30 175 115
6619 20 MAO/SiO2-M 40.2 30 732 42 7312 21 B A3 30.6 30 729 42 5583
22 B A3 30.5 30 695 42 8020 23 B A3 30.0 30 695 42 10086
Example-V
[0430] In the following examples, samples of fluorinated
metallocene catalyst compounds were prepared.
[0431] As used below "Silica P-10" refers to silica that was
obtained from Fuji Sylisia Chemical LTD (grade: Cariact P-10, 20
.mu.m), such silica having a surface area of 281 m.sup.2/g, a pore
volume of 1.41 mL/g, an average particle size of 20.5 .mu.m and a
pH of 6.3.
[0432] As used below "DEAF" refers to diethylaluminum fluoride
(26.9 wt. % in heptane) that was obtained from Akzo Nobel Polymer
Chemicals, L.L.C.
[0433] As used below "Silica H-121" refers to silica that was
obtained from Asahi Sunsphere, such silica having a surface area of
761 m.sup.2/g, a pore volume of 0.91 mL/g, and an average particle
size of 12.0 .mu.m.
[0434] Fluorinated Support A: The preparation of Fluorinated
Support A was achieved by slurrying 20.0 g of silica P10 (heat
treated at 150 C for 16 hours) in 150 mL of toluene at room
temperature. The preparation then included adding 2.36 g (0.0240
moles) of DEAF (26.9 wt. % in heptane) to the slurry and stirring
for 5 minutes. The resulting mixture was heated to a reaction
temperature of 50 C and stirred for 1 hour. The resulting solid was
filtered through a glass filter funnel and washed 3 times with 50
mL of hexane. The solid was then dried under vacuum at ambient
temperature. The solids were then transferred into a quartz tube
having a glass-fritted disc. The quartz tube was then inserted into
a tube furnace and equipped with an inverted glass fritted funnel
on the top opening of the tube. The mixture was then fluidized with
nitrogen (0.6 SLPM). Upon fluidization, the tube was heated from
room temperature to 130.degree. C. over 1.0 hour. Then the tube was
heated from 130.degree. C. to 450.degree. C. over 1.0 hour. Upon
reaching the average reaction temperature, the tube was maintained
at the average reaction temperature for another 1.0 hours. The tube
was then heated and held to an average calcining temperature of
480.degree. C. for 1.0 hour. The tube was then removed from the
heat and cooled under nitrogen.
[0435] Fluorinated Support B: The preparation of Fluorinated
Support B was achieved by slurrying 20.0 g of silica P10 (heat
treated at 150 C for 16 hours) in 150 mL of toluene at room
temperature. The preparation then included adding 2.36 g (0.0240
moles) of DEAF (26.9 wt. % in heptane) to the slurry and stirring
for 5 minutes. The resulting mixture was heated to a reaction
temperature of 50 C and stirred for 1 hour. The resulting solid was
filtered through a glass filter funnel and washed 3 times with 50
mL of hexane. The solid was then dried under vacuum at ambient
temperature. The solids were then transferred into a quartz tube
having a glass-fritted disc. The quartz tube was then inserted into
a tube furnace and equipped with an inverted glass fritted funnel
on the top opening of the tube. The mixture was then fluidized with
nitrogen (0.6 SLPM). Upon fluidization, the tube was heated from
room temperature to 130.degree. C. over 1.0 hour. Then the tube was
heated from 130.degree. C. to 450.degree. C. over 1.0 hour. Upon
reaching the average reaction temperature, the tube was maintained
at the average reaction temperature for another 1.0 hour. The tube
was then heated and held to an average calcining temperature of
480.degree. C. for 1.0 hour. The tube was then removed from the
heat and cooled under nitrogen. The tube was then heat treated for
the second time under air (0.6 SLPM) with the same heat treatment
profile.
[0436] Fluorinated Support C: The preparation of Fluorinated
Support C was achieved by slurrying 20.0 g (0.0144 moles) of silica
H-121 (heat treated at 150 C for 16 hours) in 100 mL toluene at
room temperature. The preparation then included adding 25.5 g
(0.0657 moles) of DEAF (26.9 wt. % in heptane) to the slurry and
stirring for 5 minutes. The resulting mixture was heated to a
reaction temperature of 50 C and stirred for 1 hour. The resulting
solid was filtered through a glass filter funnel and washed 3 times
with 50 mL of hexane. The solid was then dried under vacuum at
ambient temperature. The solids were then transferred into a quartz
tube having a glass-fritted disc. The quartz tube was then inserted
into a tube furnace and equipped with an inverted glass fritted
funnel on the top opening of the tube. The mixture was then
fluidized with nitrogen (0.6 SLPM). Upon fluidization, the tube was
heated from room temperature to 130.degree. C. over 1.0 hour. Then
the tube was heated from 130.degree. C. to 450.degree. C. over 1.0
hour. Upon reaching the average reaction temperature, the tube was
maintained at the average reaction temperature for another 1.0
hour. The tube was then heated and held to an average calcining
temperature of 480.degree. C. for 1.0 hour. The tube was then
removed from the heat and cooled under nitrogen.
[0437] Fluorinated Support D: The preparation of Fluorinated
Support D was achieved by slurrying 20.0 g (0.0144 moles) of silica
H-121 (heat treated at 150 C for 16 hours) in 100 mL toluene at
room temperature. The preparation then included adding 25.5 g
(0.0657 moles) of DEAF (26.9 wt. % in heptane) to the slurry and
stirring for 5 minutes. The resulting mixture was heated to a
reaction temperature of 50 C and stirred for 1 hour. The resulting
solid was filtered through a glass filter funnel and washed 3 times
with 50 mL of hexane. The solid was then dried under vacuum at
ambient temperature. The solids were then transferred into a quartz
tube having a glass-fritted disc. The quartz tube was then inserted
into a tube furnace and equipped with an inverted glass fitted
funnel on the top opening of the tube. The mixture was then
fluidized with nitrogen (0.6 SLPM). Upon fluidization, the tube was
heated from room temperature to 130.degree. C. over 1.0 hour. Then
the tube was heated from 130.degree. C. to 450.degree. C. over 1.0
hour. Upon reaching the average reaction temperature, the tube was
maintained at the average reaction temperature for another 1.0
hour. The tube was then heated and held to an average calcining
temperature of 480.degree. C. for 1.0 hour. The tube was then
removed from the heat and cooled under nitrogen. The tube was then
heat treated for the second time under air (0.6 SLPM) with the same
heat treatment profile.
[0438] Catalyst A: The preparation of Catalyst A was achieved by
slurrying 1.05 grams of the support A in 6 mL of toluene at ambient
temperature and stirring with a magnetic stir bar. The preparation
then included adding 4.04 g of TIBAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 25.2 mg of
rac-diemthylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.5 hours. The resulting
mixture was filtered through a glass filter funnel and washed once
with 5 mL toluene followed by washing once with 5 mL hexane. The
final solids were then dried under vacuum and slurried in mineral
oil.
[0439] Catalyst B: The preparation of Catalyst B was achieved by
slurrying 1.03 grams of the support B in 6 mL of toluene at ambient
temperature and stirring with a magnetic stir bar. The preparation
then included adding 4.01 g of TIBAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 20.0 mg of
rac-diemthylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.5 hours. The resulting
mixture was filtered through a glass filter funnel and washed once
with 5 mL toluene followed by washing once with 5 mL hexane. The
final solids were then dried under vacuum and slurried in mineral
oil.
