U.S. patent application number 11/218213 was filed with the patent office on 2007-03-01 for catalyst compositions comprising support materials having an improved particle-size distribution.
Invention is credited to Chi-I Kuo, Tae Hoon Kwalk, Dongming Li, Porter Clarke Shannon.
Application Number | 20070049711 11/218213 |
Document ID | / |
Family ID | 37441940 |
Filed Date | 2007-03-01 |
United States Patent
Application |
20070049711 |
Kind Code |
A1 |
Kuo; Chi-I ; et al. |
March 1, 2007 |
Catalyst compositions comprising support materials having an
improved particle-size distribution
Abstract
A catalyst composition that includes a support material having
an improved particle-size distribution is provided. Processes for
producing polyolefin composition also are provided. Polymers and
films also are provided. An example of a catalyst composition is a
supported multi-transition-metal catalyst composition that
includes: (a) at least two catalyst components selected from the
group consisting of: a nonmetallocene catalyst component and a
metallocene catalyst component; (b) a support material that has a
D.sub.50 of less than about 30 microns and a particle size
distribution having a D.sub.90/D.sub.10 ratio of less than about 6;
and (c) an activator.
Inventors: |
Kuo; Chi-I; (Humble, TX)
; Kwalk; Tae Hoon; (Belle Mead, NJ) ; Li;
Dongming; (Houston, TX) ; Shannon; Porter Clarke;
(Seabrook, TX) |
Correspondence
Address: |
Univation Technologies, LLC
Suite 1950
5555 San Felipe
Houston
TX
77056
US
|
Family ID: |
37441940 |
Appl. No.: |
11/218213 |
Filed: |
September 1, 2005 |
Current U.S.
Class: |
526/113 ;
526/129; 526/348.1 |
Current CPC
Class: |
C08J 5/18 20130101; C08F
210/16 20130101; C08F 2500/24 20130101; C08F 4/65904 20130101; C08F
210/14 20130101; C08F 4/6546 20130101; C08F 2500/17 20130101; C08F
2500/05 20130101; C08F 2500/12 20130101; C08F 4/65916 20130101;
C08F 4/65912 20130101; C08F 210/16 20130101; C08F 4/65925 20130101;
C08F 210/16 20130101; C08J 2323/04 20130101; C08F 210/16
20130101 |
Class at
Publication: |
526/113 ;
526/129; 526/348.1 |
International
Class: |
C08F 4/06 20060101
C08F004/06 |
Claims
1. A process for producing a polyolefin composition comprising:
contacting hydrogen and ethylene monomers with a supported
multi-transition-metal catalyst composition to form a polyolefin
composition; wherein the supported multi-transition-metal catalyst
composition comprises: (a) at least two catalyst components
selected from the group consisting of: a nonmetallocene catalyst
component and a metallocene catalyst component; (b) a support
material that has a D.sub.50 of less than about 30 microns and a
particle size distribution having a D.sub.90/D.sub.10 ratio of less
than about 6; and (c) an activator.
2. The process of claim 1, wherein the nonmetallocene catalyst
component is a Ziegler-Natta catalyst component that comprises a
nonmetallocene transition metal compound selected from the group
consisting of Group 4 and Group 5 halides, oxides, oxyhalides,
alkoxides, and mixtures thereof.
3. The process of claim 1, wherein the support material comprises
silica.
4. The process of claim 1, wherein the support material has a
D.sub.90 of less than about 50 microns.
5. The process of claim 1, wherein the metallocene catalyst
component is represented by the formulae: Cp.sup.ACp.sup.BMX.sub.n
and Cp.sup.A(A)Cp.sup.BMX.sub.n wherein each Cp.sup.A and Cp.sup.B
are the same or different and are substituted or unsubstituted
cyclopentadienyl rings or ligands isolobal to cyclopentadienyl,
each bound to M; M is a Group 4, 5, or 6 atom; X is selected from
the group consisting of C.sub.1 to C.sub.6 alkyls, C.sub.6 aryls,
C.sub.7 to C.sub.12 alkylaryls, fluorinated C.sub.1 to C.sub.6
alkyls, fluorinated C.sub.6 aryls, fluorinated C.sub.7 to C.sub.12
alkylaryls, chlorine and fluorine; n is 1 or 2; and (A) is a
divalent bridging group; characterized in that at least one X is a
fluorine or fluorinated hydrocarbonyl.
6. A supported multi-transition-metal catalyst composition
comprising: (a) at least two catalyst components selected from the
group consisting of: a nonmetallocene catalyst component and a
metallocene catalyst component; (b) a support material that has a
D.sub.50 of less than about 30 microns and a particle size
distribution having a D.sub.90/D.sub.10 ratio of less than about 6;
and (c) an activator.
7. The supported multitransition metal catalyst composition of
claim 6, wherein the metallocene catalyst component is represented
by the formulae: Cp.sup.ACp.sup.BMX.sub.n and
Cp.sup.A(A)Cp.sup.BMX.sub.n wherein each Cp.sup.A and Cp.sup.B are
the same or different and are substituted or unsubstituted
cyclopentadienyl rings or ligands isolobal to cyclopentadienyl,
each bound to M; M is a Group 4, 5, or 6 atom; X is selected from
the group consisting of C.sub.1 to C.sub.6 alkyls, C.sub.6 aryls,
C.sub.7 to C.sub.12 alkylaryls, fluorinated C.sub.1 to C.sub.6
alkyls, fluorinated C.sub.6 aryls, fluorinated C.sub.7 to C.sub.12
alkylaryls, chlorine and fluorine; n is 1 or 2; and (A) is a
divalent bridging group; characterized in that at least one X is a
fluorine or fluorinated hydrocarbonyl.
8. The supported multitransition metal catalyst composition of
claim 6, wherein the nonmetallocene catalyst component is a
Ziegler-Natta catalyst component that comprises a nonmetallocene
transition metal compound selected from the group consisting of
Group 4 and Group 5 halides, oxides, oxyhalides, alkoxides, and
mixtures thereof.
9. The supported multitransition metal catalyst composition of
claim 6, wherein the support material comprises silica.
10. The supported multitransition metal catalyst composition of
claim 6, wherein the support material has a D.sub.90 of less than
about 50 microns.
11. A polymer made from a process comprising: contacting hydrogen
and ethylene monomers with a supported multi-transition-metal
catalyst composition to form a polyolefin composition; wherein the
supported multi-transition-metal catalyst composition comprises:
(1) at least two catalyst components selected from the group
consisting of: a nonmetallocene catalyst component and a
metallocene catalyst component; (2) a support material that has a
D.sub.50 of less than about 30 microns and a particle size
distribution having a D.sub.90/D.sub.10 ratio of less than about 6;
and (3) an activator.
12. The polymer of claim 11, wherein the nonmetallocene catalyst
component is a Ziegler-Natta catalyst component that comprises a
nonmetallocene transition metal compound selected from the group
consisting of Group 4 and Group 5 halides, oxides, oxyhalides,
alkoxides, and mixtures thereof.
13. The polymer of claim 11, wherein the metallocene catalyst
component is represented by the formulae: Cp.sup.ACp.sup.BMX.sub.n
and Cp.sup.A(A)Cp.sup.BMX.sub.n wherein each Cp.sup.A and Cp.sup.B
are the same or different and are substituted or unsubstituted
cyclopentadienyl rings or ligands isolobal to cyclopentadienyl,
each bound to M; M is a Group 4, 5, or 6 atom; X is selected from
the group consisting of C.sub.1 to C.sub.6 alkyls, C.sub.6 aryls,
C.sub.7 to C.sub.12 alkylaryls, fluorinated C.sub.1 to C.sub.6
alkyls, fluorinated C.sub.6 aryls, fluorinated C.sub.7 to C.sub.12
alkylaryls, chlorine and fluorine; n is 1 or 2; and (A) is a
divalent bridging group; characterized in that at least one X is a
fluorine or fluorinated hydrocarbonyl.
14. The polymer of claim 11, wherein the support material comprises
silica.
15. The polymer of claim 11, wherein the support material has a
D.sub.90 of less than about 50 microns.
16. The polymer of claim 11, having a density in the range of from
about 0.940 to about 0.960 grams per cubic centimeter.
17. The polymer of claim 11, having a melt index ratio in the range
of from about 70 to about 200.
18. The polymer of claim 11, having an HLMI in the range of from
about 4 to about 15.
19. A film made from a polymer that is the product of a process
comprising: contacting hydrogen and ethylene monomers with a
supported multi-transition-metal catalyst composition to form a
polyolefin composition; wherein the supported
multi-transition-metal catalyst composition comprises: (1) at least
two catalyst components selected from the group consisting of: a
nonmetallocene catalyst component and a metallocene catalyst
component; (2) a support material that has a D.sub.50 of less than
about 30 microns and a particle size distribution having a
D.sub.90/D.sub.10 ratio of less than about 6; and (3) an
activator.
20. The film of claim 19 wherein the film has a Gel Count of less
than 30.
21. The film of claim 19 wherein the film has a Gel Count of less
than 10.
22. The film of claim 19, wherein the support material comprises
silica.
23. The film of claim 19, wherein the support material has a
D.sub.90 of less than about 50 microns.
24. The film of claim 19, wherein the metallocene catalyst
component is represented by the formulae: Cp.sup.ACp.sup.BMX.sub.n
and Cp.sup.A(A)Cp.sup.BMX.sub.n wherein each Cp.sup.A and Cp.sup.B
are the same or different and are substituted or unsubstituted
cyclopentadienyl rings or ligands isolobal to cyclopentadienyl,
each bound to M; M is a Group 4, 5, or 6 atom; X is selected from
the group consisting of C.sub.1 to C.sub.6 alkyls, C.sub.6 aryls,
C.sub.7 to C.sub.12 alkylaryls, fluorinated C.sub.1 to C.sub.6
alkyls, fluorinated C.sub.6 aryls, fluorinated C.sub.7 to C.sub.12
alkylaryls, chlorine and fluorine; n is 1 or 2; and (A) is a
divalent bridging group; characterized in that at least one X is a
fluorine or fluorinated hydrocarbonyl.
Description
FIELD OF INVENTION
[0001] The present invention relates to catalysts for polyolefin
production, and more particularly, to supported catalysts for use
in making polyolefins that may be used in producing polymer
products, wherein the supported catalyst comprises a support
material having an improved particle-size distribution, and
wherein, in a desirable embodiment, the supported catalyst is used
to produce the polyolefin in a single reactor.
BACKGROUND
[0002] Advances in polymerization and catalysis have resulted in
the ability to produce many new polymers having improved physical
and chemical properties useful in a wide variety of superior
products and applications. With the development of new catalysts,
the choice of polymerization techniques (solution, slurry, high
pressure or gas phase) for producing a particular polymer have been
greatly expanded. Also, advances in polymerization technology have
provided more efficient, highly productive and economically
enhanced processes.
[0003] As with any new technology field, particularly in the
polyolefins industry, a small savings in cost often determines
whether a commercial endeavor is even feasible. The industry has
been extremely focused on developing new and improved catalyst
systems. Some have focused on designing the catalyst systems to
produce new polymers, others on improving operability, and many
more on improving catalyst productivity. The productivity of a
catalyst usually is the key economic factor that can make or break
a new commercial development in the polyolefin industry.
[0004] Multi-modal polymers produced using multiple different
catalyst types--bimetallic, trimetallic, quadrimetallic catalysts,
and the like--are of increasing interest, especially in producing
polyethylene and other polyolefins. Improving catalyst productivity
also is of concern here, as productivity should be as high as
possible in order to optimize the economic efficiency of the
process, given the significant cost of multiple transition metal
catalysts.
[0005] Another aspect of polyolefin production pertains to the
level of gels (e.g., visible imperfections) present in the polymer
products. Polymer products, especially films, that are produced
with a high gel concentration may have limited or no commercial
value due to, inter alia, poor aesthetics, bubble stability, or
continuity. Accordingly, minimizing the concentration of gels in
the polymer product--especially gels of such size as to be visually
perceptible--is of great importance.
SUMMARY OF THE INVENTION
[0006] An example of a process of the present invention is a
process for producing a polyolefin composition comprising:
contacting hydrogen and ethylene monomers with a supported
multi-transition-metal catalyst composition to form a polyolefin
composition; wherein the supported multi-transition-metal catalyst
composition comprises: (a) at least two catalyst components
selected from the group consisting of: a nonmetallocene catalyst
component and a metallocene catalyst component; (b) a support
material that has a D.sub.50 of less than about 30 microns and a
particle size distribution having a D.sub.90/D.sub.10 ratio of less
than about 6; and (c) an activator.
[0007] An example of a catalyst composition of the present
invention is a supported multi-transition-metal catalyst
composition comprising: (a) at least two catalyst components
selected from the group consisting of: a nonmetallocene catalyst
component and a metallocene catalyst component; (b) a support
material that has a D.sub.50 of less than about 30 microns and a
particle size distribution having a D.sub.90/D.sub.10 ratio of less
than about 6; and (c) an activator.
[0008] An example of a polymer of the present invention is a
polymer made from a process comprising: contacting hydrogen and
ethylene monomers with a supported multi-transition-metal catalyst
composition to form a polyolefin composition; wherein the supported
multi-transition-metal catalyst composition comprises: (1) at least
two catalyst components selected from the group consisting of: a
nonmetallocene catalyst component and a metallocene catalyst
component; (2) a support material that has a D.sub.50 of less than
about 30 microns and a particle size distribution having a
D.sub.90/D.sub.10 ratio of less than about 6; and (3) an
activator.
[0009] An example of a film of the present invention is a film made
from a polymer that is the product of a process comprising:
contacting hydrogen and ethylene monomers with a supported
multi-transition-metal catalyst composition to form a polyolefin
composition; wherein the supported multi-transition-metal catalyst
composition comprises: (1) at least two catalyst components
selected from the group consisting of: a nonmetallocene catalyst
component and a metallocene catalyst component; (2) a support
material that has a D.sub.50 of less than about 30 microns and a
particle size distribution having a D.sub.90/D.sub.10 ratio of less
than about 6; and (3) an activator.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 illustrates a graphical depiction of the particle
size distributions of certain exemplary polymers, including an
exemplary polymer produced in accordance with a polymerization
process of the present invention, along with comparative
examples.
[0011] FIG. 2 illustrates a graphical depiction of the gel count
exhibited by certain exemplary polymers, including an exemplary
polymer produced in accordance with a polymerization process of the
present invention, along with comparative examples.
DETAILED DESCRIPTION
General Definitions
[0012] As used herein, in reference to Periodic Table "Groups" of
Elements, the "new" numbering scheme for the Periodic Table Groups
are used as in the CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R.
Lide ed., CRC Press 81.sup.st ed. 2000).
[0013] As used herein, the phrase "supported multi-transition-metal
catalyst" or "supported multi-transition-metal catalyst
composition" refers to compositions that include, inter alia, two
or more "catalyst components," at least one "activator," and a
support material of the present invention having an improved
particle size distribution. Suitable catalyst components,
activators, and support materials are described further herein. The
supported multi-transition-metal catalyst also may include other
components (e.g., fillers), and is not limited to the activators,
support materials, and the two or catalyst components. In addition
to comprising a support material of the present invention having an
improved particle size distribution, the supported
multi-transition-metal catalysts of the present invention may
include, inter alia, any number of catalyst components in any
combination as described herein, as well as any activator in any
combination as described herein.
[0014] As used herein, the phrase "catalyst compound" includes any
compound that, once appropriately activated, is capable of
catalyzing the polymerization or oligomerization of olefins, the
catalyst compound comprising at least one Group 3 to Group 12 atom,
and optionally at least one leaving group bound thereto.
