U.S. patent application number 10/301884 was filed with the patent office on 2004-05-27 for bridged metallocene catalyst component, method of making, polyolefin catalyst having c1, c2, or cs symmetry, methods of making, methods of polymerizing, olefins and products made thereof.
Invention is credited to Baekelmans, Didier, Lopez, Margarito, Razavi, Abbas.
Application Number | 20040102311 10/301884 |
Document ID | / |
Family ID | 32324614 |
Filed Date | 2004-05-27 |
United States Patent
Application |
20040102311 |
Kind Code |
A1 |
Razavi, Abbas ; et
al. |
May 27, 2004 |
Bridged metallocene catalyst component, method of making,
polyolefin catalyst having C1, C2, or Cs symmetry, methods of
making, methods of polymerizing, olefins and products made
thereof
Abstract
Bridged metallocene catalyst component in which a bridge spans
two cyclopentadienyl groups, which Cp groups are attached to same
or different heteroatoms of the bridge, which heteroatoms are also
bonded to the metal. A catalyst systems is made by contacting the
bridged component with a cocatalyst. Polymerization of olefins in
catalyzed by the system.
Inventors: |
Razavi, Abbas; (Brisee,
BE) ; Lopez, Margarito; (Pasadena, TX) ;
Baekelmans, Didier; (Munich, DE) |
Correspondence
Address: |
David Alexander
FINA Technology, Inc.
P.O. Box 674412
Houston
TX
77267-4411
US
|
Family ID: |
32324614 |
Appl. No.: |
10/301884 |
Filed: |
November 21, 2002 |
Current U.S.
Class: |
502/117 ;
502/152; 502/155; 534/15; 556/144 |
Current CPC
Class: |
C07F 17/00 20130101;
B01J 31/2204 20130101; B01J 2531/842 20130101; B01J 23/74 20130101;
B01J 2531/0258 20130101; C07F 15/065 20130101; B01J 2531/84
20130101; C08F 10/00 20130101; C08F 10/00 20130101; C08F 10/00
20130101; B01J 31/1815 20130101; C07F 15/025 20130101; B01J 31/1845
20130101; C08F 4/7042 20130101; C08F 4/80 20130101 |
Class at
Publication: |
502/117 ;
502/152; 502/155; 534/015; 556/144 |
International
Class: |
B01J 031/00; C07F
005/00; C07F 017/02 |
Claims
I claim:
1. A bridged metallocene compound having the formula: 42wherein M
is a metal; each X is an atom or group covalently or ionically
bonded to M and may be the same or different; R.sub.1 and R.sub.2
may be the same or each may be different and are substituted or
unsubstituted cyclopentadienyl rings; R.sub.B is a structural
bridge between the cyclopentadienyl rings R.sub.1 and R.sub.2 and
imparts stereorigidity to the rings, and comprises at least one
heteroatom bonded to M, with each of R.sub.1 and R.sub.2 bonded to
the same or different heteroatom of R.sub.B which heteroatom is
also bonded to M; Z is the coordination number of M and is greater
than or equal to 4; m is the number of bonds between M and
heteroatoms of R.sub.1 and to impart sterorigidity m.gtoreq.2;
because the number of bonds around M cannot exceed its coordination
number m+2.ltoreq.Z; and with R.sub.1, R.sub.2 and R.sub.B selected
to provide a catalyst component that is chiral with C.sub.1,
C.sub.2 or C.sub.S symmetry.
2. The compound of claim 1, wherein M is selected from the group
consisting of transition metals and lanthanide metals, wherein the
heteroatoms are selected from the group consisting of O, N, S, and
P,
3. The compound of claim 1, wherein R.sub.B comprises three
heteroatoms bonded to M, and wherein R.sub.1 is bonded to one of
the three heteroatoms, and R.sub.2 is bonded to a different one of
the three heteroatoms.
4. The compound of claim 1, wherein M is selected from among Fe, Co
and Ni.
5. The compound of claim 1, wherein M is Fe, R.sub.B comprises
three heteroatoms bonded to M, and wherein R.sub.1 is bonded to one
of the three heteroatoms, and R.sub.2 is bonded to a heteroatom
different than the heteroatom to which R.sub.1 is bonded; M is
selected from among Fe, Co and Ni.
6. The compound of claim 5, wherein each X is independently
selected from among halides and substituted or unsubstituted
hydrocarbyls.
7. A method of making a bridged metallocene compound comprising
contacting a metal compound of the formula M(X).sub.2 with a
bridged compound R.sub.B of the formula 43wherein M is a metal;
each X is an atom or group covalently or ionically bonded to M and
may be the same or different; R.sub.1 and R.sub.2 may be the same
or each may be different and are substituted or unsubstituted
cyclopentadienyl rings; R.sub.B is a structural bridge between the
cyclopentadienyl rings R.sub.1 and R.sub.2 and imparts
stereorigidity to the rings, and comprises at least one heteroatom
suitable for bonding to M, with each of R.sub.1 and R.sub.2 bonded
to the same or different heteroatom of R.sub.B which heteroatom; Z
is the coordination number of M and is greater than or equal to 4;
and with R.sub.1, R.sub.2 and R.sub.B selected to provide a bridged
metallocene compound that is chiral with C.sub.1, C.sub.2 or
C.sub.S symmetry.