[0440] Catalyst C: The preparation of Catalyst C was achieved by
slurrying 1.0 gram of the support B in 6 mL of toluene at ambient
temperature and stirring with a magnetic stir bar. The preparation
then included adding 4.04 g of TIBAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 21.2 mg of
Ph.sub.2C(Cp)(Flu)zirconium dichloride to the fluorinated support
at room temperature. The resulting mixture was then stirred for 3.0
hours. The resulting mixture was filtered through a glass filter
funnel and washed two times with 5 mL hexane. The final solids were
then dried under vacuum and slurried in mineral oil.
[0441] Catalyst D: The preparation of Catalyst D was achieved by
slurrying 1.02 gram of the support B in 6 mL of toluene at ambient
temperature and stirring with a magnetic stir bar. The preparation
then included adding 4.01 g of TIBAl (25.2 wt. % in heptane) to the
mixture and the mixture was then stirred for about 5 minutes at
room temperature. The preparation then included adding 22.7 mg of
iPr(3-tBu-5-Me-Cp)(Flu)zirconium dichloride to the fluorinated
support at room temperature. The resulting mixture was then stirred
for 1.0 hour. The resulting mixture was filtered through a glass
filter funnel and washed two times with 5 mL hexane. The final
solids were then dried under vacuum and slurried in mineral
oil.
[0442] Catalyst E: The preparation of Catalyst E was achieved by
slurrying 1.10 g of Fluorinated Support C in 6 mL of toluene and
stirring with a magnetic stir bar. The preparation then included
adding 4.01 g of TIBAl (25.2 wt. % in heptane) to the mixture and
the mixture was then stirred for about 5 minutes at room
temperature. The preparation then included adding 21.2 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.5 hours at room
temperature. The resulting mixture was filtered through a glass
filter funnel and washed once with 5 mL toluene followed by washing
once with 5 mL hexane. The final solids were then dried under
vacuum and slurried in mineral oil.
[0443] Catalyst F: The preparation of Catalyst F was achieved by
slurrying 1.02 g of Fluorinated Support D in 6 mL of toluene and
stirring with a magnetic stir bar. The preparation then included
adding 4.02 g of TIBAl (25.2 wt. % in heptane) to the mixture and
the mixture was then stirred for about 5 minutes at room
temperature. The preparation then included adding 21.5 mg of
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride to the fluorinated support at room temperature. The
resulting mixture was then stirred for 1.0 hour at room
temperature. The resulting mixture was filtered through a glass
filter funnel and washed once with 5 mL toluene followed by washing
once with 5 mL hexane. The final solids were then dried under
vacuum and slurried in mineral oil.
[0444] The resulting catalysts were then exposed to polymerization
with olefin monomer to form the resulting polymer. The results of
such polymerizations follow in Table VA.
TABLE-US-00017 TABLE VA (Polypropylene) Temp Co- Activity MFI (g/10
T.sub.r DH.sub.r T.sub.m DH.sub.m Catalyst (.degree. C.) Catalyst
(g/g/h) min) (.degree. C.) (J/g) (.degree. C.) (J/g) M.sub.w
M.sub.w/M.sub.n M.sub.z/M.sub.w A 67 TiBAl 1511 108.8 95.0 150.0
100.0 96747 3.8 2.0 B 67 TiBAl 5849 45.8 108.0 91.4 149.7 97.2
174815 4.7 2.7 B 67 TiBAl 6613 B 67 TEAL 405 109.5 94.2 149.9 102.0
119610 5.6 2.3 C 60 TiBAl 562 122.9 10.5 n.d. 127746 2.8 2.1 D 67
TiBAl 110 108.0 -80.1 145.4 80.3 107649 3.5 2.1 E 67 TiBAl 64 105.3
74.3 139.7 66.6 18336 3.3 4.9 F 67 TiBAl 203 109.1 90.1 143.0 103.3
38372 5.5 6.0 Polymerization Conditions: 170 g Propylene, 14 mmoles
H2, 10 mg Co-Catalyst, 30 min. n.d. = not detected, t is
polymerization time in minutes, activity is expressed in
gPP/gCat/hour, M is the catalyst loading in wt. %, T.sub.R is
recrystallization temperature in .degree. C., T.sub.M2 is the
temperature of the second melt peak in .degree. C., HLMI is
explessed in g/10 min., Catalyst E is composed of the metallocene
rac-Ethylenebis(tetrahydroindenyl)ZrCl2 supported on MAO/SiO2
support.
[0445] Unexpectedly, it has been discovered that the productivity
of polyolefin polymerizations can be controlled by the catalyst
preparation methods described herein.
[0446] As demonstrated in the examples above, a higher activity was
observed with the silica P-10 than with the silica H-121.
Example-VI
[0447] In the following examples, samples of fluorinated
metallocene catalysts were prepared according to the fourth
embodiments.
[0448] As used in the examples, the first support type "SiAl (5%)"
refers to silica alumina that was obtained from Fuji Sylisia
Chemical LTD (Silica-Alumina 205 20 .mu.m), such silica having a
surface area of 260 m.sup.2/g, a pore volume of 1.30 mL/g, an
aluminum content of 4.8 wt. %, an average particle size of 20.5
.mu.m, a pH of 6.5 and a 0.2% loss on drying.
[0449] As used in the examples, the second support type "Silica
P-10" refers to silica that was obtained from Fuji Sylisia Chemical
LTD (grade: Cariact P-10, 20 .mu.m), such silica having a surface
area of 281 m.sup.2/g, a pore volume of 1.41 mL/g, an average
particle size of 20.5 .mu.m and a pH of 6.3.
[0450] As used in the examples, "(NH.sub.4).sub.2SiF.sub.6" refers
to ammonium hexafluorosilicate that was obtained from Aldrich
Chemical Company.
[0451] As used in the examples, "DEAF" refers to diethylaluminum
fluoride (26.9 wt. % in heptane) that was obtained from Akzo Nobel
Polymer Chemicals, L.L.C.
[0452] As used in the examples, "TIBAL" refers to triisobutyl
aluminum (25 wt. % in heptane) that was obtained from Akzo
Nobel.
[0453] As used in the examples, metallocene type "A" refers to
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride.
[0454] As used in the examples, metallocene type "B" refers to
diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium
dichloride.
[0455] As used in the examples, metallocene type "C" refers to
rac-dimethylsilanylbis(2-methyl-4,5-benzo-1indenyl)zirconium
dichloride
Example 1
[0456] The first preparation of fluorinated metallocene catalyst
(Type #1) included a first support material including an
alumina-silica (SiAl (5%)) prepared in a tube furnace with 6 wt. %
(NH.sub.4).sub.2SiF.sub.6 at 450.degree. C. under nitrogen. The
second preparation of fluorinated metallocene catalyst (Type #2)
included a second support material including alumina silica
prepared by reaction of Silica P-10 with DEAF.
[0457] The support materials were slurried in mineral oil and
treated with 1 equivalent of TIBAL.
[0458] The metallocene compound was prepared in a solution of
hexane and treated with 2 equivalents of TIBAL.
[0459] The fluorinated metallocene catalysts were prepared by
mixing the prepared metallocene compound and the support material
slurry in a vessel at room temperature for a precontact time.
[0460] The prepared fluorinated metallocene catalysts were then
exposed to polymerization in 6.times. parallel reactors with
propylene monomer (170 g) at 67.degree. C. over 30 minutes to form
the resulting polypropylene. The results of such polymerizations
follow in Tables VIA (activity) and VIB (polymer properties) and in
FIGS. 3 and 4 (comp. MAO system.)