[0015] As used herein, the phrase "leaving group" refers to one or
more chemical moieties bound to the metal center of the catalyst
component that can be abstracted from the catalyst component by an
activator, thus producing a species active towards olefin
polymerization or oligomerization. Suitable activators are
described further below.
[0016] As used herein, the term "substituted" means that the group
following that term possesses at least one moiety in place of one
or more hydrogens in any position, the moieties selected from such
groups as halogen radicals (esp., Cl, F, Br), hydroxyl groups,
carbonyl groups, carboxyl groups, amine groups, phosphine groups,
alkoxy groups, phenyl groups, naphthyl groups, C.sub.1 to C.sub.10
alkyl groups, C.sub.2 to C.sub.10 alkenyl groups, and combinations
thereof. Examples of substituted alkyls and aryls includes, but are
not limited to, acyl radicals, alkylamino radicals, alkoxy
radicals, aryloxy radicals, alkylthio radicals, dialkylamino
radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals,
carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy
radicals, acylamino radicals, arylamino radicals, and combinations
thereof.
[0017] As used herein, structural formulas are employed as is
commonly understood in the chemical arts; lines ("--") used to
represent associations between a metal atom ("M", Group 3 to Group
12 atoms) and a ligand or ligand atom (e.g., cyclopentadienyl,
nitrogen, oxygen, halogen ions, alkyl, etc.), as well as the
phrases "associated with", "bonded to" and "bonding", are not
limited to representing a certain type of chemical bond, as these
lines and phrases are meant to represent a "chemical bond"; a
"chemical bond" defined as an attractive force between atoms that
is strong enough to permit the combined aggregate to function as a
unit, or "compound".
[0018] A certain stereochemistry for a given structure or part of a
structure should not be implied unless so stated for a given
structure or apparent by use of commonly used bonding symbols such
as by dashed lines and/or heavy lines.
[0019] Unless stated otherwise, no embodiment of the present
invention is herein limited to the oxidation state of the metal
atom "M" as defined below in the individual descriptions and
examples that follow. The ligation of the metal atom "M" is such
that the compounds described herein are neutral, unless otherwise
indicated.
[0020] As used herein, the term "bimodal," when used to describe a
polymer or polymer composition (e.g., polyolefins such as
polyethylene, or other homopolymers, copolymers or terpolymers)
means "bimodal molecular weight distribution," which is understood
as having the broadest definition persons in the pertinent art have
given that term as reflected in printed publications and issued
patents. For example, a single composition that includes
polyolefins with at least one identifiable high molecular weight
distribution and polyolefins with at least one identifiable low
molecular weight distribution is considered to be a "bimodal"
polyolefin, as that term is used herein. In a particular
embodiment, other than having different molecular weights, the high
molecular weight polyolefin and the low molecular weight polyolefin
may be essentially the same type of polymer, for example,
polyethylene. As used herein, the terms "trimodal," "quadrimodal,"
and "multimodal" similarly shall be understood as having the
broadest definition persons in the pertinent art have given those
terms as reflected in printed publications and issued patents.
[0021] As used herein, the term "productivity" means the weight of
polymer produced per weight of the catalyst used in the
polymerization process (e.g., grams polymer/gram catalyst).
[0022] As used herein, the term "dehydrated" is understood as
having the broadest definition persons in the pertinent art have
given that term in describing catalyst support materials (e.g.,
silica), as reflected in printed publications and issued patents,
and includes any material (for example, a support particle), from
which a majority of the contained/adsorbed water has been
removed.
[0023] The terms "D.sub.10," "D.sub.50," and "D.sub.90" will be
used herein to describe the particle size distribution of a sample
of a particular support material. As used herein, the term
"D.sub.10" is understood to mean that 10% of the particles in a
sample of a support material have a diameter smaller than the
D.sub.10 value. The term "D.sub.50" will be understood to mean the
median particle size value. The term "D.sub.90" will be understood
to mean that 90% of the particles in the sample have a diameter
smaller than the D.sub.90 value.
[0024] As referred to herein, the term "Group 8-10 metal-containing
catalyst" will be understood to refer to a catalyst compound
comprising at least one metal chosen from among Groups 8-10.
[0025] As referred to herein, the term "late transition metal" will
be understood to refer to a metal chosen from among Groups
8-10.
Supported Multi-Transition-Metal Catalysts of the Present
Invention
[0026] According to one embodiment of the present invention,
supported multi-transition-metal catalysts are provided that
include, inter alia, an activator, at least two catalyst
components, and a support material that has a D.sub.50 of less than
about 30 microns and a particle size distribution having a
D.sub.90/D.sub.10 ratio of less than about 6. In certain
embodiments, the at least two catalyst components are selected from
the group consisting of a nonmetallocene catalyst component and a
metallocene catalyst component--e.g., the at least two catalyst
components may comprise at least two nonmetallocene catalyst
components, or they may comprise at least two metallocene catalyst
components, or they may comprise at least one metallocene catalyst
component and at least one nonmetallocene catalyst component, and
the like. Examples of suitable catalyst components, activators and
support materials are set forth further below.
[0027] A variety of catalyst components may be suitable for use in
the supported multi-transition-metal catalysts of the present
invention, including, inter alia, metallocene catalyst components
and nonmetallocene catalyst components.
[0028] The supported multi-transition-metal catalysts of the
present invention may be used to produce polymer products that are
multi-modal, e.g., the polymer products may be bimodal, trimodal,
or quadrimodal, for example. Indeed, in certain embodiments, the
supported multi-transition-metal catalyst systems of the present
inventions may comprise five or more catalyst components. Thus, in
certain embodiments, a higher molecular weight resin (e.g., >ca
100,000 amu) can be produced from, for example, a catalyst
component that may comprise a titanium non-metallocene catalyst
component. In certain embodiments, a lower molecular weight resin
(e.g., <ca 100,000 amu) can be produced from, for example, a
metallocene catalyst component. Accordingly, polymerization in the
presence of multiple, differing catalyst components may provide a
multi-modal polyolefin composition that includes components of
differing molecular weight. For example, polymerization in the
presence of one nonmetallocene catalyst component and one
metallocene catalyst component may provide a bimodal polyolefin
composition that includes a low molecular weight component and a
high molecular weight component.
[0029] Certain embodiments of the present invention involve
contacting monomers with nonmetallocene and/or metallocene catalyst
components of the supported multi-transition-metal catalysts of the
present invention. In a particular embodiment, each different
catalyst component that is present in the multi-transition-metal
catalyst resides, or is supported on a single type of support such
that, on average, each particle of support material includes one of
each nonmetallocene and/or metallocene catalyst components that are
present in the multi-transition-metal catalyst. In another
embodiment, each different catalyst component may be supported
separately from the other catalyst components (e.g., in a
bimetallic catalyst system, a metallocene catalyst component may be
supported separately from a nonmetallocene catalyst component),
such that on average any given particle of support material
comprises only a single catalyst component. In this later
embodiment, each supported catalyst may be introduced into the
polymerization reactor sequentially in any order, alternately in
parts, or simultaneously.
[0030] In one embodiment of the present invention, a catalyst
component may be first combined with the support material, and then
the supported catalyst component may be combined with another
catalyst component. For example, in one embodiment, a
non-metallocene catalyst component may be first combined with a
support material, to provide a supported non-metallocene
composition; the supported non-metallocene composition then may be
combined with a metallocene catalyst component, resulting in a
bimetallic catalyst composition having enhanced productivity when
used in production of a bimodal polyolefin composition. Other
combinations are possible as will be understood by those of
ordinary skill in the art.
[0031] Various methods of affixing multiple different catalyst
components (albeit differing combinations of catalyst components)
to a support can be used. An example of one general procedure for
preparing a supported multitransitional metal catalyst can include
providing a supported nonmetallocene catalyst component, contacting
a slurry that includes the nonmetallocene catalyst component in a
non-polar hydrocarbon with a solution that includes a metallocene
catalyst component, which also may include an activator, drying the
resulting product that includes the nonmetallocene and metallocene
catalyst components, and recovering a supported bimetallic catalyst
composition. Other procedures for preparing supported bimetallic
catalyst compositions, as well as other supported multitransitional
metal catalyst compositions (e.g., those that are trimetallic,
quadrimetallic, and the like) will be recognized by those of
ordinary skill in the art.
Nonmetallocene Catalyst Component
[0032] In certain embodiments of the present invention, a
supported, multi-transition-metal catalyst composition may be
prepared that comprises one or more nonmetallocene catalyst
components. As used herein, the term "non-metallocene catalyst
component" refers to any catalyst component that is neither a
metallocene nor one of the metallocene-type catalyst compounds
identified below. A broad variety of compounds may be suitable for
use as a non-metallocene catalyst component in the present
invention. Examples of preferred nonmetallocene catalyst components
include, inter alia, Ziegler-Natta catalysts, including but not
limited to titanium- or vanadium-based Ziegler-Natta catalyst
components, such as, for example, titanium and vanadium halides,
oxyhalides or alkoxyhalides, such as titanium tetrachloride
(TiCl.sub.4), vanadium tetrachloride (VCl.sub.4) and vanadium
oxytrichloride (VOCl.sub.3), and titanium and vanadium alkoxides,
wherein the alkoxide moiety has a branched or unbranched alkyl
group of 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.
Other examples of preferred nonmetallocene catalyst components
include, but are not limited to, catalyst components comprising
early transitional metal Group 4 and 5 atoms, such as hafnium-,
zirconium-, and niobium halides. Still other examples of preferred
nonmetallocene catalyst components include, inter alia, catalyst
components comprising chromium oxide or organochromium compounds,
such as, for example, silica- or alumina-supported chromium oxide
or Cr(pi-allyl).sub.3. As another example, a preferred
nonmetallocene catalyst component may include, inter alia,
alumina-supported molybdenium oxide. Other examples of preferred
nonmetallocene catalyst components include, inter alia, catalyst
components comprising neodymium and/or lanthanum. Additional
examples of preferred nonmetallocene catalyst components include,
inter alia, late-transition-metal or post-metallocene catalyst
components, including those that are multidentate comprising
oxygen, nitrogen, phosphorus, sulfur or silica.
[0033] As noted above, in certain embodiments, the supported
multi-transition-metal catalysts of the present invention may
comprise a nonmetallocene catalyst component that is a
Ziegler-Natta catalyst compound. Ziegler-Natta catalyst components
are well known in the art and described by, for example, ZIEGLER
CATALYSTS 363-386 (G. Fink, R. Mulhaupt and H. H. Brintzinger,
eds., Springer-Verlag 1995). Examples of such catalysts include
those comprising TiCl.sub.4 and other such transition metal oxides
and chlorides. In certain embodiments, the supported
multi-transition-metal catalysts of the present invention may
comprise a nonmetallocene catalyst component that is a
Ziegler-Natta catalyst component that comprises a nonmetallocene
transition metal compound selected from the group consisting of
Group 4 and Group 5 halides, oxides, oxyhalides, alkoxides, and
mixtures thereof.
[0034] In embodiments of the present invention wherein one or more
nonmetallocene catalyst components are used, a nonmetallocene
catalyst component may be combined with a support material of the
present invention in one embodiment, either with or without another
catalyst component (e.g., a metallocene catalyst component, or the
same or different nonmetallocene catalyst component). The
nonmetallocene catalyst component can be combined with, placed on,
or otherwise affixed to a support material of the present invention
in a variety of ways. In one of those ways, a slurry of the support
material in a suitable non-polar hydrocarbon diluent may be
contacted with an organomagnesium compound, which then dissolves in
the non-polar hydrocarbon diluent of the slurry to form a solution
from which the organomagnesium compound is then deposited onto the
carrier. The organomagnesium compound can be represented by the
formula RMgR', where R' and R are the same or different
C.sub.2-C.sub.12 alkyl groups, or C.sub.4-C.sub.10 alkyl groups, or
C.sub.4-C.sub.8 alkyl groups. In at least one specific embodiment,
the organomagnesium compound is dibutyl magnesium.
[0035] In one embodiment, the amount of organomagnesium compound
included in the silica slurry is only that which will be deposited,
physically or chemically, onto the support material of the present
invention, for example, being bound to the hydroxyl groups on the
support material, and no more than that amount, since any excess
organomagnesium compound may cause undesirable side reactions.
Routine experimentation can be used to determine the optimum amount
of organomagnesium compound. For example, the organomagnesium
compound can be added to the slurry while stirring the slurry,
until the organomagnesium compound is detected in the support
solvent. Alternatively, the organomagnesium compound can be added
in excess of the amount that is deposited onto the support
material, in which case any undeposited excess amount can be
removed by filtration and washing. The amount of organomagnesium
compound (moles) based on the amount of dehydrated silica (grams)
generally range from 0.2 mmol/gram to 2 mmol/gram in one
embodiment.
[0036] Optionally, the organomagnesium compound-treated slurry may
be contacted with an electron donor, such as
tetraethylorthosiloxane (TEOS) or an organic alcohol R''OH, where
R'' is a C.sub.1-C.sub.12 alkyl group, or a C.sub.1 to C.sub.8
alkyl group, or a C.sub.2 to C.sub.4 alkyl group. In a particular
embodiment, R''OH may be n-butanol. The amount of organic alcohol
used may be an amount effective to provide an R''OH:Mg mol/mol
ratio of from 0.2 to 1.5, or from 0.4 to 1.2, or from 0.6 to 1.1,
or from 0.9 to 1.1.
[0037] The slurry (which, as noted, optionally may be
organomagnesium-treated and/or alcohol-treated) may be contacted
with a non-metallocene transition metal compound. The amount of
non-metallocene transition metal compound used is sufficient to
give a transition metal to magnesium mol/mol ratio of from 0.3 to
1.5, or from 0.5 to 0.8. The diluent can then be removed in a
conventional manner, such as by evaporation or filtering, to obtain
the dry, supported nonmetallocene catalyst component.
[0038] In embodiments in which one or more nonmetallocene catalyst
components are used (e.g., in conjunction with other nonmetallocene
catalyst components and/or with one or more metallocene catalyst
components), the catalyst components may be contacted with the
support material of the present invention in any order. In a
particular embodiment of the invention, a nonmetallocene catalyst
component is reacted first with the support material of the present
invention as described above, followed by contacting this supported
nonmetallocene catalyst component with a metallocene catalyst
component.
Metallocene Catalyst Component
[0039] In certain embodiments of the present invention, a
supported, multi-transition-metal catalyst may be prepared that
comprises one or more nonmetallocene catalyst components.
Metallocene catalyst compounds are generally described throughout
in, for example, 1 & 2 METALLOCENE-BASED POLYOLEFINS (John
Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000);
G. G. Hlatky in 181 COORDINATION CHEM. REV. 243-296 (1999) and in
particular, for use in the synthesis of polyethylene in 1
METALLOCENE-BASED POLYOLEFINS 261-377 (2000). The metallocene
catalyst compounds as described herein include "half sandwich" and
"full sandwich" compounds having one or more Cp ligands
(cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound
to at least one Group 3 to Group 12 metal atom, and one or more
leaving group(s) bound to the at least one metal atom. They also
include constrained-geometry catalyst compounds, including metal
atoms from Groups 3, 4, 5, and 6B. Hereinafter, these compounds
will be referred to as "metallocenes" or "metallocene catalyst
components". Where included, a metallocene catalyst component may
be supported on a support material of the present invention in a
particular embodiment as described further below, and may be
supported with or without one or more nonmetallocene catalyst
components (with one or more nonmetallocene catalyst components, in
a particular embodiment).