8. The method of claim 7, wherein M is selected from the group
consisting of transition metals and lanthanide metals, wherein the
heteroatoms are selected from the group consisting of O, N, S, and
P,
9. The method of claim 7, wherein R.sub.B comprises three
heteroatoms suitable for bonding to M, and wherein R.sub.1 is
bonded to one of the three heteroatoms, and R.sub.2 is bonded to a
different one of the three heteroatoms.
10. The method of claim 7, wherein M is selected from among Fe, Co
and Ni.
11. The method of claim 7, wherein M is Fe, R.sub.B comprises three
heteroatoms suitable for bonding to M, and wherein R.sub.1 is
bonded to one of the three heteroatoms, and R.sub.2 is bonded to a
heteroatom different than the heteroatom to which R.sub.1 is
bonded; M is selected from among Fe, Co and Ni.
12. The method of claim 11, wherein each X is independently
selected from among halides and substituted or unsubstituted
hydrocarbyls.
13. A catalyst system comprising an activated bridged metallocene
compound having the formula: 44wherein M is a metal; each X is an
atom or group covalently or ionically bonded to M and may be the
same or different; R.sub.1 and R.sub.2 may be the same or each may
be different and are substituted or unsubstituted cyclopentadienyl
rings; R.sub.B is a structural bridge between the cyclopentadienyl
rings R.sub.1 and R.sub.2 and imparts stereorigidity to the rings,
and comprises at least one heteroatom bonded to M, with each of
R.sub.1 and R.sub.2 bonded to the same or different heteroatom of
R.sub.B which heteroatom is also bonded to M; Z is the coordination
number of M and is greater than or equal to 4; m is the number of
bonds between M and heteroatoms of R.sub.B and to impart
sterorigidity m.gtoreq.2; because the number of bonds around M
cannot exceed its coordination number m+2.ltoreq.Z; and with
R.sub.1, R.sub.2 and R.sub.B selected to provide a catalyst
component that is chiral with C.sub.1, C.sub.2 or C.sub.S
symmetry.
14. The system of claim 13, wherein M is selected from the group
consisting of transition metals and lanthanide metals, wherein the
heteroatoms are selected from the group consisting of O, N, S and
P,
15. The system of claim 13, wherein R.sub.B comprises three
heteroatoms bonded to M, and wherein R.sub.1 is bonded to one of
the three heteroatoms, and R.sub.2 is bonded to a different one of
the three heteroatoms.
16. The system of claim 13, wherein M is selected from among Fe, Co
and Ni.
17. The system of claim 13, wherein M is Fe, R.sub.B comprises
three heteroatoms bonded to M, and wherein R.sub.1 is bonded to one
of the three heteroatoms, and R.sub.2 is bonded to a heteroatom
different than the heteroatom to which R.sub.1 is bonded; M is
selected from among Fe, Co and Ni.
18. The system of claim 17, wherein each X is independently
selected from among halides and substituted or unsubstituted
hydrocarbyls.
19. A method of making a catalyst system comprising contacting an
activator with a bridged metallocene compound having the formula:
45wherein M is a metal; each X is an atom or group covalently or
ionically bonded to M and may be the same or different; R.sub.1 and
R.sub.2 may be the same or each may be different and are
substituted or unsubstituted cyclopentadienyl rings; R.sub.B is a
structural bridge between the cyclopentadienyl rings R.sub.1 and
R.sub.2 and imparts stereorigidity to the rings, and comprises at
least one heteroatom bonded to M, with each of R.sub.1 and R.sub.2
bonded to the same or different heteroatom of R.sub.B which
heteroatom is also bonded to M; Z is the coordination number of M
and is greater than or equal to 4; m is the number of bonds between
M and heteroatoms of R.sub.B and to impart sterorigidity
m.gtoreq.2; because the number of bonds around M cannot exceed its
coordination number m+2.ltoreq.Z; and with R.sub.1, R.sub.2 and
R.sub.B selected to provide a catalyst component that is chiral
with C.sub.1, C.sub.2 or C.sub.S symmetry.