TABLE-US-00018 TABLE VIA Pre- Tac- Tac- Prep. Co- contact ticity
ticity Type Met. Cata- Time Activity (% (% Run No. Type lyst (min)
(g/g/h) mmmm) rrrr) 1 1 A TIBAL 0 267 2 1 A TIBAL 30 2900 3 2 A
TIBAL 35 4967 97.9 0.0 4 2 A TEAL 30 6143 5 2 B TIBAL 30 2620 0.3
68.6 6 1 C N/A 30 3321 Poly. Cond.: polypropylene 170 g, hydrogen
14 mmol, catalyst 30 mg, catalyst support/TIBAL 1/2, polym temp.
67.degree. C., polym. time 30 min; Tc is crystallization
temperature, Tm is melting point
TABLE-US-00019 TABLE VIB .DELTA.Hc Tm .DELTA.Hm Mw/ Peak Mz/ # Tc
(.degree. C.) (J/g) (.degree. C.) (J/g) Mn Mw Mz Mn Mw Mw 1 107.63
86.01 147.87 87.77 21571 106771 255439 4.9 107380 2.4 2 106.47 93.3
149.37 102.55 26926 121119 329054 4.7 -- 2.7 3 105.97 -90.77 149.7
90.27 44563 189440 406144 4.3 158431 2.1 5 -- -- N/A -- 59384
155947 319497 2.6 2.1 2.0 6 87.47 -69.93 128.9 75.82 3082 110039
235125 3.2 106832 2.1
[0461] It was observed that increasing the pre-contact time
resulted in increased catalyst activity. In addition, no reactor
fouling was experienced.
Example 2
[0462] Fluorinated metallocene catalysts were prepared in-situ via
the methods used in Example 1. The first type of fluorinated
metallocene catalyst (see, example 1) was prepared with a support
material to TIBAL weight ratio of 1:0.5 with 2 wt. % of "A"
metallocene. The second type of fluorinated metallocene differed
from Type 1 in that the support material to TIBAL weight ratio was
1:1 and the metallocene used was 1 wt. %. The third type of
fluorinated metallocene differed from Type 2 in that the support
material to TIBAL weight ratio was 1:2.
[0463] In addition, two samples of standard catalysts were prepared
for comparison. The standard catalysts were prepared by mixing the
first support with TIBAL in a toluene/heptane slurry. The first
metallocene was then added at ambient temperature. The resulting
mixture was stirred for 1 hour and then filtered. The solids were
washed with hexane and dried under vacuum. The dried solids were
then slurried in mineral oil.
[0464] The resulting metallocene catalysts were exposed to
propylene polymerizations as in Example 1. The results of such
polymerizations follow in Table VIC.
TABLE-US-00020 TABLE VIC MFI Type Precontact Activity (g/10 Run No.
Time (g/g/h) min) 1 1 30 min 3896 -- 2 1 24 hrs 2884 10.4 3 1 48
hrs 5466 -- 4 1 72 hrs 4994 -- 5 2 30 min 6019 -- 6 2 24 hrs 5861
1.6 7 2 48 hrs 4672 -- 8 2-std -- 3764 -- 9 3 30 min 5734 -- 10 3
24 hrs 4688 -- 11 3 48 hrs 2341 -- 12 3 144 hrs 2658 -- 13 3-std --
4015 -- Poly. Cond.: 170 g polypropylene, 30 mg. catalyst, 83 ppm
H2, poly temp. 67.degree. C., poly time 30 min., The standard MAO
systems further include 10 mg TIBAL cocatalyst, precontact time is
at 20.degree. C.
[0465] The above results illustrate that the optimal pre-contact
time varied depending on the specific catalyst used. Therefore,
embodiments of the invention (in-situ prep) provide the ability to
set specific precontact times based on desired transition metal
compounds. It was further observed that the in-situ preparation
methods provided higher catalyst activity than the standard
preparation.
[0466] Example 3: Catalysts (using the first catalyst compound and
the first support in a ratio of support to TIBAL of 1:1) were
prepared in-situ via the methods used in Example 1 and exposed to
propylene polymerization. However the amount of catalyst was varied
by sample. The polymerization results follow in Table VID.
TABLE-US-00021 TABLE VID precontact time Cat amount Activity Run
(@20.degree. C.) H.sub.2 (ppm) (mg) (g/g/hr) 1 30 min 83 30 6019 2
30 min 83 20 7459 3 30 min 119 20 8292 Poly cond.: 170 g propylene,
poly temp. 67.degree. C., poly time 30 min
[0467] It was observed that the catalyst activity increased at
higher catalyst and hydrogen concentrations.
Example 4
[0468] Catalysts were prepared in-situ via the methods used in
Example 1 and exposed to propylene/ethylene copolymerization. In
comparative experiments 3 and 4, type "A" metallocene was supported
on MAO/SiO.sub.2 support. The amount of ethylene was varied in each
run. The polymerization results follow in Table VIE.
TABLE-US-00022 TABLE VIE C.sub.2, wt. % in Activity Run Supp Type
Cat Type Cat. (mg) H.sub.2 (mmol) feed (g/g/h) Tm (.degree. C.) MF
1 1 A 20 10 2 11900 141.4 13.0 2 1 A 10 10 3 17000 -- 17 3 2 A 10
10 2 8400 -- 66.9 4 2 A 10 10 3 8200 -- 61.7 5 1 A + B 30 10 2 6600
141.4 5.4 6 1 C 20 10 2 4300 -- 150 Poly cond.: propylene 170 g,
poly temp 67.degree. C., poly time 30 min
[0469] Unexpectedly, no fouling was observed during the
polymerizations while maintaining sufficient activity.
Example-VII
[0470] In the following examples, samples of fluorinated
metallocene catalysts were prepared.
[0471] As used in the examples, the first support type "SiAl (5%)"
refers to silica alumina that was obtained from Fuji Silysia
Chemical LTD (Silica-Alumina 205 20 .mu.m), such silica having a
surface area of 260 m.sup.2/g, a pore volume of 1.30 mL/g, an
aluminum content of 4.8 wt. %, an average particle size of 20.5
.mu.m, a pH of 6.5 and a 0.2% loss on drying.
[0472] As used in the examples, the second support type "Silica
P-10" refers to silica that was obtained from Fuji Silysia Chemical
LTD (grade: Cariact P-10, 20 .mu.m), such silica having a surface
area of 296 m.sup.2/g, a pore volume of 1.41 mL/g, an average
particle size of 20.5 .mu.m and a pH of 6.3.
[0473] As used in the examples, the fluorinating agent refers to
ammonium hexafluorosilicate ((NH.sub.4).sub.2SiF.sub.6) that was
obtained from Aldrich Chemical Company.
[0474] As used in the examples, "DEAF" refers to diethylaluminum
fluoride (26.9 wt. % in heptane) that was obtained from Akzo Nobel
Polymer Chemicals, L.L.C.
[0475] As used in the examples, "TIBAL" refers to triisobutyl
aluminum (25 wt. % in heptane) that was obtained from Akzo Nobel
Polymer Chemicals, L.L.C.