[0040] The Cp ligands are typically .alpha.-bonded and/or fused
ring(s) or ring systems. The ring(s) or ring system(s) typically
comprise atoms selected from the group consisting of Groups 13 to
16 atoms, and more particularly, the atoms that make up the Cp
ligands are selected from the group consisting of carbon, nitrogen,
oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum
and combinations thereof, wherein carbon makes up at least 50% of
the ring members. Even more particularly, the Cp ligand(s) may be
selected from the group consisting of substituted and unsubstituted
cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl,
non-limiting examples of which include cyclopentadienyl, indenyl,
fluorenyl and other structures. Further non-limiting examples of
such ligands include cyclopentadienyl, cyclopentaphenanthreneyl,
indenyl, benzindenyl, fluorenyl, octahydrofluorenyl,
cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl,
3,4-benzofluorenyl, 9-phenylfluorenyl,
8-H-cyclopent[a]acenaphthylenyl, 7H-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. In a particular embodiment, the metallocenes
useful in the present invention may be selected from those
including one or two (two, in a more particular embodiment), of the
same or different Cp rings selected from the group consisting of
cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, and
substituted versions thereof.
[0041] The metal atom "M" of the metallocene catalyst compound, as
described throughout the specification and claims, may be selected
from the group consisting of Groups 3 through 12 atoms and
lanthanide Group atoms in one embodiment; and selected from the
group consisting of Groups 3 through 10 atoms in a more particular
embodiment, and selected from the group consisting of Sc, Ti, Zr,
Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more
particular embodiment; and selected from the group consisting of
Groups 4, 5 and 6 atoms in yet a more particular embodiment, and
from Ti, Zr, Hf atoms in yet a more particular embodiment, and may
be Zr in yet a more particular embodiment. The oxidation state of
the metal atom "M" may range from 0 to +7 in one embodiment; and in
a more particular embodiment, is +1, +2, +3, +4 or +5; and in yet a
more particular embodiment is +2, +3 or +4. The groups bound to the
metal atom "M" are such that the compounds described below in the
formulas and structures are electrically neutral, unless otherwise
indicated. The Cp ligand(s) form at least one chemical bond with
the metal atom M to form the "metallocene catalyst compound". The
Cp ligands are distinct from the leaving groups bound to the
catalyst compound in that they are not highly susceptible to
substitution/abstraction reactions.
[0042] In one aspect of the invention, the one or more metallocene
catalyst components of the invention are represented by the formula
(I): Cp.sup.ACp.sup.BMX.sub.n (I) wherein M is as described above;
each X is chemically bonded to M; each Cp group is chemically
bonded to M; and n is an integer from 0 to 4, and either 1 or 2 in
a particular embodiment.
[0043] The ligands represented by Cp.sup.A and Cp.sup.B in formula
(I) may be the same or different cyclopentadienyl ligands or
ligands isolobal to cyclopentadienyl, either or both of which may
contain heteroatoms and either or both of which may be substituted
by a group R. In one embodiment, Cp.sup.A and Cp.sup.B are
independently selected from the group consisting of the group
consisting of cyclopentadienyl, indenyl, tetrahydroindenyl,
fluorenyl, and substituted derivatives of each.
[0044] Independently, each Cp.sup.A and Cp.sup.B of formula (I) may
be unsubstituted or substituted with any one or combination of
substituent groups R. Non-limiting examples of substituent groups R
as used in formula (I) as well as ring substituents in formulas
(Va-d) include groups selected from the group consisting of
hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls,
acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines,
alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl-
and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and
combinations thereof.
[0045] More particular non-limiting examples of alkyl substituents
R associated with formula (I) through (V) include methyl, ethyl,
propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl,
phenyl, methylphenyl, and tert-butylphenyl groups and the like,
including all their isomers, for example tertiary-butyl, isopropyl,
and the like. Other possible radicals include substituted alkyls
and aryls such as, for example, fluoromethyl, fluroethyl,
difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl
substituted organometalloid radicals including trimethylsilyl,
trimethylgermyl, methyldiethylsilyl and the like; and
halocarbyl-substituted organometalloid radicals including
tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,
bromomethyldimethylgermyl and the like; and disubstituted boron
radicals including dimethylboron for example; and disubstituted
Group 15 radicals including dimethylamine, dimethylphosphine,
diphenylamine, methylphenylphosphine, Group 16 radicals including
methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.
Other substituents R include olefins such as, but not limited to,
olefinically-unsaturated substituents including vinyl-terminated
ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like.
In one embodiment, at least two R groups (two adjacent R groups in
one embodiment) are joined to form a ring structure having from 3
to 30 atoms selected from the group consisting of carbon, nitrogen,
oxygen, phosphorous, silicon, germanium, aluminum, boron and
combinations thereof. Also, a substituent group R group such as
1-butanyl may form a bonding association to the element M.
[0046] Non-limiting examples of X groups include alkyls, amines,
phosphines, ethers, carboxylates, dienes, hydrocarbon radicals
having from 1 to 20 carbon atoms; fluorinated hydrocarbon radicals
(e.g., --C.sub.6F.sub.5 (pentafluorophenyl)), fluorinated
alkylcarboxylates (e.g., CF.sub.3C(O)O.sup.-), hydrides and halogen
ions and combinations thereof. Other examples of X ligands include
alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl,
trifluoromethyl, tetramethylene, pentamethylene, methylidene,
methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),
dimethylamide, dimethylphosphide radicals and the like. In one
embodiment, two or more X's form a part of a fused ring or ring
system. In certain embodiments, X may be selected from the group
consisting of C.sub.1 to C.sub.6 alkyls, C.sub.6 aryls, C.sub.7 to
C.sub.12 alkylaryls, fluorinated C.sub.1 to C.sub.6 alkyls,
fluorinated C.sub.6 aryls, fluorinated C.sub.7 to C.sub.12
alkylaryls, chlorine and fluorine.
[0047] In another aspect of the invention, the metallocene catalyst
component includes those of formula (I) where Cp.sup.A and Cp.sup.B
are bridged to each other by at least one bridging group, (A), such
that the structure is represented by formula (II):
Cp.sup.A(A)Cp.sup.BMX.sub.n (II)
[0048] These bridged compounds represented by formula (II) are
known as "bridged metallocenes". Cp.sup.A, Cp.sup.B, M, X and n in
formula (II) are as defined above for formula (I); and wherein each
Cp ligand is chemically bonded to M, and (A) is chemically bonded
to each Cp. Non-limiting examples of bridging group (A) 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 and tin atom
and combinations thereof; wherein the heteroatom also may be
C.sub.1 to C.sub.12 alkyl or aryl substituted to satisfy neutral
valency. The bridging group (A) also may contain substituent groups
R as defined above (for formula (I)) including halogen radicals and
iron. More particular non-limiting examples of bridging group (A)
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.,
R'P.dbd. (wherein ".dbd." represents two chemical bonds), where R'
is independently selected from the group consisting of hydride,
hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted
halocarbyl, hydrocarbyl-substituted organometalloid,
halocarbyl-substituted organometalloid, disubstituted boron,
disubstituted Group 15 atoms, substituted Group 16 atoms, and
halogen radical; and wherein two or more R' may be joined to form a
ring or ring system. In one embodiment, the bridged metallocene
catalyst component of formula (II) has two or more bridging groups
(A).
[0049] Other non-limiting examples of bridging group (A) 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 diethylgermyl.
[0050] In another embodiment, bridging group (A) also may be
cyclic, comprising, for example 4 to 10 ring members (5 to 7 ring
members in a more particular embodiment). The ring members may be
selected from the elements mentioned above, from one or more of B,
C, Si, Ge, N and O in a particular embodiment. Non-limiting
examples of ring structures which may be present as or part of the
bridging moiety are cyclobutylidene, cyclopentylidene,
cyclohexylidene, cycloheptylidene, cyclooctylidene and the
corresponding rings where one or two carbon atoms are replaced by
at least one of Si, Ge, N and O (in particular, Si and Ge). The
bonding arrangement between the ring and the Cp groups may be
either cis-, trans-, or a combination.
[0051] The cyclic bridging groups (A) may be saturated or
unsaturated and/or may carry one or more substituents and/or may be
fused to one or more other ring structures. If present, the one or
more substituents are selected from the group consisting of
hydrocarbyl (e.g., alkyl such as methyl) and halogen (e.g., F, Cl)
in one embodiment. The one or more Cp groups to which the above
cyclic bridging moieties may optionally be fused may be saturated
or unsaturated, and may be selected from the group consisting of
those having 4 to 10 (more particularly 5, 6 or 7) ring members
(selected from the group consisting of C, N, O and S in a
particular embodiment) such as, for example, cyclopentyl,
cyclohexyl and phenyl. Moreover, these ring structures may
themselves be fused such as, for example, in the case of a naphthyl
group. Moreover, these (optionally fused) ring structures may carry
one or more substituents. Illustrative, non-limiting examples of
these substituents are hydrocarbyl (particularly alkyl) groups and
halogen atoms.
[0052] The ligands Cp.sup.A and Cp.sup.B of formulae (I) and (II)
may be different from each other in one embodiment, and the same in
another embodiment.
[0053] In yet another aspect of the invention, the metallocene
catalyst components include bridged mono-ligand metallocene
compounds (e.g., mono cyclopentadienyl catalyst components). In
this embodiment, the at least one metallocene catalyst component is
a bridged "half-sandwich" metallocene represented by the formula
(III): Cp.sup.A(A)QMX.sub.n (III) wherein Cp.sup.A is defined above
and is bound to M; (A) is a bridging group bonded to Q and
Cp.sup.A; and wherein an atom from the Q group is bonded to M; and
n is an integer 0, 1 or 2. In formula (III) above, Cp.sup.A, (A)
and Q may form a fused ring system. The X groups and n of formula
(III) are as defined above in formula (I) and (II). In one
embodiment, Cp.sup.A is selected from the group consisting of
cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,
substituted versions thereof, and combinations thereof.
[0054] In formula (III), Q is a heteroatom-containing ligand in
which the bonding atom (the atom that is bonded with the metal M)
is selected from the group consisting of Group 15 atoms and Group
16 atoms in one embodiment, and selected from the group consisting
of nitrogen, phosphorus, oxygen or sulfur atom in a more particular
embodiment, and nitrogen and oxygen in yet a more particular
embodiment. Non-limiting examples of Q groups include alkylamines,
arylamines, mercapto compounds, ethoxy compounds, carboxylates
(e.g., pivalate), carbamates, azenyl, azulene, pentalene,
phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl,
borabenzene, and other compounds comprising Group 15 and Group 16
atoms capable of bonding with M.
[0055] In yet another aspect of the invention, the at least one
metallocene catalyst component may be an unbridged "half sandwich"
metallocene represented by the formula (IVa):
Cp.sup.AMQ.sub.qX.sub.n (IVa) wherein Cp.sup.A is defined as for
the Cp groups in (I) and is a ligand that is bonded to M; each Q is
independently bonded to M; X is a leaving group as described above
in (I); n ranges from 0 to 3, and is 0 or 3 in one embodiment; q
ranges from 0 to 3, and is 0 or 3 in one embodiment. In one
embodiment, Cp.sup.A is selected from the group consisting of
cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,
substituted version thereof, and combinations thereof.
[0056] In formula (IVa), Q is selected from the group consisting of
ROO.sup.-, RO--, R(O)--, --NR--, --CR.sub.2--, --S--, --NR.sub.2,
--CR.sub.3, --SR, --SiR.sub.3, --PR.sub.2, --H, and substituted and
unsubstituted aryl groups, wherein R is selected from the group
consisting of C.sub.1 to C.sub.6 alkyls, C.sub.6 to C.sub.12 aryls,
C.sub.1 to C.sub.6 alkylamines, C.sub.6 to C.sub.12
alkylarylamines, C.sub.1 to C.sub.6 alkoxys, C.sub.6 to C.sub.12
aryloxys, and the like. Non-limiting examples of Q include C.sub.1
to C.sub.12 carbamates, C.sub.1 to C.sub.12 carboxylates (e.g.,
pivalate), C.sub.2 to C.sub.20 allyls, and C.sub.2 to C.sub.20
heteroallyl moieties.
[0057] Described another way, the "half sandwich" metallocenes
above can be described as in formula (IVb), such as described in,
for example, U.S. Pat. No. 6,069,213: Cp.sup.AM(Q.sub.2GZ)X.sub.n
or (IVb) T(Cp.sup.AM(Q.sub.2GZ)X.sub.n).sub.m wherein: [0058] M,
Cp.sup.A, X and n are as defined above; [0059] Q.sub.2GZ forms a
polydentate ligand unit (e.g., pivalate), wherein at least one of
the Q groups form a bond with M, and is defined such that each Q is
independently selected from the group consisting of --O--, --NR--,
--CR.sub.2-- and --S--; G is either carbon or silicon; and Z is
selected from the group consisting of R, --OR, --NR.sub.2,
--CR.sub.3, --SR, --SiR.sub.3, --PR.sub.2, and hydride, providing
that when Q is --NR--, then Z is selected from the group consisting
of --OR, --NR.sub.2, --SR, --SiR.sub.3, --PR.sub.2; and provided
that neutral valency for Q is satisfied by Z; and wherein each R is
independently selected from the group consisting of C.sub.1 to
C.sub.10 heteroatom containing groups, C.sub.1 to C.sub.10 alkyls,
C.sub.6 to C.sub.12 aryls, C.sub.6 to C.sub.12 alkylaryls, C.sub.1
to C.sub.10 alkoxys, and C.sub.6 to C.sub.12 aryloxys; [0060] n is
1 or 2 in a particular embodiment; and [0061] T is a bridging group
selected from the group consisting of C.sub.1 to C.sub.10
alkylenes, C.sub.6 to C.sub.12 arylenes and C.sub.1 to C.sub.10
heteroatom containing groups, and C.sub.6 to C.sub.12 heterocyclic
groups; wherein each T group bridges adjacent
"Cp.sup.AM(Q.sub.2GZ)X.sub.n" groups, and is chemically bonded to
the Cp.sup.A groups. m is an integer from 1 to 7; m is an integer
from 2 to 6 in a more particular embodiment.