Example 1
[0476] The first type of fluorinated metallocene catalyst (Type #1)
included
rac-dimethylsilanlbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride supported on a first support material including an
alumina-silica (SiAl (5%)) prepared with 3 wt. % fluorinating
agent. The second type of fluorinated metallocene catalyst (Type
#2) differs from Type #1 in that it was prepared with 6 wt. %
fluorinating agent while the third type (Type #3) was prepared with
10 wt. % fluorinating agent. The fourth type of fluorinated
metallocene catalyst (Type #4) included a second support material
including an alumina-silica (SiAl (1%)) prepared with 6 wt. %
fluorinating agent.
[0477] The prepared fluorinated metallocene catalysts were then
exposed to polymerization in 6.times. parallel reactors with
propylene monomer at 67.degree. C. over 30 minutes to form the
resulting polypropylene. The results of such polymerizations follow
in Table VIIA.
TABLE-US-00023 TABLE VIIA Support Activity T.sub.recryst
.DELTA.H.sub.rec T.sub.m .DELTA.H.sub.2nd Run Type (g/g/h)
(.degree. C.) (J/g) (.degree. C.) .sub.Tm(J/g) Mw Mw/Mn Mz/Mw 1
MAO/SiO.sub.2 10,786 107.6 -90.9 149.0 72.1 200,199 5.2 3.3 P10 2 1
200 108.5 91.1 147.7 99.45 96,239 7.2 2.8 3 2 1,334 107.9 94.24
148.7 104.6 105,258 5.2 2.3 4 3 472 108.8 -87.3 146.7 87.5 76,055
5.9 2.6 5 4 108 105.3 -76.1 140.4 75.4.sup.a 47,833 5.2 3.2 170 g
propylene, 14 mmoles H.sub.2, 10 mg TEAL co-catalyst .sup.aA second
melt was observed at 146.9.degree. C.
[0478] While runs 2-5 produced polymers having lower molecular
weights than that of the comparison polymer (run 1), it was
observed that variations of the fluoride to alumina ratios show an
effect on both the melting point and the molecular weight of the
polymers produced.
Example 2
[0479] The effect of different co-catalysts on the second type of
fluorinated metallocene catalyst used in Example 1 above was
observed. The catalyst was exposed to polymerization in a 6.times.
parallel reactor with propylene monomer at 67.degree. C. over 30
minutes to form the resulting polypropylene. The results of such
polymerizations follow in Table VIIB.
TABLE-US-00024 TABLE VIIB Co- Activity T.sub.recryst
.DELTA.H.sub.rec T.sub.m .DELTA.H.sub.2nd Run Catalyst (g/g/h)
(.degree. C.) (J/g) (.degree. C.) .sub.Tm(J/g) Mw Mw/Mn Mz/Mw 1
TEAl 1,334 108.0 94.2 148.7 104.6 105,258 5.2 2.3 2 TIBAl 5,272
107.1 91.5 149.4 96.1 200,708 4.8 2.6 3 TEAl 255 108.8 93.0 147.9
102.9 106,002 5.7 2.5 4 TIBAl 1,972 109.3 93.9 150.2 102.9 126,714
4.6 2.2 5 IPA 708 110.6 93.1 149.7 103.4 148,002 5.9 2.7 170 g
propylene, 14 mmoles H.sub.2, 10 mg co-catalyst
[0480] It was observed that use of TIBAl rather than TEAl resulted
in increased activity and Mw. Generally, the melting point
(T.sub.m) was not affected by the type of co-catalyst.
Example 3
[0481] The effect of contacting the support material (Type #2) with
different second aluminum containing compounds was observed. The
catalyst was then exposed to polymerization in a 6.times. parallel
reactor with propylene monomer at 67.degree. C. over 30 minutes to
form the resulting polypropylene. Runs 1 and 2 utilized a 1:1
catalyst to Al.sup.2 ratio, while runs 3 and 4 utilized a 1:0.5
catalyst to Al.sup.2 ratio. The results of such polymerizations
follow in Table VIIC.
TABLE-US-00025 TABLE VIIC Activity T.sub.recryst .DELTA.H.sub.rec
T.sub.m .DELTA.H.sub.2nd Run Al.sup.2 (g/g/h) (.degree. C.) (J/g)
(.degree. C.) .sub.Tm(J/g) Mw Mw/Mn Mz/Mw 1 TIBAl 5,272 107.1 91.5
149.4 96.1 200,708 4.8 2.6 2 TIBAl 3,127 108.3 92.4 150.2 105.3
210,975 5.6 2.6 3 TIBAl 1,069 109.5 91.1 150.0 100.8 134,190 5.2
2.2 4 MAO 1,544 108.6 92.9 149.2 103.1 151,747 8.1 2.6 170 g
propylene, 14 mmoles H.sub.2, 10 mg TIBAl co-catalyst
[0482] It was observed that use of MAO rather than TIBAl as the
second aluminum containing compound resulted in decreased Mw with
an increase in molecular weight distribution (Mw/Mn). Further,
bimodal molecular weight distributions were observed. (See, FIG.
5.) Generally, the melting point (T.sub.m) was not affected by the
type of second aluminum containing compound.
Example-VIII
[0483] In the following examples, samples of copolymers were
prepared.
[0484] As used in the examples, metallocene type "M1" refers to
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride.
[0485] As used in the examples, metallocene type "M2" refers to
rac-dimethylsilanylbis(2-methyl-4,5-benzo-1indenyl)zirconium
dichloride.
[0486] As used in the examples, metallocene type "M3" refers to
diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium
dichloride.
[0487] As used in the examples, silica alumina refers to silica
alumina that was obtained from Fuji Sylisia Chemical LTD
(Silica-Alumina 205 20 .mu.m), such silica having a surface area of
260 m.sup.2/g, a pore volume of 1.30 mL/g, an aluminum content of
4.8 wt. %, an average particle size of 20.5 .mu.m and a pH of
6.5.
[0488] As used in the examples, Support Type B refers to silica
obtained from Fuji Sylisia Chemical LTD (grade: Cariact P-10, 20
.mu.m), such silica having a surface area of 281 m.sup.2/g, a pore
volume of 1.41 mL/g, an average particle size of 20.5 .mu.m and a
pH of 6.3, which was treated with methyl alumoxane (0.7 g per 1 g
of silica).
[0489] As used in the examples, Support Type A1 was prepared by dry
mixing silica alumina with 6 wt. % (NH.sub.4).sub.2SiF.sub.6 and
then transferring the mixture into a quartz tube having a
glass-fitted disc. The quartz tube was then inserted into a tube
furnace and equipped with an inverted glass fritted funnel on the
top opening of the tube. The mixture was then fluidized with
nitrogen (0.4 SLPM). Upon fluidization, the tube was heated from
room temperature to an average reaction temperature of 450.degree.
C. over a period of 6 hours.
[0490] As used in the examples, Support Type A2 was prepared by
mixing silica alumina with 6 wt. % NH.sub.4F.HF in water, drying in
a rotavap and then transferring the mixture into a muffle furnace.
The muffle furnace was then heated from room temperature to an
average reaction temperature of 400.degree. C. over a period of 3
hours.
[0491] As used in the examples, Support Type A3 was prepared by
mixing silica alumina with 8 wt. % NH.sub.4F.HF, drying in a
rotavap and then transferring the mixture into a muffle furnace.
The muffle furnace was then heated from room temperature to an
average reaction temperature of 400.degree. C. over a period of 3
hours.
[0492] The preparations of the supported catalyst systems were
achieved by mixing a support material (A1, A2, A3 or B) with from 5
to 10 mg of one or more metallocene compounds (M1, M2 and/or M3)
and from 2 to 4 g of triisobutyl aluminum (25% solution in hexane)
for 30 min at room temperature. The preparation then included
adding 4 g. of mineral oil to the mixture to form a catalyst
slurry.
[0493] Ethylene/Propylene Polymerizations: Each catalyst slurry was
then contacted with ethylene and/or propylene monomer to form
polymer. The polymerization conditions and results of each
polymerization follow in Tables VIIIA and VIIIB.
TABLE-US-00026 TABLE VIIIA Ethylene MFI Support Metallocene
Cocat/Cat (wt. % in Activity (g/10 Run # Type Type Cat. (mg) wt.
ratio feed) H.sub.2 (ppm) (g/g/h) min.) 1 A1 M1 19.7 NA 0 119 8292
4.0 2 A1 M1 20.1 NA 2 119 11934 4.4 3 A1 M1 9.9 NA 2 116 8348 95.0
4 A1 M1 10.0 NA 3 115 16903 17.0 5 A1 M1 9.9 NA 5 113 34378 8.9
.sup. 6 (comp) B M1 10.2 0.49 2 116 8392 66.9 .sup. 7 (comp) B M1
9.9 0.5 3 115 8192 61.7 .sup. 8 (comp) B M1 10.0 0.5 5 113 8025
61.4 9 A2 M1 20.1 NA 0 119 7409 16.0 10 A1 M1 10.2 NA 0 119 6664
9.1 11 A2 M1 7.0 NA 0 59 5735 1.6 12 A2 M1 7.1 NA 2 58 10632 4.6 13
A2 M1 7.0 NA 3 58 12350 4.2 14 A1 M2 20 NA 0 10 3321 FAST 15 A1 M2
20 NA 2 10 4274 >150 16 A2 M1 + M3 NR NA 0 119 4751 13.0 17 A2
M1 + M3 NR NA 2 119 6607 5.4 18 A2 M1 10 NA 0 42 10396 16.5 19 A2
M1 10 NA 1 42 15173 7.3 20 A2 M1 10 NA 2 42 17460 6.2 21 A3 M1 10
NA 0 10 mmol 10320 17 22 A3 M1 7 NA 2 10 mmol 18888 18 23 A3 M1 7
NA 5 10 mmol 38028 7 *MFI refers to melt flow index and is measured
via ASTM-D-1238-E, Runs 1-17, 21-23 in 6X parallel reactor, Runs
18-20 in 2L reactor, Runs 1-17, 21-23 170 g. propylene, Runs 18-20
700 g propylene), 67.degree. C., Runs 1-22 over 30 minutes, Run 23
over 20 minutes)
TABLE-US-00027 TABLE VIIIB Run # T.sub.r (.degree. C.)
.DELTA.H.sub.r (J/g) T.sub.m (.degree. C.) .DELTA.H.sub.m (J/g) Mw
Mw/Mn Mz/Mw 1 108.5 97.0 150.1 102.2 394172 8.1 3.4 2 99.2 83.9
141.3 94.4 488946 8.6 2.8 3 98.3 81.6 140.0 81.8 NR NR NR 4 93.3
75.4 135.5 75.3 NR NR NR 5 83.5 59.6 127.9 58.5 NR NR NR 6 99.0
78.0 140.2 79.3 NR NR NR 7 94.3 72.4 135.9 75.5 NR NR NR 8 83.8
61.1 131.0 59.6 NR NR NR 9 106.0 91.0 150.2 98.5 230521 4.8 2.3 10
NR NR NR NR NR NR NR 11 NR NR NR NR NR NR NR 12 NR NR NR NR NR NR
NR 13 NR NR NR NR NR NR NR 14 NR NR NR NR NR NR NR 15 NR NR NR NR
NR NR NR 16 108.3 83.2 150.3 93.0 276433 5.5 2.4 17 99.9 77.9 141.4
88.4 420871 6.3 3.5 18 107.6 95.4 151.5 116.8 NR NR NR 19 101.1
90.1 143.4 113.7 NR NR NR 20 95.0 76.7 136.7 93.7 NR NR NR 21 109.2
94.6 150.7 111.3 NR NR NR 22 99.6 84.3 140.6 104.1 NR NR NR 23 83.9
64.2 125.1 90.8 NR NR NR *Tr refers to recrystallization
temperature, .DELTA.Hr refers to heat of recrystallization, Tm
refers to melting point, .DELTA.Hm refers to heat of melt, Mw
refers to weight average molecular weight, Mn refers to number
average molecular weight and Mz refers to z average molecular
weight, NR means not recorded, NA means not applicable
[0494] Unexpectedly, it was observed that the activity of the
Fl-Al--Si supported catalyst systems increased with an increasing
ethylene content (in contrast to an essentially unchanged activity
with the MAO based systems). In addition, a decrease in the polymer
melt flow was observed with the Fl-Al-Si supported catalyst
systems. Further, a slight increase in the polymer ethylene
incorporation was observed with the Fl-Al--Si supported catalyst
systems over the MAO based systems.
[0495] Propylene/1-Hexene Polymerizations: Each catalyst slurry was
then contacted with propylene and/or 1-hexene monomer to form
polymer. The polymerization conditions and results of each
polymerization follow in Tables VIIIC and VIIID.
TABLE-US-00028 TABLE VIIIC 1-Hexene MFI Support Metallocene
Cocat/Cat (wt. % in Activity (g/10 Run # Type Type Cat. (mg) wt.
ratio feed) H.sub.2 (ppm) (g/g/h) min.) 24 A3 M1 10(1 wt. %) 0 10
mmol 11634 6.6 25 A3 M1 10(1 wt. %) 0 10 mmol 10320 17.1 26 A3 M1
10(1 wt. %) 2 10 mmol 8782 27 A3 M1 10(1 wt. %) 3 10 mmol 5595 19.9
28 A3 M1 10(1 wt. %) 4 10 mmol 4704 34.9 *MFI refers to melt flow
index and is measured via ASTM-D-1238-E, 6X parallel reactor, 170
g. propylene, 67.degree. C., 30 minutes, TIBAL: Support = 1:1 by
wt.
TABLE-US-00029 TABLE VIIID T.sub.r .DELTA.H.sub.r T.sub.m
.DELTA.H.sub.m Run # (.degree. C.) (J/g) (.degree. C.) (J/g) Mw
Mw/Mn Mz/Mw 24 107.8 94.4 150.9 114.1 313277 3.5 2.2 25 109.2 94.6
150.7 111.3 207249 4.6 2.1 26 98.6 82.5 138.4 94.9 212221 3.7 2.0
27 94.9 82.1 135.6 107.0 181861 3.8 2.0 28 90.2 76.6 130.7 100.2
161261 3.3 1.9 *Tr refers to recrystallization temperature,
.DELTA.Hr refers to heat of recrystallization, Tm refers to melting
point, .DELTA.Hm refers to heat of melt, Mw refers to weight
average molecular weight, Mn refers to number average molecular
weight and Mz refers to z average molecular weight, NR means not
recorded, NA means not applicable
[0496] A decrease in the activity of the Fl-Al--Si supported
catalyst systems was observed with an increasing 1-hexene content.
In addition, an increase in the polymer melt flow was observed with
an increasing 1-hexene content.
[0497] Propylene/Ethylene/1-Hexene Polymerizations: Each catalyst
slurry was then contacted with propylene, ethylene and/or 1-hexene
monomer to form polymer. The polymerization conditions and results
of each polymerization follow in Tables VIIIE and VIIIF.