[0062] In another aspect of the invention, the at least one
metallocene catalyst component can be described more particularly
in formulae (Va), (Vb), (Vc) and (Vd): ##STR1## [0063] wherein in
formulae (Va) to (Vd) M is selected from the group consisting of
Group 3 to Group 12 atoms, and selected from the group consisting
of Group 3 to Group 10 atoms in a more particular embodiment, and
selected from the group consisting of Group 3 to Group 6 atoms in
yet a more particular embodiment, and selected from the group
consisting of Group 4 atoms in yet a more particular embodiment,
and selected from the group consisting of Zr and Hf in yet a more
particular embodiment; and is Zr in yet a more particular
embodiment; [0064] wherein Q in (Va-i) and (Va-ii) is selected from
the group consisting of halogen ions, alkyls, alkylenes, aryls,
arylenes, alkoxys, aryloxys, amines, alkylamines, phosphines,
alkylphosphines, substituted alkyls, substituted aryls, substituted
alkoxys, substituted aryloxys, substituted amines, substituted
alkylamines, substituted phosphines, substituted alkylphosphines,
carbamates, heteroallyls, carboxylates (non-limiting examples of
suitable carbamates and carboxylates include trimethylacetate,
trimethylacetate, methylacetate, p-toluate, benzoate,
diethylcarbamate, and dimethylcarbamate), fluorinated alkyls,
fluorinated aryls, and fluorinated alkylcarboxylates; [0065] q is
an integer ranging from 1 to 3; [0066] wherein each R* is
independently: selected from the group consisting of hydrocarbyls
and heteroatom-containing hydrocarbyls in one embodiment; and
selected from the group consisting of alkylenes, substituted
alkylenes and heteroatom-containing hydrocarbyls in another
embodiment; and selected from the group consisting of C.sub.1 to
C.sub.12 alkylenes, C.sub.1 to C.sub.12 substituted alkylenes, and
C.sub.1 to C.sub.12 heteroatom-containing hydrocarbons in a more
particular embodiment; and selected from the group consisting of
C.sub.1 to C.sub.4 alkylenes in yet a more particular embodiment;
and wherein both R* groups are identical in another embodiment in
formulae (Vb-d); [0067] A is as described above for (A) in formulae
(II), and more particularly, selected from the group consisting of
--O--, --S--, --SO.sub.2--, --NR--, =SiR.sub.2, .dbd.GeR.sub.2,
.dbd.SnR.sub.2, --R.sub.2SiSiR.sub.2--, RP.dbd., C.sub.1 to
C.sub.12 alkylenes, substituted C.sub.1 to C.sub.12 alkylenes,
divalent C.sub.4 to C.sub.12 cyclic hydrocarbons and substituted
and unsubstituted aryl groups in one embodiment; and selected from
the group consisting of C.sub.5 to C.sub.8 cyclic hydrocarbons,
--CH.sub.2CH.sub.2--, .dbd.CR.sub.2 and .dbd.SiR.sub.2 in a more
particular embodiment; wherein R is selected from the group
consisting of alkyls, cycloalkyls, aryls, alkoxys, fluoroalkyls and
heteroatom-containing hydrocarbons in one embodiment; and R is
selected from the group consisting of C.sub.1 to C.sub.6 alkyls,
substituted phenyls, phenyl, and C.sub.1 to C.sub.6 alkoxys in a
more particular embodiment; and R is selected from the group
consisting of methoxy, methyl, phenoxy, and phenyl in yet a more
particular embodiment; [0068] wherein A may be absent in yet
another embodiment, in which case each R* is defined as for
R.sup.1-R.sup.12; [0069] each X is as described above in (I);
[0070] n is an integer from 0 to 4, and from 1 to 3 in another
embodiment, and 1 or 2 in yet another embodiment; and [0071]
R.sup.1 through R.sup.12 are independently: selected from the group
consisting of hydrogen radical, halogen radicals, C.sub.1 to
C.sub.12 alkyls, C.sub.2 to C.sub.12 alkenyls, C.sub.6 to C.sub.12
aryls, C.sub.7 to C.sub.20 alkylaryls, C.sub.1 to C.sub.12 alkoxys,
C.sub.1 to C.sub.12 fluoroalkyls, C.sub.6 to C.sub.12 fluoroaryls,
and C.sub.1 to C.sub.12 heteroatom-containing hydrocarbons and
substituted derivatives thereof in one embodiment; selected from
the group consisting of hydrogen radical, fluorine radical,
chlorine radical, bromine radical, C.sub.1 to C.sub.6 alkyls,
C.sub.2 to C.sub.6 alkenyls, C.sub.7 to C.sub.18 alkylaryls,
C.sub.1 to C.sub.6 fluoroalkyls, C.sub.2 to C.sub.6 fluoroalkenyls,
C.sub.7 to C.sub.18 fluoroalkylaryls in a more particular
embodiment; and hydrogen radical, fluorine radical, chlorine
radical, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
tertiary butyl, hexyl, phenyl, 2,6-di-methylphenyl, and
4-tertiarybutylphenyl groups in yet a more particular embodiment;
wherein adjacent R groups may form a ring, either saturated,
partially saturated, or completely saturated.
[0072] The structure of the metallocene catalyst component
represented by (Va) may take on many forms such as disclosed in,
for example, U.S. Pat. No. 5,703,187, and U.S. Pat. No. 5,747,406,
including a dimer or oligomeric structure, such as disclosed in,
for example, U.S. Pat. No. 5,026,798 and U.S. Pat. No.
6,069,213.
[0073] In a particular embodiment of the metallocene represented in
(Vd), R.sup.1 and R.sup.2 form a conjugated 6-membered carbon ring
system that may, or may not, be substituted.
[0074] Non-limiting examples of metallocene catalyst components
consistent with the description herein include: [0075]
cyclopentadienylzirconium X.sub.n, [0076] indenylzirconium X.sub.n,
[0077] (1-methylindenyl)zirconium X.sub.n, [0078]
(2-methylindenyl)zirconium X.sub.n, [0079]
(1-propylindenyl)zirconium X.sub.n, [0080]
(2-propylindenyl)zirconium X.sub.n, [0081]
(1-butylindenyl)zirconium X.sub.n, [0082] (2-butylindenyl)zirconium
X.sub.n, [0083] (methylcyclopentadienyl)zirconium X.sub.n, [0084]
tetrahydroindenylzirconium X.sub.n, [0085]
(pentamethylcyclopentadienyl)zirconium X.sub.n, [0086]
cyclopentadienylzirconium X.sub.n, [0087]
pentamethylcyclopentadienyltitanium X.sub.n, [0088]
tetramethylcyclopentyltitanium X.sub.n, [0089]
1,2,4-trimethylcyclopentadienylzirconium X.sub.n, [0090]
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(cyclopentadienyl)zirco-
nium X.sub.n, [0091]
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2,3-trimethylcyclope-
ntadienyl)zirconium X.sub.n, [0092]
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2-dimethylcyclopenta-
dienyl)zirconium X.sub.n, [0093]
dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(2-methylcyclopentadie-
nyl)zirconium X.sub.n, [0094]
dimethylsilyl(cyclopentadienyl)(indenyl)zirconium X.sub.n, [0095]
dimethylsilyl(2-methylindenyl)(fluorenyl)zirconium X.sub.n, [0096]
diphenylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-propylcyclopentadie-
nyl)zirconium X.sub.n, [0097]
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-t-butylcyclopentadie-
nyl)zirconium X.sub.n, [0098]
dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-isopropylcyclopentadienyl)-
zirconium X.sub.n, [0099]
dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-methylcyclopentadie-
nyl)zirconium X.sub.n, [0100]
diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium
X.sub.n, [0101]
diphenylmethylidene(cyclopentadienyl)(indenyl)zirconium X.sub.n,
[0102] iso-propylidenebis(cyclopentadienyl)zirconium X.sub.n,
[0103] iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium
X.sub.n, [0104]
iso-propylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconium
X.sub.n, [0105] ethylenebis(9-fluorenyl)zirconium X.sub.n, [0106]
meso-ethylenebis(1-indenyl)zirconium X.sub.n, [0107]
ethylenebis(1-indenyl)zirconium X.sub.n, [0108]
ethylenebis(2-methyl-1-indenyl)zirconium X.sub.n, [0109]
ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconium
X.sub.n, [0110]
ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl)zirconium
X.sub.n, [0111]
ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-indenyl)zirconium
X.sub.n, [0112]
ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X.sub.n,
[0113]
ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-indenyl)zirconium
X.sub.n, [0114]
dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X.sub.n,
[0115] diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X.sub.n,
[0116] ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium X.sub.n,
[0117] dimethylsilylbis(cyclopentadienyl)zirconium X.sub.n, [0118]
dimethylsilylbis(9-fluorenyl)zirconium X.sub.n, [0119]
dimethylsilylbis(1-indenyl)zirconium X.sub.n, [0120]
dimethylsilylbis(2-methylindenyl)zirconium X.sub.n, [0121]
dimethylsilylbis(2-propylindenyl)zirconium X.sub.n, [0122]
dimethylsilylbis(2-butylindenyl)zirconium X.sub.n, [0123]
diphenylsilylbis(2-methylindenyl)zirconium X.sub.n, [0124]
diphenylsilylbis(2-propylindenyl)zirconium X.sub.n, [0125]
diphenylsilylbis(2-butylindenyl)zirconium X.sub.n, [0126]
dimethylgermylbis(2-methylindenyl)zirconium X.sub.n, [0127]
dimethylsilylbis(tetrahydroindenyl)zirconium X.sub.n, [0128]
dimethylsilylbis(tetramethylcyclopentadienyl)zirconium X.sub.n,
[0129] dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium
X.sub.n, [0130]
diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X.sub.n,
diphenylsilylbis(indenyl)zirconium X.sub.n, [0131]
cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)zirc-
onium X.sub.n, [0132]
cyclotetramethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)zi-
rconium X.sub.n, [0133]
cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2-methylindenyl)zirco-
nium
cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(3-methylcyclopent-
adienyl)zirconium X.sub.n, [0134]
cyclotrimethylenesilylbis(2-methylindenyl)zirconium X.sub.n, [0135]
cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2,3,5-trimethylcyclop-
entadienyl)zirconium X.sub.n, [0136]
cyclotrimethylenesilylbis(tetramethylcyclopentadienyl)zirconium
X.sub.n, [0137]
dimethylsilyl(tetramethylcyclopentadienyl)(N-tert-butylamido)tita-
nium X.sub.n, [0138] bis(cyclopentadienyl)chromium X.sub.n, [0139]
bis(cyclopentadienyl)zirconium X.sub.n, [0140]
bis(n-butylcyclopentadienyl)zirconium X.sub.n, [0141]
bis(n-dodecyclcyclopentadienyl)zirconium X.sub.n, [0142]
bis(ethylcyclopentadienyl)zirconium X.sub.n, [0143]
bis(iso-butylcyclopentadienyl)zirconium X.sub.n, [0144]
bis(iso-propylcyclopentadienyl)zirconium X.sub.n, [0145]
bis(methylcyclopentadienyl)zirconium X.sub.n, [0146]
bis(n-oxtylcyclopentadienyl)zirconium X.sub.n, [0147]
bis(n-pentylcyclopentadienyl)zirconium X.sub.n, [0148]
bis(n-propylcyclopentadienyl)zirconium X.sub.n, [0149]
bis(trimethylsilylcyclopentadienyl)zirconium X.sub.n, [0150]
bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirconium X.sub.n,
[0151] bis(1-ethyl-2-methylcyclopentadienyl)zirconium X.sub.n,
[0152] bis(1-ethyl-3-methylcyclopentadienyl)zirconium X.sub.n,
[0153] bis(pentamethylcyclopentadienyl)zirconium X.sub.n, [0154]
bis(pentamethylcyclopentadienyl)zirconium X.sub.n, [0155]
bis(1-propyl-3-methylcyclopentadienyl)zirconium X.sub.n, [0156]
bis(1-n-butyl-3-methylcyclopentadienyl)zirconium X.sub.n, [0157]
bis(1-isobutyl-3-methylcyclopentadienyl)zirconium X.sub.n, [0158]
bis(1-propyl-3-butylcyclopentadienyl)zirconium X.sub.n, [0159]
bis(1,3-n-butylcyclopentadienyl)zirconium X.sub.n, [0160]
bis(4,7-dimethylindenyl)zirconium X.sub.n, [0161]
bis(indenyl)zirconium X.sub.n, [0162] bis(2-methylindenyl)zirconium
X.sub.n, [0163] cyclopentadienylindenylzirconium X.sub.n, [0164]
bis(n-propylcyclopentadienyl)hafnium X.sub.n, [0165]
bis(n-butylcyclopentadienyl)hafnium X.sub.n, [0166]
bis(n-pentylcyclopentadienyl)hafnium X.sub.n, [0167] (n-propyl
cyclopentadienyl)(n-butyl cyclopentadienyl)hafnium X.sub.n, [0168]
bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium X.sub.n, [0169]
bis(trimethylsilyl cyclopentadienyl)hafnium X.sub.n, [0170]
bis(2-n-propylindenyl)hafnium X.sub.n, [0171]
bis(2-n-butylindenyl)hafnium X.sub.n, [0172]
dimethylsilylbis(n-propylcyclopentadienyl)hafnium X.sub.n, [0173]
dimethylsilylbis(n-butylcyclopentadienyl)hafnium X.sub.n, [0174]
bis(9-n-propylfluorenyl)hafnium X.sub.n, [0175]
bis(9-n-butylfluorenyl)hafnium X.sub.n, [0176]
(9-n-propylfluorenyl)(2-n-propylindenyl)hafnium X.sub.n, [0177]
bis(1-n-propyl-2-methylcyclopentadienyl)hafnium X.sub.n, [0178]
(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium
X.sub.n, [0179]
dimethylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium
X.sub.n, [0180]
dimethylsilyl(tetramethyleyclopentadienyl)(cyclobutylamido)titanium
X.sub.n, [0181]
dimethylsilyl(tetramethyleyclopentadienyl)(cyclopentylamido)titanium
X.sub.n, [0182]
dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium
X.sub.n, [0183]
dimethylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium
X.sub.n, [0184]
dimethylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium
X.sub.n, [0185]
dimethylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium
X.sub.n, [0186]
dimethylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium
X.sub.n, [0187]
dimethylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium
X.sub.n, [0188]
dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium
X.sub.n, [0189]
dimethylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium
X.sub.n, [0190]
dimethylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium
X.sub.n, [0191]
dimethylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium
X.sub.n, [0192]
dimethylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium
X.sub.n, [0193]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium
X.sub.n, [0194]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium
X.sub.n, [0195]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium
X.sub.n, [0196]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium
X.sub.n, [0197]
methylphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium
X.sub.n, [0198]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium
X.sub.n, [0199]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium
X.sub.n, [0200]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium,
X.sub.n, [0201]
methylphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium
X.sub.n, [0202]
methylphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium
X.sub.n, [0203]
methylphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium
X.sub.n, [0204]
methylphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium
X.sub.n, [0205]
methylphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium
X.sub.n, [0206]
methylphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium
X.sub.n, [0207]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium
X.sub.n, [0208]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium
X.sub.n, [0209]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium
X.sub.n, [0210]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium
X.sub.n, [0211]
diphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium
X.sub.n, [0212]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium
X.sub.n, [0213]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium
X.sub.n, [0214]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium
X.sub.n, [0215]
diphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium
X.sub.n, [0216]
diphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium
X.sub.n, [0217]
diphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium
X.sub.n, [0218]
diphenylsilyl(tetramethyleyclopentadienyl)(n-octylamido)titanium
X.sub.n, [0219]
diphenylsilyl(tetramethyleyclopentadienyl)(n-decylamido)titanium
X.sub.n, [0220]
diphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium
X.sub.n, and derivatives thereof, wherein the value of n is 1, 2 or
3. By "derivatives thereof", it is meant any substitution or ring
formation as described above for formulae (Va-d) in one embodiment;
and in particular, replacement of the metal "M" (Cr, Zr, Ti or Hf)
with an atom selected from the group consisting of Cr, Zr, Hf and
Ti; and replacement of the "X" group with any of C.sub.1 to C.sub.5
alkyls, C.sub.6 aryls, C.sub.6 to C.sub.10 alkylaryls, fluorine,
chlorine, or bromine.
[0221] It is contemplated that the metallocene catalyst components
described above include their structural or optical or enantiomeric
isomers (racemic mixture), and may be a pure enantiomer in one
embodiment.
[0222] As used herein, a single, bridged, asymmetrically
substituted metallocene catalyst component having a racemic and/or
meso isomer does not, itself, constitute at least two different
bridged, metallocene catalyst components.
[0223] A "metallocene catalyst component" useful in the present
invention may comprise any combination of any "embodiment"
described herein.
Support Materials of the Present Invention Having a Improved
Particle Size Distribution
[0224] The multi-transition-metal catalysts of the present
invention further comprise a support material of the present
invention having an improved particle size distribution. Supports,
methods of supporting, modifying, and activating supports for
single-site catalysts such as metallocenes are discussed in, for
example, 1 METALLOCENE-BASED POLYOLEFINS 173-218 (J. Scheirs &
W. Kaminsky eds., John Wiley & Sons, Ltd. 2000). The terms
"support" or "carrier", as used herein, are used interchangeably
and refer to the support materials of the present invention.