TABLE-US-00030 TABLE VIIIE Ethylene 1-Hexene MFI Support
Metallocene (wt. % in (wt. % in H.sub.2 Activity (g/10 Run # Type
Type Cat. (mg) feed) feed) (mmol) (g/g/h) min.) 29 A3 M1 10(1 wt.
%) 0 0 10 10320 17.1 30 A3 M1 10(1 wt. %) 0 3 10 5595 19.9 31 A3 M1
10(1 wt. %) 0 4 10 4704 34.9 32 A3 M1 10(1 wt. %) 1 3 10 16334 31
33 A3 M1 10(1 wt. %) 1 5 10 16888 17 34 A3 M1 10(1 wt. %) 2 3 10
5974 33.3 35 A3 M1 10(1 wt. %) 2 5 10 20210 26 36 A3 M1 10(1 wt. %)
3 3 10 9136 17 37 A3 M1 10(1 wt. %) 3 5 10 16183 27 *MFI refers to
melt flow index and is measured via ASTM-D-1238-E, 6X parallel
reactor, 170 g. propylene, 67.degree. C., 30 minutes, TIBAL:
Support = 1:1 by wt.
TABLE-US-00031 TABLE VIIIF T.sub.r .DELTA.H.sub.r T.sub.m
.DELTA.H.sub.m Run # (.degree. C.) (J/g) (.degree. C.) (J/g) Mw
Mw/Mn Mz/Mw 29 109.2 94.6 150.7 111.3 207249 4.6 2.1 30 94.9 82.1
135.6 107.0 181861 3.8 2.0 31 90.2 76.6 130.7 100.2 161261 3.3 1.9
32 88.0 -68.1 134.3 66.6 201567 3.7 2.0 33 74.8 -62.9 123.7 60.4
187627 3 1.9 34 84.5 73.5 126.7 88.0 160585 3.5 2.0 35 73.5 -55.7
120.7 62.3 176025 3.1 1.9 36 76.5 -64.2 122.0 58.1 194615 3.2 2.0
37 73.8 -55.0 118.0 60.6 162713 2.9 1.9 *Tr refers to
recrystallization temperature, .DELTA.Hr refers to heat of
recrystallization, Tm refers to melting point, .DELTA.Hm refers to
heat of melt, Mw refers to weight average molecular weight, Mn
refers to number average molecular weight and Mz refers to z
average molecular weight, NR means not recorded, NA means not
applicable
[0498] A decrease in the polymer melt flow was observed with and
increase in the 1-hexene content and/or the ethylene content.
[0499] Propylene/Ethylene/Styrene Polymerizations: Each catalyst
slurry was then contacted with propylene, ethylene and/or strene
monomer to form polymer. The polymerization conditions and results
of each polymerization follow in Tables VIIIG and VIIIH.
TABLE-US-00032 TABLE VIIIG Ethylene Styrene Support Metallocene
(wt. % in (wt. % in H.sub.2 Activity Run # Type Type Cat. (mg)
feed) feed) (mmol) (g/g/h) 38 A3 M1 10 0 0 10 4110 39 A3 M1 10 0
1.9 10 1063 40 A3 M1 10 1.0 2.0 10 992 *MFI refers to melt flow
index and is measured via ASTM-D-1238-E, 2L reactor, 360 g.
propylene, 67.degree. C., 30 minutes
TABLE-US-00033 TABLE VIIIH T.sub.r .DELTA.H.sub.r T.sub.m
.DELTA.H.sub.m Run # (.degree. C.) (J/g) (.degree. C.) (J/g) Mw
Mw/Mn 38 108.3 97.8 149.8 115.9 482449 6.5 39 112.3 106.8 143.8
116.7 10663 1.9 40 108.3 105.5 139.8 116.5 11715 1.9 *Tr refers to
recrystallization temperature, .DELTA.Hr refers to heat of
recrystallization, Tm refers to melting point, .DELTA.Hm refers to
heat of melt, Mw refers to weight average molecular weight, Mn
refers to number average molecular weight and Mz refers to z
average molecular weight, NR means not recorded, NA means not
applicable
Example IX
[0500] As used in the examples, the second support type "Silica
P-10" refers to silica that was obtained from Fuji Sylisia Chemical
LTD (grade: Cariact P-10, 20 .mu.m), such silica having a surface
area of 281 m.sup.2/g, a pore volume of 1.41 mL/g, an average
particle size of 20.5 .mu.m and a pH of 6.3. Unmodified P-10 silica
is referred to herein as Support Type "A".
[0501] Support Type "B" as used herein is unmodified
Al.sub.2O.sub.3.
[0502] Support Type "C" refers to alumina-silica that was obtained
from Fuji Sylisia Chemical LTD, such silica including 4.8 wt. %
Al.sub.2O.sub.3 and having a surface area of 260 m.sup.2/g, a pore
volume of 1.3 mL/g, an average particle size of 20.5 .mu.m and a pH
of 6.5.
[0503] Support Type "D" refers to alumina-silica that was obtained
from Fuji Sylisia Chemical LTD, such silica including 4.7 wt. %
Al.sub.2O.sub.3 and having a surface area of 261 m.sup.2/g, a pore
volume of 1.12 mL/g, an average particle size of 20.29 .mu.m and a
pH of 5.9.
[0504] Support Type "E" refers to alumina-silica that was obtained
from Fuji Sylisia Chemical LTD, such silica including 5.3 wt. %
Al.sub.2O.sub.3 and having a surface area of 213 m.sup.2/g, a pore
volume of 1.24 mL/g, an average particle size of 21.13 .mu.m and a
pH of 7.8.
[0505] Support Type "F" refers to alumina-silica that was obtained
from Fuji Sylisia Chemical LTD, such silica including 7.5 wt. %
Al.sub.2O.sub.3 and having a surface area of 253 m.sup.2/g, a pore
volume of 1.16 mL/g, an average particle size of 20.4 .mu.m and a
pH of 8.6.
[0506] Support Type "G" refers to alumina-silica that was obtained
from Fuji Sylisia Chemical LTD, such silica including 7.7 wt. %
Al.sub.2O.sub.3 and having a surface area of 396 m.sup.2/g, a pore
volume of 1.11 mL/g, an average particle size of 31.7 .mu.m and a
pH of 8.8.
[0507] Support Type "H" refers to alumina-silica that was obtained
from Fuji Sylisia Chemical LTD, such silica including 7.5 wt. %
Al.sub.2O.sub.3 and having a surface area of 418 m.sup.2/g, a pore
volume of 1.16 mL/g, an average particle size of 31.7 .mu.m and a
pH of 8.3.
[0508] Support Type "I" refers to alumina-silica that was obtained
from Fuji Sylisia Chemical LTD, such silica including 1.3 wt. %
Al.sub.2O.sub.3 and having a surface area of 264 m.sup.2/g, a pore
volume of 1.3 mL/g, an average particle size of 21.7 .mu.m and a pH
of 6.7.
[0509] Support Type "J" refers to alumina-silica that was obtained
from Grace Davison, such silica including 13 wt. % Al.sub.2O.sub.3
and having a surface area of 400 m.sup.2/g, a pore volume of 1.2
mL/g, an average particle size of 76 .mu.m.