[0225] The support materials of the present invention, having an
improved, particle size distribution, generally have a
D.sub.90/D.sub.10 ratio of less than about 6. In certain
embodiments, the support materials of the present invention have a
D.sub.90/D.sub.10 ratio of less than about 5, and in certain
embodiments, less than about 4.5. In certain embodiments, the
support materials of the present invention has a D.sub.90 of less
than about 60 microns, and in certain embodiments a D.sub.90 of
less than about 55 microns, and in certain embodiments a D.sub.90
of less than about 50 microns, and in certain embodiments a
D.sub.90 of less than about 45 microns. In certain embodiments, the
support materials of the present invention have a D.sub.50 of less
than about 30 microns, and in certain embodiments a D.sub.50 of
less than about 25 microns. In certain embodiments, the support
materials of the present invention have a D.sub.10 of less than
about 5 microns, and in certain embodiments a D.sub.10 of less than
about 8 microns, and in certain embodiments a D.sub.10 of less than
about 10 microns. In certain preferred embodiments, the support
materials of the present invention have a D.sub.50 of less than
about 30 and a particle size distribution having a
D.sub.90/D.sub.10 ratio of less than about 6.
[0226] The D.sub.10, D.sub.50, and D.sub.90 values for a sample
support material may be calculated with the use of a conventional,
commercially-available particle size analyzer. An example of a
suitable particle size analyzer is commercially available from
Malvern Instruments, Ltd., of Worcestershire, UK, under the trade
name Mastersizer S long bench. An example of suitable software that
may be used with the aforementioned particle size analyzer is
commercially available from Malvern and referred to as Mastersizer
Series Software Version 2.19. The use of a Malvern particle size
analyzer to generate D.sub.10, D.sub.50, and D.sub.90 values for a
particular sample is described in a Malvern manual titled "Getting
Started, MAN 0101, Issue 1.3 (August 1997)," particularly at page
7.6, the disclosure of which is hereby incorporated by
reference.
[0227] Non-limiting examples of materials that may be suitable for
use as the support materials of the present invention having
improved particle size distributions include inorganic oxides and
inorganic chlorides, and in particular such materials as talc,
clay, silica, alumina, magnesia, zirconia, iron oxides, boria,
calcium oxide, zinc oxide, barium oxide, titanium dioxide, aluminum
phosphate gel, glass beads, and polymers such as polyvinylchloride
and substituted polystyrene, functionalized or crosslinked organic
supports such as polystyrene divinyl benzene polyolefins or
polymeric compounds, and mixtures thereof, and graphite, in any of
its various forms. In a preferred embodiment, the support materials
of the present invention comprise silica. In a particularly
preferred embodiment, the support materials of the present
invention comprise a synthetic amorphous silicon dioxide having a
pore volume ranging from 1.5 to 2.0 cm.sup.3/g and a surface area
of from 280 to 350 m.sup.2/g, with a D.sub.90 of about 44 micron, a
D.sub.50 of about 25 micron, and a D.sub.10 of about 10 micron,
commercially available from Ineos, under the trade name ES-757.
[0228] The use of the support materials of the present invention,
having an improved particle size distribution, in the supported,
multitransition metal catalysts of the present invention is
believed to provide a number of benefits, including, inter alia,
enhancing the productivity of the multitransition metal catalyst in
polymerization processes that produce polymer products such as
polyolefins. Moreover, the use of the supports of the present
invention in the catalysts of the present invention also is
believed to favorably impact the film appearance rating and gel
count of such polymer products. Though not wishing to be limited by
theory, it is believed that the improved particle size distribution
of the supports of the present invention may improve the absorption
of activators (e.g., trimethylaluminum, and the like) onto the
multitransition metal catalyst, particularly as such absorption is
thought to be surface-area-dependent. Additionally, because the
catalysts of the present invention comprise multiple transition
metal catalyst components, the improved particle size distribution
of the supports of the present invention may improve the
distribution of each component (e.g., one or more metallocene
catalyst components and one or more nonmetallocene catalyst
components) on the catalyst.
[0229] A support of the present invention may be contacted with the
other components of the catalyst system in any number of ways. In
one embodiment, the support material of the present invention is
contacted with the activator to form an association between the
activator and the support material, e.g., a "bound activator". In
another embodiment, the catalyst component may be contacted with
the support material of the present invention to form a "bound
catalyst component". In yet another embodiment, the support
material of the present invention may be contacted with the
activator and catalyst component together, or with each partially
in any order. The components may be contacted by any suitable means
as in a solution, slurry, or solid form, or some combination
thereof, and may be heated to any desirable temperature to
effectuate a desirable chemical/physical transformation.
[0230] In certain embodiments of the present invention, the support
material of the present invention, especially an inorganic support
or graphite support, may be pretreated such as by a halogenation
process or other suitable process that, for example, associates a
chemical species with the support material either through chemical
bonding, ionic interactions, or other physical or chemical
interaction. It is within the scope of the present invention to
co-contact (or "co-immobilize") more than one catalyst component
with a support material of the present invention. Non-limiting
examples of co-immobilization of catalyst components include two or
more of the same or different metallocene catalyst components, one
or more metallocenes with a Ziegler-Natta type catalyst, one or
more metallocenes with a chromium or "Phillips" type catalyst, one
or more metallocenes with a Group 8-10 metal-containing catalyst,
and any of these combinations with one or more activators. More
particularly, co-supported combinations include metallocene
A/metallocene A; metallocene A/metallocene B; metallocene/Ziegler
Natta; metallocene/Group 8-10 metal-containing catalyst;
metallocene/chromium catalyst; metallocene/Ziegler Natta/Group
8-10-containing catalyst; metallocene/chromium catalyst/Group
8-10-containing catalyst, any of the these with an activator, and
combinations thereof.
[0231] In certain embodiments of the present invention, the support
materials of the present invention having an improved particle size
distribution may be dehydrated prior to use in the multitransition
metal catalysts of the present invention. An example of a procedure
for dehydrating silica at 600.degree. C. is set forth in U.S. Pat.
No. 5,525,678.
[0232] The support materials of the present invention may be
combined with a non-polar hydrocarbon diluent to form a support
slurry, which can be stirred and optionally heated during
mixing.
[0233] A variety of non-polar hydrocarbon diluents can be used to
form the support slurry, but any non-polar hydrocarbon selected
preferably remains in liquid form at all relevant reaction
temperatures, and the ingredients used to form a nonmetallocene
catalyst component is preferably at least partially soluble in the
non-polar hydrocarbon. Accordingly, a non-polar hydrocarbon diluent
is considered to be a "solvent" herein, even though in certain
embodiments the ingredients are only partially soluble in the
hydrocarbon.
[0234] Examples of suitable non-polar hydrocarbons include
C.sub.4-C.sub.10 linear or branched alkanes, cycloalkanes and
aromatics. More specifically, a non-polar alkane can be isopentane,
hexane, isohexane, n-heptane, octane, nonane, or decane; a
non-polar cycloalkane such as cyclohexane; or an aromatic such as
benzene, toluene, or ethylbenzene. Mixtures of different non-polar
hydrocarbons can also be used.
[0235] The support slurry can be heated both during and after
mixing of the support particles with a non-polar hydrocarbon
solvent, but at the point when catalyst components are combined
with the support slurry, the temperature of the slurry is
preferably sufficiently low so that none of the catalysts are
inadvertently deactivated. Thus, the temperature of the support
slurry (e.g., silica slurry) is preferably maintained at a
temperature below 90.degree. C., for example, from 25 to 70.degree.
C., or from 40 to 60.degree. C. in another embodiment.
Activator
[0236] As used herein, the term "activator" is defined to be any
compound or combination of compounds, supported or unsupported,
which can activate a catalyst compound (e.g., Ziegler-Natta,
metallocenes, Group 8-10-containing catalysts, etc.), such as by
creating a cationic species from the catalyst component. Typically,
this involves the abstraction of at least one leaving group (X
group in the formulas above) from the metal center of the catalyst
component. The catalyst components of the present invention are
thus activated towards olefin polymerization using such activators.
Embodiments of such activators include Lewis acids such as cyclic
or oligomeric poly(hydrocarbylaluminum oxides), alkylaluminum
compounds and so called non-coordinating ionic activators ("NCA")
(alternately, "ionizing activators" or "stoichiometric
activators"), or any other compound that can convert a neutral
metallocene catalyst component to a metallocene cation that is
active with respect to olefin polymerization.
[0237] More particularly, it is within the scope of this invention
to use Lewis acids such as alumoxane (e.g., "MAO"), modified
alumoxane (e.g., "TIBAO"), and alkylaluminum compounds as
activators, and/or ionizing activators (neutral or ionic) such as
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron and/or a
trisperfluorophenyl boron metalloid precursors to activate
desirable metallocenes described herein. MAO and other
aluminum-based activators are well known in the art. Ionizing
activators are well known in the art. The activators may be
associated with or bound to a support material of the present
invention, either in association with the catalyst component (e.g.,
metallocene) or separate from the catalyst component, such as
described by Gregory G. Hlatky, Heterogeneous Single-Site Catalysts
for Olefin Polymerization 100(4) CHEMICAL REVIEWS 1347-1374
(2000).
[0238] Non-limiting examples of aluminum alkyl compounds that may
be utilized as activators for catalyst precursor compounds that may
be used in the methods of the present invention include
trimethylaluminum, triethylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, tri-n-octylaluminum and the like.
[0239] Examples of neutral ionizing activators include Group 13
tri-substituted compounds, in particular, tri-substituted boron,
thallium, aluminum, gallium and indium compounds, and mixtures
thereof. The three substituent groups are each independently
selected from the group consisting of alkyls, alkenyls, halogen,
substituted alkyls, aryls, arylhalides, alkoxy and halides. In one
embodiment, the three groups are independently selected from the
group consisting of halogen, mono or multicyclic (including
halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures
thereof. In another embodiment, the three groups are selected from
the group consisting of alkenyl groups having 1 to 20 carbon atoms,
alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to
20 carbon atoms and aryl groups having 3 to 20 carbon atoms
(including substituted aryls), and combinations thereof. In yet
another embodiment, the three groups are selected from the group
consisting of alkyls having 1 to 4 carbon groups, phenyl, naphthyl
and mixtures thereof. In yet another embodiment, the three groups
are selected from the group consisting of highly halogenated alkyls
having 1 to 4 carbon groups, highly halogenated phenyls, and highly
halogenated naphthyls and mixtures thereof. By "highly
halogenated", it is meant that at least 50% of the hydrogens are
replaced by a halogen group selected from the group consisting of
fluorine, chlorine and bromine.
[0240] In another embodiment, the neutral tri-substituted Group 13
compounds are boron compounds. Other suitable neutral ionizing
activators are described in U.S. Pat. No. 6,399,532 B1, U.S. Pat.
No. 6,268,445 B1, and in 19 ORGANOMETALLICS 3332-3337 (2000), and
in 17 ORGANOMETALLICS 3996-4003 (1998).
[0241] Illustrative, non-limiting examples of ionic ionizing
activators include trialkyl-substituted ammonium salts such as
triethylammonium tetra(phenyl)boron, tripropylammonium
tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron,
trimethylammonium tetra(p-tolyl)boron, trimethylammonium
tetra(o-tolyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tripropylammonium
tetra(o,p-dimethylphenyl)boron, tributylammonium
tetra(m,m-dimethylphenyl)boron, tributylammonium
tetra(p-tri-fluoromethylphenyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium
tetra(o-tolyl)boron and the like; N,N-dialkyl anilinium salts such
as N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium
tetra(phenyl)boron, N,N-2,4,6-pentamethylanilinium
tetra(phenyl)boron and the like; dialkyl ammonium salts such as
di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,
dicyclohexylammonium tetra(phenyl)boron and the like; and triaryl
phosphonium salts such as triphenylphosphonium tetra(phenyl)boron,
tri(methylphenyl)phosphonium tetra(phenyl)boron,
tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like, and
their aluminum equivalents.
[0242] In yet another embodiment, an activator may be used that
comprises an alkylaluminum in conjunction with a heterocyclic
compound. The ring of the heterocyclic compound may include at
least one nitrogen, oxygen, and/or sulfur atom, and may include at
least one nitrogen atom in one embodiment. The heterocyclic
compound may include 4 or more ring members in one embodiment, and
5 or more ring members in another embodiment.
[0243] The heterocyclic compound for use as an activator with an
alkylaluminum may be unsubstituted or substituted with one or a
combination of substituent groups. Examples of suitable
substituents include halogen, alkyl, alkenyl or alkynyl radicals,
cycloalkyl radicals, aryl radicals, aryl substituted alkyl
radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy
radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl
radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or
dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,
aroylamino radicals, straight, branched or cyclic, alkylene
radicals, or any combination thereof. The substituent groups also
may be substituted with halogens, particularly fluorine or bromine,
or heteroatoms or the like. Non-limiting examples of hydrocarbon
substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl,
cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like,
including all their isomers, for example tertiary butyl, isopropyl,
and the like. Other examples of substituents include fluoromethyl,
fluoroethyl, difluoroethyl, iodopropyl, bromohexyl or
chlorobenzyl.
[0244] In one embodiment, the heterocyclic compound is
unsubstituted. In another embodiment one or more positions on the
heterocyclic compound are substituted with a halogen atom or a
halogen atom containing group, for example a halogenated aryl
group. In one embodiment the halogen is selected from the group
consisting of chlorine, bromine and fluorine.
[0245] Non-limiting examples of heterocyclic compounds that may be
suitable as activators include substituted and unsubstituted
pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines,
carbazoles, and indoles, phenyl indoles, 2,5-dimethylpyrroles,
3-pentafluorophenylpyrrole, 4,5,6,7-tetrafluoroindole or
3,4-difluoropyrroles.
[0246] In one embodiment, the heterocyclic compound described above
is combined with an alkyl aluminum or an alumoxane to yield an
activator compound which, upon reaction with a catalyst component
(e.g., a metallocene), produces an active polymerization catalyst.
Non-limiting examples of alkylaluminums include trimethylaluminum,
triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,
tri-n-octylaluminum, tri-iso-octylaluminum, triphenylaluminum, and
combinations thereof.
[0247] Other activators that may be suitable include those
described in WO 98/07515 such as
tris(2,2',2''-nonafluorobiphenyl)fluoroaluminate. The present
invention further contemplates the use of combinations of
activators, such as, for example, alumoxanes and ionizing
activators in combinations. Other suitable activators include
aluminum/boron complexes, perchlorates, periodates and iodates
including their hydrates; lithium
(2,2'-bisphenylditrimethylsilicate)-4THF; silylium salts in
combination with a non-coordinating compatible anion. Also, methods
of activation such as using radiation, electro-chemical oxidation,
and the like also are contemplated as activating methods for the
purposes of rendering a neutral metallocene-type catalyst compound
or precursor to a metallocene-type cation capable of polymerizing
olefins. Other activators or methods for activating a
metallocene-type catalyst compound are described in, for example,
U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO
98/32775.
[0248] In general, the activator and catalyst component(s) are
combined in mole ratios of activator to catalyst component(s) from
1000:1 to 0.1:1 in one embodiment, and from 300:1 to 1:1 in a more
particular embodiment, and from 150:1 to 1:1 in yet a more
particular embodiment, and from 50:1 to 1:1 in yet a more
particular embodiment, wherein a desirable range may include any
combination of any upper mole ratio limit with any lower mole ratio
limit described herein. When the activator is a cyclic or
oligomeric poly(hydrocarbylaluminum oxide) (e.g., "MAO"), the mole
ratio of activator to catalyst component(s) ranges from 2:1 to
100,000:1 in one embodiment, and from 10:1 to 10,000:1 in another
embodiment, and from 50:1 to 2,000:1 in a more particular
embodiment. When the activator is a neutral or ionic ionizing
activator such as a boron alkyl and the ionic salt of a boron
alkyl, the mole ratio of activator to catalyst component(s) ranges
from 0.5:1 to 10:1 in one embodiment, and from 1:1 to 5:1 in yet a
more particular embodiment.
Gas Phase Polymerization Process
[0249] The supported, multi-transition-metal catalysts of the
present invention are used to make polyolefin compositions. In
certain embodiments of the present invention that use supported
bimetallic catalyst compositions, these catalyst compositions may
be used to make bimodal polyolefin compositions, e.g., compositions
having a bimodal molecular weight distribution; in a particular
embodiment, bimetallic catalysts described herein may be used in a
single polymerization reactor to make a bimodal polyolefin
composition. Once a supported multi-transition-metal catalyst of
the present invention is prepared, as described above, a variety of
processes can be carried out using that composition. Among the
varying approaches that can be used include procedures set forth in
U.S. Pat. No. 5,525,678 in which those processes are modified in
accordance with the inventions claimed herein. The equipment,
process conditions, reactants, additives and other materials of
course will vary in a given process, depending on the desired
composition and properties of the polymer being formed.
[0250] More particularly, in one embodiment, the processes of the
present invention comprise a gas phase polymerization process of
one or more olefin monomers having from 2 to 30 carbon atoms, from
2 to 10 carbon atoms in a more particular embodiment, and from 2 to
6 carbon atoms in yet a more particular embodiment. The invention
is particularly well suited to the polymerization of two or more
olefin monomers of ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-isobutene,
isobutylene and 3-methyl-1-butene.
[0251] Other monomers useful in the processes of the invention
include ethylenically unsaturated monomers, diolefins having 4 to
18 carbon atoms, conjugated or nonconjugated dienes, polyenes,
vinyl monomers and cyclic olefins. Non-limiting monomers useful in
the invention may include norbornene, norbornadiene, isoprene,
vinylbenzocyclobutane, styrenes, alkyl substituted styrene,
ethylidene norbornene, dicyclopentadiene and cyclopentene.
[0252] In a preferred embodiment of the processes of the present
invention, a copolymer of ethylene is produced, where with
ethylene, a comonomer (having at least one .alpha.-olefin having
from 4 to 15 carbon atoms, from 4 to 12 carbon atoms in yet a more
particular embodiment, and from 4 to 8 carbon atoms in yet a more
particular embodiment), is polymerized in a gas phase process. In
another embodiment of the processes of the invention, ethylene may
be polymerized with at least two different comonomers, optionally
one of which may be a diene, to form a terpolymer. In another
embodiment of the processes of the invention, hydrogen and ethylene
monomers may be polymerized.
[0253] Typically, in a gas phase polymerization process, a
continuous cycle is employed where in one part of the cycle of a
reactor system, a cycling gas stream (otherwise known as a recycle
stream or fluidizing medium) is heated in the reactor by the heat
of polymerization. This heat is removed from the recycle
composition in another part of the cycle by a cooling system
external to the reactor. Generally, in a gas fluidized bed process
for producing polymers, a gaseous stream containing one or more
monomers is continuously cycled through a fluidized bed in the
presence of a catalyst under reactive conditions. The gaseous
stream is withdrawn from the fluidized bed, cooled, and recycled
back into the reactor as a gas or as a mixture of gas and liquid.
Simultaneously, polymer product is withdrawn from the reactor and
fresh monomer is added to replace the polymerized monomer.
[0254] Optionally, a condensable inert component may be added to
increase the capability of removing heat from the reactor. In
certain embodiments, suitable condensable inert components may
comprise saturated hydrocarbons having from about 4 to about 7
carbon atoms.
[0255] The reactor pressure in a gas phase process may vary from
100 psig (690 kPa) to 500 psig (3448 kPa) in one embodiment, from
200 psig (1379 kPa) to 400 psig (2759 kPa) in a more particular
embodiment, and from 250 psig (1724 kPa) to 350 psig (2414 kPa) in
yet a more particular embodiment.
[0256] The reactor temperature in a gas phase process may vary from
30.degree. C. to 120.degree. C. in one embodiment, from 60.degree.
C. to 115.degree. C. in a more particular embodiment, from
70.degree. C. to 110.degree. C. in yet a more particular
embodiment, and from 85.degree. C. to 100.degree. C. in yet a more
particular embodiment, or as set out further below.
[0257] In an embodiment of the invention, the process may be
operated by introducing a carboxylate metal salt such as aluminum
stearate or other metal-fatty acid compound into the reactor and/or
contacting a carboxylate metal salt with a supported,
multi-transition-metal catalyst of the present invention prior to
its introduction into the reactor.
[0258] In certain embodiments of the present invention, the
multi-transition-metal catalysts of the present invention may be
activated by any suitable means known in the art, either before
introduction into the polymerization reactor or in situ. The
catalyst system is fed to the reactor in a dry (no diluent) state
in a particular embodiment. In another embodiment, the catalyst
system is suspended in a diluent (e.g., C.sub.3 to C.sub.15
hydrocarbon) comprising from 0.01 wt % to 100 wt % mineral oil or
silicon oil and fed into the reactor.
[0259] The gas-phase process of the present invention includes
contacting the multi-transition-metal catalysts of the present
invention (including support material of the present invention
having an improved particle size distribution, catalyst components,
and activators) with monomers in a reactor vessel of desirable
configuration to form a polyolefin. In one embodiment, the
contacting may take place in a first reactor vessel, followed by
transfer of the formed polymer into another second, third, etc.
reactor vessel to allow further polymerization, optionally by
adding the same or different monomers and optionally by adding the
same or different catalyst components, activators, etc. In a
particular embodiment of the present invention, the supported,
multi-transition-metal catalyst of the present invention is
contacted with monomers in a single reactor vessel (or "reactor"),
followed by isolation of a finished polyolefin resin.
[0260] To effectuate the polymerization processes of the present
invention, the composition of the recycling gas stream is measured
with a gas chromatograph. The partial pressure of ethylene is
controlled at a value in the range of from about 100 psia (690
kpaa) to about 250 psia (1720 kpaa). In certain embodiments of the
present invention, the mole ratio of hydrogen to ethylene may be in
the range of from about 0.007 to about 0.016.
[0261] An alkylaluminum compound, or mixture of compounds, such as
trimethylaluminum or triethylaluminum may be fed into the reactor
in one embodiment at a rate of from 10 wt. ppm to 500 wt. ppm
(weight parts per million alkylaluminum feed rate compared to
ethylene feed rate), and from 50 wt. ppm to 400 wt. ppm in a more
particular embodiment, and from 60 wt. ppm to 300 wt. ppm in yet a
more particular embodiment, and from 80 wt. ppm to 250 wt. ppm in
yet a more particular embodiment, and from 75 wt. ppm to 150 wt.
ppm in yet another embodiment, wherein a desirable range may
comprise any combination of any upper limit with any lower limit.
The alkylaluminum can be represented by the general formula
AlR.sub.3, wherein each R is the same or different and
independently selected from C.sub.1 to C.sub.10 alkyls.
[0262] Also, water also may be fed into the reactor in another
embodiment at a rate of from 0.01 wt. ppm to 200 wt. ppm (weight
parts per million water feed rate compared to ethylene feed rate),
and from 0.1 wt. ppm to 150 wt. ppm in another embodiment, and from
0.5 wt. ppm to 100 wt. ppm in yet another embodiment, and from 1
wt. ppm to 60 wt. ppm in yet another embodiment, and from 5 wt. ppm
to 40 wt. ppm in yet a more particular embodiment, wherein a
desirable range may comprise any combination of any upper limit
with any lower limit described herein.
[0263] Optionally, oxygen may be fed into the recycling gas system.
In certain embodiments, oxygen optionally may be fed into the
recycling gas system at a rate in the amount of from about 0.01 to
about 1.0 weight ppm compared to the ethylene feed rate. The oxygen
may serve as an antifoulant, and may reduce or eliminate fouling
of, for example, the recycling gas cooler or fluidized bed
distributor plate. Optionally, other compounds may be employed as
optional antifoulants.
Bimodal Polymer Product and Films Made Therefrom
[0264] The polymers produced by the processes described herein,
utilizing the supported, multitransition metal catalysts of the
present invention described herein, can be used in a wide variety
of products and end-use applications such as films, pipes and
tubing, wire coating, and other applications. The polymers produced
by the processes of the invention include linear low density
polyethylene, elastomers, plastomers, high density polyethylenes,
medium density polyethylenes, and low density polyethylenes.
[0265] Polymers that can be made using the described processes can
have a variety of compositions, characteristics and properties. At
least one of the advantages of the supported, multitransition metal
catalysts of the present invention is that the processes utilized
can be tailored to form a polymer composition with a desired set of
properties. For example, it is contemplated that in certain
embodiments in which the supported, multitransition metal catalysts
of the present invention comprise bimetallic catalysts, polymers
having the same properties as the bimodal polymer compositions in
U.S. Pat. No. 5,525,678 can be formed.
[0266] The polymers produced by the processes of the present
invention, typically ethylene-based polymers, have a density in the
range of from 0.860 g/cm.sup.3 to 0.970 g/cm.sup.3 in one
embodiment, from 0.880 g/cm.sup.3 to 0.965 g/cm.sup.3 in a more
particular embodiment, from 0.900 g/cm.sup.3 to 0.960 g/cm.sup.3 in
yet a more particular embodiment, from 0.905 g/cm.sup.3 to 0.955
g/cm.sup.3 in yet a more particular embodiment, from 0.910
g/cm.sup.3 to 0.955 g/cm.sup.3 in yet a more particular embodiment,
greater than 0.915 g/cm.sup.3 in yet a more particular embodiment,
greater than 0.920 g/cm.sup.3 in yet a more particular embodiment,
and greater than 0.925 g/cm.sup.3 in yet a more particular
embodiment. In another embodiment, the polymers produced by the
processes of the present invention have a density in the range of
from about 0.940 g/cm.sup.3 to about 0.960 g/cm.sup.3.
[0267] The polymers derived from the use of the supported,
multitransitional metal catalysts and processes of the invention
have a bulk density of from 0.350 to 0.900 g/cm.sup.3 in one
embodiment, and from 0.420 to 0.800 g/cm.sup.3 in another
embodiment, and from 0.430 to 0.500 g/cm.sup.3 in yet another
embodiment, and from 0.440 to 0.60 g/cm.sup.3 in yet another
embodiment, wherein a desirable range may comprise any upper bulk
density limit with any lower bulk density limit described
herein.
[0268] The polymers produced by the processes of the present
invention have a molecular weight distribution (e.g., a weight
average molecular weight to number average molecular weight
(M.sub.w/M.sub.n)) of from 5 to 100 in one embodiment, of from 10
to 80 in a more particular embodiment, of from 15 to 60 in yet a
more particular embodiment, and of from 20 to 50 in yet a more
particular embodiment.
[0269] The polymers made by the described processes have a melt
index (MI) (I.sub.2, as measured by ASTM D-1238, 190/2.16) in the
range of from 0.01 dg/min to 100 dg/min in one embodiment, from
0.01 dg/min to 50 dg/min in a more particular embodiment, from 0.02
dg/min to 20 dg/min in yet a more particular embodiment, and from
0.03 dg/min to 2 dg/min in yet a more particular embodiment, and
from 0.03 dg/min to 1 dg/min in yet a more particular embodiment,
wherein a desirable range may comprise any combination of any upper
I.sub.2 limit with any lower I.sub.2 limit.
[0270] Polymers made by the method of the invention have an HLMI
(I.sub.21, as measured by ASTM-D-1238, 190/21.6) value that ranges
from 0.01 to 50 dg/min in one embodiment, and from 0.1 to 30 in
another embodiment, and from 0.5 to 20 in yet a more particular
embodiment, and from 3 to 15 in yet a more particular embodiment,
and from about 4 to about 15 in a preferred embodiment, and from 5
to 15 in another preferred embodiment, wherein a desirable range is
any combination of any upper I.sub.21 limit with any lower I.sub.21
limit.
[0271] Polymers made by the described processes have a melt index
ratio (MIR, or I.sub.21/I.sub.2) of from 20 to 500 in one
embodiment, from 30 to 300 in a more particular embodiment, and
from 60 to 200 in yet a more particular embodiment, and from about
70 to about 200 in yet a more particular embodiment. Expressed
differently, polymers made by the described processes have a melt
index ratio of from greater than 40 in one embodiment, greater than
50 in a more particular embodiment, greater than 60 in yet a more
particular embodiment, greater than 65 in yet a more particular
embodiment, and greater than 70 in yet a more particular
embodiment.
[0272] The polymers produced by certain embodiments of the present
invention may have a certain average particle size, or APS
(determined by using standard sieves), ranging from greater than
150 microns in one embodiment, and from 150 to 2000 microns in a
more particular embodiment, and from 150 to 1000 microns in yet
another embodiment, and from 300 to 800 microns in yet a more
particular embodiment. Fines (e.g., particles having a size less
than 125 .mu.m) are typically present to less than 5 wt %, or less
than 4 wt %, or less than 3 wt %.
[0273] Granules of polymer material are formed from the processes
described herein in making the polymer products. Optionally, one or
more additives may be blended with the polymer products. In certain
preferred embodiments, the polymers of the present invention may be
blended and/or coextruded with any other polymer. Non-limiting
examples of other polymers include linear low density polyethylenes
produced via conventional Ziegler-Natta and/or metallocene-type
catalysis, elastomers, plastomers, high pressure low density
polyethylene, high density polyethylenes, and the like.
[0274] With respect to the physical process of producing the blend
of polymers and one or more additives (which one or more additives,
as noted above, may include other polymers), sufficient mixing
preferably takes place to assure that a uniform blend will be
produced prior to conversion into a finished product. One method of
blending the additives with the polyolefin is to contact the
components in a tumbler or other physical blending means, the
polyolefin being in the form of reactor granules. This can then be
followed, if desired, by melt blending in an extruder. Another
method of blending the components is to melt blend the reactor
product with the additives directly in an extruder, Brabender or
any other melt blending means, preferably an extruder. Examples of
suitable extruders include those made by Farrel and Kobe. While not
expected to influence the measured properties of the polymer
compositions of the present invention described herein, the
density, rheological and other properties of the polymer
compositions of the present invention described in the Examples are
measured after blending additives with the polymer
compositions.
[0275] Non-limiting examples of additives include processing aids
such as fluoroelastomers, polyethylene glycols and
polycaprolactones, antioxidants, nucleating agents, acid
scavengers, plasticizers, stabilizers, anticorrosion agents,
blowing agents, other ultraviolet light absorbers such as
chain-breaking antioxidants, etc., quenchers, antistatic agents,
slip agents, pigments, dyes and fillers and cure agents such as
peroxide.
[0276] In particular, antioxidants and stabilizers such as organic
phosphites, hindered amines, and phenolic antioxidants may be
present in the polymer products of the present invention from 0.001
to 2 wt % in one embodiment, and from 0.01 to 1 wt % in another
embodiment, and from 0.05 to 0.8 wt % in yet another embodiment;
described another way, from 1 to 5000 ppm by weight of the total
polymer composition, and from 100 to 3000 ppm in a more particular
embodiment. Non-limiting examples of organic phosphites that are
suitable are tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168)
and di(2,4-di-tert-butylphenyl)pentaerithritol diphosphite
(ULTRANOX 626). Non-limiting examples of hindered amines include
poly[2-N,N'-di(2,2,6,6-tetramethyl-4-piperidinyl)-hexanediamine-4-(1-amin-
o-1,1,3,3-tetramethylbutane)symtriazine] (CHIMASORB 944);
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN 770).