[0510] Fluorinated alumina-silica supports were prepared by adding
10.0 g of the corresponding alumina-silica to a 250 mL round bottom
flask including 31.4 mL of water at ambient temperature. The
preparation further included dissolving 1.0 g of NH.sub.4F.HF in
8.6 mL of water and adding the solution to the round bottom flask.
The resulting slurry was mixed by shaking the flask for about 2
minutes. The remaining water was then removed under vacuum (30 in.
Hg) at 90.degree. C.
[0511] The resulting white free flowing solids were placed in a
small glass dish and heated in a muffle furnace at 400.degree. C.
for 3 hours. The hot solids were poured into a hot 250 mL, 1-neck,
shlenk round bottom flask. The flask was then capped with a rubber
septum and placed under vacuum for about 15 to 20 minutes. The
flask was then stored under nitrogen.
Example 1
[0512] First, indication of metallocene activation was tested by
slurrying each support material in toluene. The preparation of
supported catalyst systems was then achieved by mixing a support
material with
rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium
dichloride, shaken and leaving the resulting solid to settle. The
resulting solids were then checked for color. The active species
(solid) is generally dark red. The results of such tests are
illustrated in Table IXA below.
TABLE-US-00034 TABLE IXA Type of Counter Ion of pH of Color of
Supported Run # Support Type support support Fluorination process
Metallocene* 1 Unsupported Yellow 2 A H 6.3 Yellow 3 A H 6.3 6% of
F-Agent, F1- Yellow method 4 B Yellow 5 B 6% of F-Agent, F1- Yellow
method 6 C H 6.5 No Yellow 7 C H 6.5 6% of F-Agent, F1- Red method
8 C H 6.5 6% of F-Agent, F2 Red method 9 D H 5.9 No Yellow 10 D H
5.9 6% of F-Agent, F2 Red method 11 E H 7.8 No Yellow 12 E H 7.8 6%
of F-Agent, F2 Red method 13 F Na 8.6 No Yellow 14 F Na 8.6 6% of
F-Agent, F2 Red method 14 F Na 8.6 6% of F-Agent, F2 Red method 15
G Na, H 8.8 No Yellow 16 G Na, H 8.8 6% of F-Agent, F1 Red method
17 H Na, NH.sub.3 8.3 No Yellow 18 H Na, NH.sub.3 8.3 6% of
F-Agent, F1 Red method 19 C H 6.5 10% of F-Agent, F2 N/A method 20
I -- 6.7 No N/A 21 I -- 6.7 6% of F-Agent, F2 N/A method 22 H Na,
NH.sub.3 8.3 10% of F-Agent, F1 N/A method 23 J -- -- No N/A 24 J
-- -- 10% of F-Agent, F2 N/A method 25 J -- -- 15% of F-Agent, F2
N/A method *Red Color indicates cation formation with the
metallocene.
[0513] The un-fluorinated catalyst systems did not show an
indication of active species. Further, the catalyst systems
including only silica or alumina were absent an indication of
active species. However, the fluorinated alumina-silica supports
exhibited a red or orange color, an indication of active
species.
Example 2
[0514] First, about 0.30 g or each support was weighed out in a 20
mL screw cap vial and 5 mL of Methyl red indicator solution (0.5 mg
of methyl red in 250 mL of isohexane) was added to from a red
acidic solid. The solid was then titrated with a 0.12 N
n-butylamine solution in isohexane. Titration was continued until
the the red color of the solids disappeared. The results of such
tests are illustrated in Table IXB below.
TABLE-US-00035 TABLE IXB 0.1N n- Support Sample Butylamine in
equivalent Run # Type (g) isohexane (mL) acid/g support.sup.(1) 1 I
0.315 0.95 3.62E-04 2 C 0.308 1.19 4.64E-04 3 F 0.309 0.85 3.30E-04
4 G 0.300 0.80 3.20E-04 5 J 0.309 1.45 5.63E-04 6 I 0.308 1.40
5.45E-04 7 C 0.307 1.65 6.45E-04 8 C 0.304 1.25 4.93E-04 9 F 0.307
1.50 5.86E-04 10 F 0.307 1.40 5.47E-04 11 J 0.303 1.95 7.72E-04 12
J 0.300 1.75 7.00E-04 .sup.(1)Measurement of surface acidity was
performed according to the method described by B. C. Roy, M. S.
Rahman and M. A. Tahman, Journal of Applied Sciences 5(7):
1275-1278, 2005 with minor modifications where the aliphatic
solvent used was isohexane instead of hexane.
Example 3
[0515] The supported catalyst systems from Examples 1 and 2 were
contacted with propylene monomer to form polymer (in 6.times.
parallel reactor or 2 L bench reactor, 170 g. propylene, 67.degree.
C.). The polymerization conditions and results of each
polymerization follow in Table IXC.
TABLE-US-00036 TABLE IXC Support non Co-cat to MFI Support to
Catalyst Cat aging Co-Cat Cat wt Propylene H.sub.2 Activity (g/10
Run # Type TIBAL Mixing (mg) Co-Cat (mg) ratio (g) (ppm) (g/g/h)
min) 1 2 0 2 3 0 3 5 0 4 6 0 5 7 1:1 RT 30 10 0.0 170 119 6664 9.1
min. 6 10 1:1 RT 30 10 0.0 170 119 6519 8.3 min. 7 12 1:1 RT 30 10
0.0 170 119 6142 11.9 min. 8 7 1:2 RT 1 hour 45 TiBAl 90 2.0 1350
36 3175 9 14 1:2 RT 1 hour 30 TiBAL 15 0.5 170 83 0 10 16 1:1 RT
1.5 hours 30 TIBAL 10 0.3 170 166 0 11 18 0
[0516] The catalyst systems absent activated metallocene (yellow
color for activation test) did not show any activities in propylene
polymerization. Unexpectedly, it has been discovered that only
fluorinated alumina-silica supports having a pH of less than about
8.0 are active in propylene polymerization.
Example-X
[0517] In the following examples, samples of fluorinated
metallocene catalyst compounds utilizing various Group 12 to 13
metal compounds were prepared.
[0518] As used below "alumina-silica support composition" refers to
alumina-silica that was obtained from Grace Davison (13 wt. %
Al).
[0519] Support Preparation Method A: The preparation of support
material A was achieved by mixing 15.0 g of the alumina-silica
support composition in 60 mL of water with 3.1 g of
NH.sub.4Fl.sub.2 (dissolved in 25 mL of water) within a 250 mL
round bottom flask to form a fluorided support including 20 wt. %
fluorinating agent. The water was then removed under vacuum at
90.degree. C. The resulting solids were then heated in a muffle
furnace at 400.degree. C. for 3 hours.
[0520] Support Preparation Method B: The preparation of support
material B was achieved by mixing the alumina-silica support
composition with Et.sub.3B in hexane at ambient conditions to form
a fluorided support, which was subsequently dried.
[0521] The dried support material was then contacted with
(NH.sub.4).sub.2SiF.sub.6 to form a fluorided support including 20
wt. % fluorinating agent. The resulting solids were then heated
under air in a tube furnace at 400.degree. C. for 2 hours.
[0522] Catalyst Preparation Method A: The preparation of support
material A was achieved by mixing 15.0 g of the alumina-silica
support composition (15 wt. % of alumina) in 60 mL of water with
3.0 g of NH.sub.4F.HF (dissolved in 25 mL of water) within a 250 mL
round bottom flask to form a fluorided support including 20 wt. %
fluorinating agent. The water was then removed under vacuum at
90.degree. C. The resulting solids were then heated in a muffle
furnace at 400.degree. C. for 3 hours.