Non-limiting examples of phenolic antioxidants include
pentaerythrityl
tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IRGANOX
1010); 1,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate
(IRGANOX 3114); tris(nonylphenyl)phosphite (TNPP); and
Octadecyl-3,5-Di-(tert)-butyl-4-hydroxyhydrocinnamate (IRGANOX
1076); other additives include those such as zinc stearate and zinc
oleate.
[0277] Optionally, fillers also may be included in the polymer
products of the present invention. Fillers may be present from 0.01
to 5 wt % in one embodiment, and from 0.1 to 2 wt % of the
composition in another embodiment, and from 0.2 to 1 wt % in yet
another embodiment and most preferably, between 0.02 and 0.8 wt %.
Desirable fillers include, but are not limited to, titanium
dioxide, silicon carbide, silica (and other oxides of silica,
precipitated or not), antimony oxide, lead carbonate, zinc white,
lithopone, zircon, corundum, spinel, apatite, Barytes powder,
barium sulfate, magnesiter, carbon black, acetylene black,
dolomite, calcium carbonate, talc and hydrotalcite compounds of the
ions Mg, Ca, or Zn with Al, Cr or Fe and CO.sub.3 and/or HPO.sub.4,
hydrated or not; quartz powder, hydrochloric magnesium carbonate,
glass fibers, clays, alumina, and other metal oxides and
carbonates, metal hydroxides, chrome, phosphorous and brominated
flame retardants, antimony trioxide, silica, silicone, and blends
thereof. These fillers may particularly include any other fillers
and porous fillers and supports known in the art.
[0278] In total, fillers, antioxidants and other such additives are
preferably present to less than 2 wt % in the polyethylene
compositions of the present invention, preferably less than 1 wt %,
and most preferably to less than 0.8 wt % by weight of the total
composition.
[0279] Polymers produced by the process of the invention and blends
thereof are useful in such forming operations as film, sheet, pipe
and fiber extrusion and co-extrusion as well as blow molding,
injection molding and rotary molding. Films include blown or cast
films formed by coextrusion 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, cable and wire sheathing, medical packaging, industrial
liners, membranes, etc. in food-contact and non-food contact
applications. Fibers include melt spinning, solution spinning and
melt blown fiber operations for use in woven or non-woven form to
make filters, diaper fabrics, medical garments, geotextiles, etc.
Extruded articles include medical tubing, wire and cable coatings,
geomembranes, and pond liners. Molded articles include single and
multi-layered constructions in the form of bottles, tanks, large
hollow articles, rigid food containers and toys, etc.
[0280] More particularly, the polymers made by the methods of the
present invention are useful in making films. The films may be of
any desirable thickness or composition, in one embodiment from 1 to
100 microns, and from 2 to 50 microns in a more particular
embodiment, and from 5 to 30 microns in yet a more particular
embodiment, and from 5 to 25 microns in a most preferred
embodiment; and comprise copolymers of ethylene with a C.sub.3 to
C.sub.10 olefin in one embodiment, ethylene with C.sub.3 to C.sub.8
.alpha.-olefins in a particular embodiment, and ethylene with
C.sub.4 to C.sub.6 .alpha.-olefins in yet a more particular
embodiment. The resins used to make the films may be blended with
other additives such as pigments, antioxidants, fillers, etc., as
is known in the art, as long as they do not interfere with the
desired film properties.
[0281] The films that may be made from polymers made by the methods
of the present invention may have a Gel Count of less than 100 in
one embodiment, and a Gel Count of less than 60 in another
embodiment, and a Gel Count of less than 50 in another embodiment,
and a Gel Count of less than 40 in yet another embodiment, and a
Gel Count of less than 30 in yet another embodiment, and a Gel
Count of less than 20 in still another embodiment, and a Gel Count
of less than 10 in a most preferred embodiment. As referred to
herein, "Gel Count" is defined as the total number of gels having a
dimension greater than 300 .mu.m, per square meter of 25 micron
film. The determination of Gel Count for a particular polymer
product is further described hereinbelow.
[0282] Described alternately, the films may have a Film Appearance
Rating ("FAR value") of greater than +20 in one embodiment, and
greater than +30 in another embodiment, and greater than +40 in yet
another embodiment. "Film Appearance Rating" is an internal test
method in which resin is extruded under standard operating
guidelines and the resulting film is examined visually for surface
imperfections. The film is compared to a reference set of standard
film and a FAR rating is assigned based on operator's assessment.
This evaluation is conducted by an operator with considerable
experience. The FAR reference films are available for the range of
-50 to +50. FAR ratings of +20 and better are considered
commercially acceptable by customers.
[0283] In certain embodiments of the present invention in which the
polymers produced from the polymerization processes of the present
invention are used to make films, the resultant pelletized polymer
compositions of the present invention, with or without additives,
are processed by any suitable means for forming films: film blowing
or casting and all methods of film formation to achieve, for
example, uniaxial or biaxial orientation such as described in
PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp. 1986). In
a particularly preferred embodiment, the polymer compositions of
the present invention may be formed into films such as described in
the FILM EXTRUSION MANUAL, PROCESS, MATERIALS, PROPERTIES (TAPPI,
1992). Even more particularly, the films of the present invention
may be blown films, the process for which is described generally in
FILM EXTRUSION MANUAL, PROCESS, MATERIALS, PROPERTIES pp. 16-29,
for example.
[0284] Any extruder suitable for extrusion of a HDPE (density
greater than 0.940 grams/cm.sup.3) operating under any desirable
conditions for the polyethylene compositions described herein can
be used to produce the films of the present invention. Such
extruders are known to those skilled in the art. Such extruders
include those having screw diameters ranging from 30 to 150 mm in
one embodiment, and from 35 to 120 mm in another embodiment, and
having an output of from 100 to 1,500 lbs/hour in one embodiment,
and from 200 to 1,000 lbs/hour in another embodiment. In one
embodiment, a grooved feed extruder is used. The extruder may
possess a L/D ratio of from 80:1 to 2:1 in one embodiment, and from
60:1 to 6:1 in another embodiment, and from 40:1 to 12:1 in yet
another embodiment, and from 30:1 to 16:1 in yet another
embodiment.
[0285] A mono or multi-layer die can be used. In one embodiment a
50 to 200 mm monolayer die is used, and a 90 to 160 mm monolayer
die in another embodiment, and a 100 to 140 mm monolayer die in yet
another embodiment, the die having a nominal die gap ranging from
0.6 to 3 mm in one embodiment, and from 0.8 to 2 run in another
embodiment, and from 1 to 1.8 mm in yet another embodiment, wherein
a desirable die can be described by any combination of any
embodiment described herein. In a particular embodiment, the
advantageous specific throughputs claimed herein are maintained in
a 50 mm grooved feed extruder with an LID of 21:1 in a particular
embodiment.
[0286] The temperature across the zones of the extruder, neck and
adapter of the extruder ranges from 150.degree. C. to 230.degree.
C. in one embodiment, and from 160.degree. C. to 210.degree. C. in
another embodiment, and from 170.degree. C. to 190.degree. C. in
yet another embodiment. The temperature across the die ranges from
160.degree. C. to 250.degree. C. in one embodiment, and from
170.degree. C. to 230.degree. C. in another embodiment, and from
180.degree. C. to 210.degree. C. in yet another embodiment.
[0287] To facilitate a better understanding of the present
invention, the following examples of some exemplary embodiments are
given. In no way should such examples be read to limit, or to
define, the scope of the invention.
EXAMPLES
Example 1
[0288] In the following example, three samples of supported,
multitransition metal catalysts were prepared. Two samples are
comparative samples, while one sample constitutes a supported,
multitransition metal catalyst of the present invention. Specific
properties of the samples are displayed in Table 1.
Preparation of Comparative Sample Catalyst 1.
[0289] A comparative sample catalyst (referred to herein as
Comparative Sample Catalyst Composition No. 1) was prepared as
follows. About 2,000 pounds of anhydrous iso-hexane was transferred
into a nitrogen-purged, agitated and jacketed reaction vessel. The
temperature of the jacket was set at 54.degree. C.
[0290] A conventional silica was provided (Davison 955 silica),
which typically has the following properties: TABLE-US-00001
Average Particle Size: 40 microns Surface Area: 300 m.sup.2/gram
Porosity: 1.6 cm.sup.3/gram D.sub.10: 10 microns D.sub.50: 40
microns D.sub.90: 90 microns D.sub.90/D.sub.10: 9.0
[0291] The conventional silica was dried under nitrogen at
875.degree. C. About 750 pounds of the dehydrated conventional
silica then was combined with the anhydrous iso-hexane, while under
constant stirring. Once the slurry of silica and hexane reached a
temperature of about 40.degree. C., about 525 pounds of a 15 weight
% solution of dibutyl magnesium in heptane (supplied by FMC
Corporation) was added to the slurry over a period of 35 minutes.
The slurry then was mixed for an additional 60 minutes at
54.degree. C.
[0292] Butanol (41.1 pounds) was diluted with iso-hexane to form a
65 weight % solution. This pre-diluted solution of butanol in
iso-hexane was added into the vessel containing the slurry over 30
minutes, and then the slurry was held at a temperature of
54.degree. C. for 60 minutes while under constant agitation.
[0293] Titanium tetrachloride (61.5 pounds) was diluted with
iso-hexane to form a 70 weight % solution. This pre-diluted
solution of titanium tetrachloride in iso-hexane then was added
into the vessel containing the slurry over 45 minutes. Following
the addition of the solution, the slurry was allowed to stand for
60 minutes at a temperature of 54.degree. C.
[0294] A MAO-metallocene mixture then was added to the slurry. This
mixture had been prepared in a separate nitrogen-purged and
agitated vessel. This vessel first had received about 975 pounds of
a 30 weight % solution of methylaluminoxane (MAO) in toluene
(supplied by Albemarle) at ambient temperature. Then, a toluene
solution of 18.5 pounds of bis-n-butyl-cyclopentadienyl zirconium
difluoride was added into the MAO solution under constant
agitation. Mixing of the MAO/metallocene mixture continued for at
least 30 minutes.
[0295] The MAO/Metallocene mixture then was added via spray nozzle
into the first reaction vessel (containing the previously-prepared
titanium reaction slurry) over a period of three hours. After the
end of the MAO/metallocene addition, agitation continued in the
first reaction vessel for another hour. The resulting mixture that
included the comparative sample catalyst then was dried at a jacket
temperature of 70.degree. C. with vacuum applied until the volatile
content was less than 3 weight percent. The comparative sample
catalyst then was used in a polymerization run in a gas phase
reactor, under the conditions identified in Table 1 to form a
polyethylene polymer composition.
Preparation of Comparative Sample Catalyst No. 2
[0296] A second comparative sample catalyst (referred to herein as
Comparative Sample Catalyst Composition No. 2) was prepared as
follows. About 1,100 pounds of anhydrous iso-hexane was transferred
into a nitrogen-purged, agitated and jacketed reaction vessel. The
temperature of the jacket was set at 54.degree. C.
[0297] A conventional silica was provided (Davison 955 silica, as
was used in the preparation of Comparative Sample Catalyst No. 1,
except that the sample of Davison 955 silica used to prepare
Comparative Sample Catalyst No. 2 was dehydrated in air at
875.degree. C., rather than in nitrogen). About 400 pounds of the
dehydrated conventional silica then was combined with the anhydrous
iso-hexane, while under constant stirring. Once the slurry of
silica and hexane reached a temperature of about 40.degree. C.,
about 280 pounds of a 15 weight % solution of dibutyl magnesium in
heptane (supplied by FMC Corporation) was added to the slurry over
a period of 60 minutes. The slurry then was mixed for an additional
60 minutes at 54.degree. C.
[0298] Butanol (21.9 pounds) was diluted with iso-hexane to form a
65 weight % solution. This pre-diluted solution of butanol in
iso-hexane was added into the vessel containing the slurry over 30
minutes, and then the slurry was held at a temperature of
54.degree. C. for 60 minutes while under constant agitation.
[0299] Titanium tetrachloride (36.1 pounds) was diluted with
iso-hexane to form a 70 weight % solution. This pre-diluted
solution of titanium tetrachloride in iso-hexane then was added
into the vessel containing the slurry over 45 minutes. Following
the addition of the solution, the slurry was allowed to stand for
60 minutes at a temperature of 54.degree. C.
[0300] A MAO-metallocene mixture then was added to the slurry. This
mixture had been prepared in a separate nitrogen-purged and
agitated vessel. This vessel first had received about 520 pounds of
a 30 weight % solution of methylaluminoxane (MAO) in toluene
(supplied by Albemarle) at ambient temperature. Then, a toluene
solution of 15.7 pounds of bis-n-butyl-cyclopentadienyl zirconium
difluoride was added into the MAO solution under constant
agitation. Mixing of the MAO/metallocene mixture continued for at
least 30 minutes.
[0301] The MAO/Metallocene mixture then was added via spray nozzle
into the first reaction vessel (containing the previously-prepared
titanium reaction slurry) over a period of three hours. After the
end of the MAO/metallocene addition, agitation continued in the
first reaction vessel for another hour. The resulting mixture that
included the comparative sample catalyst then was dried at a jacket
temperature of 70.degree. C. with vacuum applied until the volatile
content was less than 3 weight percent. The comparative sample
catalyst then was used in a polymerization run in a gas phase
reactor, under the conditions identified in Table 1 to form a
polyethylene polymer composition.
Preparation of Catalyst Compositions of the Present Invention.
[0302] A sample catalyst composition of the present invention
(Sample Catalyst Composition No. 3) then was prepared as follows.
About 1,100 pounds of anhydrous iso-hexane was transferred into a
nitrogen-purged, agitated and jacketed reaction vessel. The
temperature of the jacket was set at 54.degree. C.
[0303] A silica having an improved particle size distribution was
provided (Ineos ES-757 silica), which typically has the following
properties: TABLE-US-00002 Average Particle Size: 25 microns
Surface Area: 300 m.sup.2/gram Porosity: 1.6 cm.sup.3/gram
D.sub.10: 10 microns D.sub.50: 25 microns D.sub.90: 44 microns
D.sub.90/D.sub.10: 4.4
[0304] The Ineos ES-757 silica was dried in air at 875.degree. C.
About 400 pounds of the dehydrated Ineos ES-757 silica then was
combined with the anhydrous iso-hexane, while under constant
stirring. Once the slurry of Ineos ES-757 silica and iso-hexane
reached a temperature of about 40.degree. C., about 280 pounds of a
15 weight % solution of dibutyl magnesium in heptane (supplied by
FMC Corporation) was added to the slurry over a period of 150
minutes. The slurry then was mixed for an additional 60 minutes at
54.degree. C.
[0305] Butanol (21.9 pounds) was diluted with iso-hexane to form a
65 weight % solution. This pre-diluted solution of butanol in
iso-hexane was added into the vessel containing the slurry over 30
minutes, and then the slurry was held at a temperature of
54.degree. C. for 60 minutes while under constant agitation.
[0306] Titanium tetrachloride (39.2 pounds) was diluted with
iso-hexane to form a 70 weight % solution. This pre-diluted
solution of titanium tetrachloride in iso-hexane then was added
into the vessel containing the slurry over 45 minutes. Following
the addition of the solution, the slurry was allowed to stand for
60 minutes at a temperature of 54.degree. C.
[0307] A MAO-metallocene mixture then was added to the slurry. This
mixture had been prepared in a separate nitrogen-purged and
agitated vessel. This vessel first had received about 520 pounds of
a 30 weight % solution of methylaluminoxane (MAO) in toluene
(supplied by Albemarle) at ambient temperature. Then, a toluene
solution of 14.1 pounds of bis-n-butyl-cyclopentadienyl zirconium
difluoride was added into the MAO solution under constant
agitation. Mixing of the MAO/metallocene mixture continued for at
least 30 minutes.