[0523] Support Preparation Method B: 3.0 grams of alumina-silica
(13 wt. % of alumina) was placed in a 250, 1-neck, schlenk round
bottom flask and placed in a glass-drying oven at 145.degree. C.
for 16 hours. The flask was capped with a rubber septum and placed
under vacuum. After the flask cooled to ambient temperature, it was
stored in a glove box under nitrogen.
[0524] 15.0 grams of the dry alumina-silica was slurried in 30.0 mL
of isohexane followed by adding 7.72 mL Et.sub.3B (Aldrich, 1M in
Hexane). After stirring at room temperature for about 1.5 hours,
the slurry was filtered though a glass fitted filter funnel and
washed 3.times. each with 30.0 mL of isohexane. The resulting
solids were dried under vacuum at ambient temperature. The dry
boron-treated AlSiO.sub.2 was then dry mixed with 3.0 grams of
(NH.sub.4).sub.2SiF.sub.6 and transferred into a glass quartz tube.
The solids were then heated at 450.degree. C. for 2 hours under 0.6
SLPM N.sub.2 flow. After cooling to room temperature, the solids
were collected and stored under nitrogen in a glove box.
[0525] The preparation of support material B was achieved by mixing
the alumina-silica support composition with Et.sub.3B in hexane at
ambient conditions to form a fluorided support, which was
subsequently dried.
[0526] Catalyst Preparation Method C: The preparation of Catalyst C
was achieved by slurrying a support material in hexane. The slurry
was then contacted with Et.sub.3B (5 wt. %). The treated slurry was
then filtered and washed with hexane.
[0527] The preparation further included contacting
dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride
with AlR.sub.3 (AlR.sub.3/support weight ratio is 1) at ambient
conditions. The resulting mixture was then added to the slurry to
form a supported catalyst system including 1 wt. % metallocene. The
supported catalyst system was then stirred for 1.0 hour.
[0528] Catalyst Preparation Method D: The preparation of Catalyst D
was achieved by slurrying a support material (B) in hexane. The
slurry was then contacted with TIBAl (TIBAl/support weight ratio is
0.5).
[0529] The preparation further included contacting
dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride
with AlR.sub.3 (AlR.sub.3/support weight ratio is 0.5) at ambient
conditions. The resulting mixture was then added to the slurry to
form a supported catalyst system including 1 wt. % metallocene. The
supported catalyst system was then stirred for 30 minutes.
[0530] Catalyst Preparation Method E: The preparation of Catalyst E
was achieved by slurrying a support material in hexane. The slurry
was then contacted with AlR.sub.3. (AlR.sub.3/support weight ratio
is 0.5).
[0531] The preparation further included contacting
dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride
with AlR.sub.S at ambient conditions. The resulting mixture was
then added to the slurry to form a supported catalyst system
including 1 wt. % metallocene. The supported catalyst system was
then stirred for 30 minutes.
[0532] Polymerizations: The resulting catalysts were then contacted
with propylene monomer to form polypropylene. The polymerizations
were conducted in a 6-.times. pack (6.times.500 ml) parallel bench
reactor and in 2 L Zipperclave bench reactor. The results of such
polymerizations follow in Tables XA and XB, respectively.
TABLE-US-00037 TABLE XA Cat H.sub.2 Time Activity Run Support
Catalyst R (mg) (ppm) (min) (g/g/h) 1 A A1 N/A 15 78 30 2317 2 A
E.sup.1 i-Bu 15 78 30 11873 3 A E.sup.2 i-Bu 30 42 30 10777 4 A
E.sup.2 i-Bu 30 42 30 11248 5 A B.sup.1 i-Bu 15 78 30 6373 6 A
C.sup.2 i-Bu 30 42 30 11466 7 B D.sup.2 i-Bu 30 42 30 11344 8 A
E.sup.1 n-Oct 15 78 30 13804 9 A E.sup.1 n-Oct 15 78 30 15203 10 A
E.sup.1 n-Oct 15 78 60 9178 11 A E.sup.1 n-Oct 15 156 30 12626 12 A
B.sup.1 n-Oct 15 78 30 12875 13 A B.sup.1 n-Oct 10 78 30 13890 14 A
B.sup.1 n-Oct 10 78 60 10710 15 A B.sup.1 n-Oct 10 156 30 18193 16
A E.sup.1 n-Hex 15 78 30 12457 17 A E.sup.1 i-prenyl 15 78 30 13 1
= 500 mL reactor, 180 g PP, 2 = 2L reactor, 700 g PP, all at
67.degree. C.
[0533] Acceptable catalyst activities were observed with
tri-n-hexyl aluminum (TNHAl), tri-n-octyl aluminum (TNOAl), and
tri-iso-butyl aluminum (TIBAl). However, in contrast to isolation
methods (wherein TIBAl generally exhibits higher activities than
TNOAl), TNOAl demonstrated the highest catalyst activity with
in-situ catalyst preparation methods.
[0534] However, it has been discovered that when triethyl borane
(Et.sub.3B) is present during the catalyst preparation, the
activity of the TIBAl system decreased, while the TNOAl system
demonstrated about the same or increased catalytic activity.
TABLE-US-00038 TABLE XB MFI (g/10 Run min.) XS (%) T.sub.r(.degree.
C.) .DELTA.H.sub.r(J/g) T.sub.m(.degree. C.) .DELTA.H.sub.m(J/g) Mw
Mw/Mn Mz/Mw 1 19.4 0.28 110.1 95.7 150.8 95.5 193507 4.0 2.0 2 1.4
ND 107.9 92.2 150.1 90.2 627243 6.4 2.5 3 6.0 ND 109.4 91.3 150.7
107.8 321580 7.9 2.8 4 5.6 ND 109.4 98.6 150.5 97.2 393365 7.6 3.1
5 19.8 ND 106.6 92.7 1506 91.5 225149 4.2 2.1 6 9.7 NR 108.4 88.1
151.0 100.4 282459 5.5 2.4 7 3.0 NR 107.8 94.9 150.6 104.1 370879
5.8 2.4 8 <1 NR 105.7 89.1 149.9 102.3 567369 3.9 2.2 9 7.6
<0.2 106.0 64.7 150.5 95.6 332279 5.1 2.3 10 3.4 <0.2 106.7
93.6 150.1 93.4 409637 6.4 2.4 11 62.2 0.20 110.2 97.7 150.3 100.6
137059 5.1 2.1 12 1.1 <0.2 106.8 90.5 150.4 100.8 NR NR NR 13
5.7 <0.2 108.3 95.5 150.5 96.0 395923 4.6 2.3 14 <1 ND 105.6
96.1 149.9 97.7 484894 5.9 2.3 15 6.8 ND 109.2 96.5 150.9 95.8
315293 6.8 2.9 16 1.0 NR 106.6 95.8 149.6 108.4 536058 4.3 2.3 17
NR NR NR NR NR NR NR NR NR T.sub.r is recrystallization
temperature, T.sub.M is the peak melt temperature
[0535] While the polymers produces showed consistent Tm and Hr
regardless of the polymerization conditions or type of reactor, the
melt flow and Mw varied depending on the type of reactor system.
Further, the melt flow of the polymers increased with an increase
of hydrogen.
[0536] While the foregoing is directed to embodiments of the
present invention, other and further embodiments of the invention
may be devised without departing from the basic scope thereof and
the scope thereof is determined by the claims that follow.
* * * * *