[0308] The MAO/Metallocene mixture then was added via spray nozzle
into the first reaction vessel (containing the previously-prepared
titanium reaction slurry) over a period of three hours. After the
end of the MAO/metallocene addition, agitation continued in the
first reaction vessel for another hour. The resulting mixture that
included the sample catalyst of the present invention then was
dried at a jacket temperature of 70.degree. C. with vacuum applied
until the volatile content was less than 3 weight percent. The
sample catalyst of the present invention then was used in a
polymerization run in a gas phase reactor, under the conditions
identified in Table 1 to form a polyethylene polymer
composition.
Fluid-Bed Polymerization.
[0309] The polymerizations were conducted in a continuous gas phase
fluidized bed reactor. The fluidized bed is made up of polymer
granules. The gaseous feed streams of ethylene and hydrogen
together with liquid comonomer were mixed together in a mixing tee
arrangement and introduced into the recycle gas line upstream of
the reactor bed. Monomers of 1-butene were used as the comonomer.
The individual flow rates of ethylene, hydrogen and comonomer were
controlled to maintain fixed composition targets. The ethylene
concentration was controlled to maintain a constant ethylene
partial pressure of about 175 psia. The hydrogen was controlled to
maintain a constant hydrogen-to-ethylene mole ratio of about 0.011.
Similarly, the ratio of the flow rate to the reactor of 1-butene to
that of ethylene was controlled at about 0.013 pounds of 1-butene
per pound of ethylene. When oxygen was fed to the reactor as an
antifoulant, the feedrate was 0.25 pounds of oxygen per million
pounds of ethylene. The concentration of all the gases were
measured by an on-line gas chromatograph to ensure relatively
constant composition in the recycle gas stream.
[0310] The solid catalyst was injected directly into the fluidized
bed using purified nitrogen as a carrier. Trimethylaluminum (TMA)
was injected into the recycling gas as a cocatalyst for the
Ziegler-Natta catalyst. Its rate was adjusted to maintain a
constant TMA-to-ethylene mass flow ratio. The reacting bed of
growing polymer particles is maintained in a fluidized state by the
continuous flow of the make up feed and recycle gas through the
reaction zone. A superficial gas velocity of 1-3 ft/sec was used to
achieve this. The reactor was operated at a total pressure of about
270 psig. To maintain a constant reactor fluidized bed temperature,
the temperature of the recycle gas is continuously adjusted up or
down to accommodate any changes in the rate of heat generation due
to the polymerization.
[0311] The fluidized bed was maintained at a constant height by
withdrawing a portion of the bed at a rate equal to the rate of
formation of particulate product. The product is removed
semi-continuously via a series of valves into a fixed volume
chamber. The reactor gas removed with the product during a
discharge is vented to a flare, and not recycled back to the
reactor. The product is purged to remove entrained hydrocarbons and
treated with a small stream of humidified nitrogen to deactivate
any trace quantities of residual catalyst and cocatalyst.
[0312] The catalyst activity may be calculated using titanium as a
basis by dividing the titanium content of the catalyst by the
residual titanium content found in the product. The titanium
content of the product was determined using a calibrated x-ray
fluorescene technique. Linear relations were used to correct
catalyst activity for any differences in ethylene partial pressure
and reactor residence time between polymerization runs.
Resin Properties.
[0313] The properties of the polymer were determined by the
following test methods: [0314] 1. Melt Index: ASTM D-1238-Condition
E. The resin is melt-blended (compounded) with 1500 ppm I-1010,
1500 ppm 1-168, and 500 ppm zinc stearate (ZnSt), pelletized, and
measured on a Goettfert plastometer instrument type 011.5/2001,
following ASTM D-1238-190.degree. C./2160 grams using a five-minute
cut. [0315] 2. Density: ASTM D-105. The resin is melt-blended with
1500 ppm I-1010, 1500 ppm 1-168, and 500 ppm ZnSt, pelletized,
compression molded according to ASTM 4703-03 with a 40 hour
conditioning time and density gradient column according to ASTM
D1505-03. [0316] 3. Bulk Density: The resin is poured via a 7/8
inch diameter funnel into a fixed volume cylinder of 400 cc. The
bulk density is measured as the weight of resin divided by 400 cc
to give a value in g/cc. [0317] 4. Dynamic Rheology: The resin is
melt-blended with 1500 ppm 1-1010, 1500 ppm 1-168, and 500 ppm
ZnSt, pelletized, and pressed into a disk 25 mm in diameter and 2.0
mm thick. Measurement occurred on a Rheometrics SR 5000 using 25 mm
plates, a 1.5 mm die gap at 200.degree. C. and a frequency of 0.1
to 100 rad/sec. [0318] 5. Flow Index: Resin is melt-blended with
1500 ppm 1-1010, 1500 ppm I-168, and 500 ppm ZnSt, pelletized, and
measured on a Goettfert plastometer instrument type 011.5/2001,
primarily following ASTM D-1238-190.degree. C./21600 grams timed
method. Exceptions to the ASTM-D1238-190.degree. C./21600 are the
use of a full 1 inch travel for resins with a flow index less than
10 dg/min and the total time that the resin is in the plastometer
prior to initiating measurement is 7-10 minutes rather than the 6.5
to 7.5 min specified in the ASTM procedure. [0319] 6. XRF: ASTM
procedure D 6247-98 (reapproved 2004). Calibration standards were
prepared from bimodal HDPE material from actual production runs
that were independently analyzed for metals content by Elemental
Analysis, Inc., of Lexington, Ky. [0320] 7. GPC: Polymer solutions
were prepared in filtered 1,2,4-Trichlorobenzene containing about
250 ppm of butylated hydroxy toluene (BHT). The same solvent was
used as the SEC eluent. Polymer solutions were prepared by
dissolving the desired amount of dry polymer in the appropriate
volume of SEC eluent to yield concentrations ranging from 1.0 to
1.5 mg/ml. The sample vials were capped and placed in an air oven
for 2 hours at 160.degree. C. The instrument used was a Waters
Alliance 2000 gel permeation chromatograph equipped with a Waters
differential refractometer that measures the difference between the
refractive index of the solvent and that of the solvent containing
the fractionated polymer. The system was used at 145 C, a nominal
flow rate of 1.0 mL/min and a nominal injection volume of 300
microliters. Three Polymer Laboratories (PL) gel Mixed-B columns
were used. [0321] The separation efficiency of the column set was
calibrated using a series of narrow MWD polystyrene standards,
which reflects the expected molecular weight (MW) range for
samples, and the exclusion limits of the column set. At least 10
individual polystyrene standards, ranging from M.sub.p of about 580
to 10,000,000 were used to generate the calibration curve. The
polystyrene standards were obtained from Polymer Laboratories of
Amherst, Mass., or an equivalent source. To assure internal
consistency, the flow rate was corrected for each calibrant run, to
give a common peak position for the flow rate marker (taken to be
the positive inject peak) before determining the retention volume
for each polystyrene standard. The flow marker peak position thus
assigned was also used to correct the flow rate when analyzing
samples. [0322] A calibration curve (logM.sub.p v. retention
volume) was generated by recording the retention volume at the peak
in the DRI signal for each polystyrene standard, and fitting this
data set to a 2nd-order polynomial. Polystyrene standards were
graphed using Viscotec 3.0 software. Samples were analyzed using
WaveMetrics, Inc. IGOR Pro and Viscotec 3.0 software, using updated
calibration constants.
[0323] Each catalyst was evaluated in the fluidized bed reactor,
wherein the residence time varied from about 4-6 hours. Each run
was conducted using the same continuous gas phase fluidized bed
reactor. The fluidized bed of that reactor was made up of polymer
granules. During each run, the gaseous feed streams of ethylene and
hydrogen were introduced upstream of the reactor bed into the
recycle gas line. Butene comonomer also was introduced into the
recycle gas line upstream of the reactor bed. The individual flows
of ethylene and hydrogen were controlled to maintain fixed
composition targets. The concentrations of gases were measured by
an on-line chromatograph.
Gel Count Test Procedure
[0324] The gel content of the polymer products was tested by the
OCS Method. The equipment used consisted of an Optical Control
Systems GmbH (OCS) Model ME-20 extruder, and OCS Model CR-8 cast
film system, and an OCS Model FS-5 gel counter.
[0325] The ME-20 extruder consists of a 3/4'' standard screw with
3/1 compression ratio, and 25/1 L/D. It includes a feed zone, a
compression zone, and a metering zone. The extruder utilizes all
solid state controls, a variable frequency AC drive for the screw,
5 heating zones including 3 for the barrel, 1 for the melt temp and
pressure measurement zone, and one for the die. The die is a 4''
fixed lip die of a "fishtail" design, with a die gap of approx. 20
mils.
[0326] The cast film system includes dual stainless steel chrome
plated and polished chill rolls, a machined precision air knife,
rubber nip rolls that pull the film through the gel counter, and a
torque driven wind up roll. The nip rolls are driven separately
from the chill rolls and are controlled by speed or tension. A
circulation cooling/heating system for the chill rolls is also
included, and utilizes ethylene glycol. Steel SS rails, film break
sensors, and other items are included.
[0327] The gel counter consists of a digital 2048 pixel line
camera, a halogen based line lighting system, an image processing
computer, and Windows NT4 software. The camera/light system is
mounted on the cast film system between the chill roll and nip
rolls, and is set up for a 50-micron resolution on film. This means
that the smallest defect that can be seen is 50 microns by 50
microns in size. The OCS cast film system is designed to provide
the highest quality and most consistent film possible for the gel
measurement.
[0328] The pellet samples were run with constant extruder
temperatures (180 C for the feed zone, 190 C for all remaining
zones), and constant chill roll temperature of 40 C. The extruder
and chill roll speeds had to be varied somewhat between samples to
provide an optimum film for each sample.
[0329] The gel counter was set up with 10 different size classes
beginning at 50-100 microns and increasing at 100 micron intervals,
4 different shape classes beginning with a perfect circular shape
and increasing to more oblong shapes, and two detection levels (one
for gels and one for black specks). The gel detection level or
sensitivity used is normally set to 35.
[0330] Once the camera set up parameters were determined, the
extruder was purged with the first sample (typically about 20
minutes) or until it was apparent that the test conditions were at
steady state, or "equilibrium". This was done by looking at a trend
line chart of gel count number on the "y" axis, and time on the "x"
axis. Tests were then run on 4-9 square meters of film, typically
of 25 .mu.m gauge. As noted above, "Gel Count" is defined as the
total number of gels having a dimension greater than 300 .mu.m, per
square meter of 25 micron film.
[0331] In Table 1 below, gel count results are reported as the
total number of gels greater than 300 .mu.m per square meter of
film. TABLE-US-00003 TABLE 1 Comparative Comparative Comparative
Sample Sample Sample Sample Catalyst Catalyst Catalyst Catalyst
Comp. Comp. No. 1 Comp. No. 2 Comp. No. 2 No. 3 Oxygen Antifoulant
Yes Yes No No FI [dg/min] 11.1 13.3 12.1 6.3 MI [dg/min] 0.0805
0.0985 0.0985 0.0705 MFR 138 135 123 90 MFR @ 10FI 130 112 108 116
GP 0.1 [dyne/cm.sup.2] 46639 32334 33504 38739 GPP 0.1
[dyne/cm.sup.2] 84498 64142 62894 78266 Elasticity 0.55 0.50 0.53
0.49 Density.sup.(1) [g/cc] 0.952 0.953 0.953 0.951 Eta 0.1 [P]
965250 718310 712620 931385 Eta 100 [P] 28343 20784 20144 29739 Eta
0.1/100 34 35 35 31 Ti [ppm] 1.79 2.23 1.72 1.43 Al [ppm] 54.61
51.98 49.69 48.84 Cat_Ti [wt. %] 1.25 1.31 1.31 1.45 Cat_Al [wt. %]
10.29 10.36 10.36 10.39 Productivity (gram PE/gram catalyst) 6972
5864 7596 10119 LMW_Mw.sup.(2) [Daltons] 4801 6343 6451 6881
HMW_Mw.sup.(2) [Daltons] 442869 441048 413055 390875 Gel Count
[#>300 um/SqM] 50 59 53 6 .sup.(1)Determined via the ASTM
method. .sup.(2)Determined from a data fit using a Wesslau
distribution.
[0332] The results of the abovedescribed Example are further
illustrated with reference to FIGS. 1 and 2. Referring now to FIG.
1, the polymers produced from Sample Catalyst Composition 3 (a
supported, multitransition metal catalyst of the present invention)
demonstrate a narrower particle size distribution as compared to
those produced from Comparative Sample Catalyst Compositions Nos. 1
and 2; this narrower particle size distribution is believed to be
attributable to the narrower particle size distribution of the
improved supports of the present invention. Referring now to FIG.
2, the polymers produced from Sample Catalyst Composition 3
demonstrate a reduced gel count as compared to those produced from
Comparative Sample Catalyst Compositions Nos. 1 and 2; this also is
believed to be attributable to the narrower particle size
distribution of the improved supports of the present invention.
[0333] While the present invention has been described and
illustrated by reference to particular embodiments, those of
ordinary skill in the art will appreciate that the invention lends
itself to many different variations not illustrated herein. For
these reasons, then, reference should be made solely to the
appended claims for purposes of determining the scope of the
present invention. Further, certain features of the present
invention are described in terms of a set of numerical upper limits
and a set of numerical lower limits. It should be appreciated that
ranges formed by any combination of these limits are within the
scope of the invention unless otherwise indicated.
[0334] Unless otherwise indicated, all numbers expressing
quantities of ingredients, properties, reaction conditions, and so
forth, used in the specification and claims are to be understood as
approximations based on the desired properties sought to be
obtained by the present invention, and the error of measurement,
etc., and should at least be construed in light of the number of
reported significant digits and by applying ordinary rounding
techniques. Notwithstanding that the numerical ranges and values
setting forth the broad scope of the invention are approximations,
the numerical values set forth are reported as precisely as
possible.
[0335] For the purpose of legal systems outside the United States
in which preferred or optional features can be linked to or be
dependent on multiple other features in the claims (such as under
the European Patent Convention) specific embodiments are set forth
as follows:
(1) A supported, multi-transition-metal catalyst composition
comprising:
[0336] (a) at least two catalyst components selected from the group
consisting of: a nonmetallocene catalyst component and a
metallocene catalyst component; [0337] (b) a support material that
has a D.sub.50 of less than 30 microns and a particle size
distribution having a D.sub.90/D.sub.10 ratio of less than 6; and
[0338] (c) an activator. (2) The supported catalyst composition of
claim 1, wherein the support material comprises silica. (3) The
supported catalyst composition of either claim 1 or claim 2,
wherein the nonmetallocene catalyst component is a Ziegler-Natta
catalyst component that comprises a nonmetallocene transition metal
compound selected from the group consisting of Group 4 and Group 5
halides, oxides, oxyhalides, alkoxides, and mixtures thereof. (4)
The supported catalyst composition of any of claims 1-3, wherein
the activator comprises aluminum. (5) A process for making
polyolefins, comprising contacting monomers with the supported
catalyst composition of any one or all of claims 1-4 for a time
sufficient to form a multimodal polyolefin composition. (6) A
polymer product made from the process of claim 5. (7) An extruded
pellet of the polymer product of claim 6. (8) A film made from the
polymer product of claim 6. (9) The film of claim 8 having a gel
count of less than 30. (10) The film of claim 8 having a gel count
of less than 10.
* * * * *