20. A method of forming polyolefins comprising contacting olefin
monomer or mixture of monomers in the presence of an activated
bridged metallocene compound having the formula: 46wherein M is a
metal; each X is an atom or group covalently or ionically bonded to
M and may be the same or different; R.sub.1 and R.sub.2 may be the
same or each may be different and are substituted or unsubstituted
cyclopentadienyl rings; R.sub.B is a structural bridge between the
cyclopentadienyl rings R.sub.1 and R.sub.2 and imparts
stereorigidity to the rings, and comprises at least one heteroatom
bonded to M, with each of R.sub.1 and R.sub.2 bonded to the same or
different heteroatom of R.sub.B which heteroatom is also bonded to
M; Z is the coordination number of M and is greater than or equal
to 4; m is the number of bonds between M and heteroatoms of R.sub.B
and to impart sterorigidity m.gtoreq.2; because the number of bonds
around M cannot exceed its coordination number m+2.ltoreq.Z; and
with R.sub.1, R.sub.2 and R.sub.B selected to provide a catalyst
component that is chiral with C.sub.1, C.sub.2 or C.sub.S symmetry.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to catalyst components, to
methods of making such components, to catalyst systems comprising
such components, to methods of making such systems, to methods of
polymerization using such systems, to polymer compositions, and to
articles made from such polymer compositions. In another aspect,
the present invention relates to olefin polymerization catalyst
components, to methods of making such components, to olefin
polymerization catalyst systems comprising such components, to
methods of making such systems, to methods of polymerization using
such systems, to polymer compositions, and to articles made from
such polymer compositions. In even another aspect, the present
invention, the present invention relates to chiral catalysts having
C.sub.1, C.sub.2 or C.sub.S symmetry, to methods of making such
catalysts, methods of polymerization using such catalysts, to
polymer compositions, and to articles made from such polymer
compositions. In still another aspect, the present invention
relates to chiral polyolefin catalysts having C.sub.1, C.sub.2 or
C.sub.S symmetry, to methods of making such catalysts, to methods
of polymerizing or copolymerizing olefins, to polyolefin
compositions, and to articles made from such polyolefin
compositions.
[0003] 2. Description of the Related Art
[0004] As is well known, various processes and catalysts exist for
the production of polyolefins.
[0005] First commercialized in the 1950's, the traditional
Ziegler-Natta catalyst systems utilize a transition metal compound
cocatalyzed by an aluminum alkyl.
[0006] Commercialized in the 1980's, "metallocene" catalysts for
olefin polymerization comprise a metallocene and an aluminum alkyl
component, with the transition metal compound having two or more
cyclopentadienyl ring ligands. Accordingly, titanocenes,
zirconocenes and hafnocenes have all been utilized as the
transition metal component in such "metallocene" containing
catalyst systems for the production of polyolefins. Metallocene
catalysts are cocatalyzed with an alumoxane, rather than an
aluminum alkyl, to provide a metallocene catalyst system of high
activity for the production of polyolefins.
[0007] In addition to Ziegler-Natta catalysts and metallocene
catalysts, a number of "non-metallocene" type catalysts have been
suggested for the polymerization of olefins.
[0008] Specifically, for example, in The Search for New-Generation
Olefin Polymerization Catalysts: Life Beyond Metallocenes, Angew.
Chem. Int. Ed. 1999, 38, 428-447, Britovsek et al. review a number
of olefin catalyst systems, including: Group 3 metal catalysts such
as scandium and yttrium complexes; Rare Earth Metal catalysts such
as lanthanide and actinide-based catalysts stabilized with
substituted cyclopentadienyl ligands; cationic Group 4 metal
complexes including carbon-based ligands (such as alkyl ligands,
allyl ligands, Cp analogues), including nitrogen-based ligands
(such as amide ligands either along or in combination with other
ligands, amidinate ligands either alone or in combination with
other ligands, and .beta.-diketimate ligands), and including
oxygen-based ligands (such as alkoxide ligands either alone or in
combination with other ligands, bis-alkoxides with additional
donors); neutral Group 4 metal complexes; Group 5 metal catalysts;
Group 6 metal catalysts; Group 8 metal catalysts; Group 9 metal
catalysts; Group 10 metal catalysts; Group 13 metal catalysts.
[0009] Additionally, in Iron and Cobalt Ethylene Polymerization
Catalysts Bearing 2,6-Bis (Imino)Pyridyl Ligands; Synthesis,
Structures, and Polymerization Studies, J. Am. Chem. Soc. 1999,
121, 8728-8740, Britovsek et al. disclose certain iron and cobalt
catalysts for the polymerization of ethylene.
[0010] WO 98/30612, published Jul. 16, 1998, discloses selected
iron complexes of 2,6-pyridinecarboxaldehydebis(imines) and
2,6-diacyclpyridinebis(imines) as catalysts for the polymerization
of propylene.
[0011] WO 99/12981, published Mar. 18, 1999, discloses catalyst
complexes having a bridge comprising heteroatoms bridging R groups
R.sup.5 and R.sup.7, with these complexes taught as being useful
"especially for polymerizing ethylene alone or for copolymerizing
ethylene with higher 1-olefins" (page 2, lines 28-29). The bridged
R groups R.sup.5 and R.sup.7 are independently selected from
hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl or substituted heterohydrocarbyl. There is no
teaching or suggestion to make a chiral complex suitable for
producing high tacticity, crystallinity polypropylene.
[0012] The following patents disclose bridged metallocene catalyst
systems: U.S. Pat. No. 5,145,819, issued Sep. 8, 1992 to Winter et
al.; U.S. Pat. No. 5,158,920, issued Oct. 27, 1992 to Razavi; U.S.
Pat. No. 5,243,001, issued Sep. 7, 1993 to Winter et al.; U.S. Pat.
No. 6,002,033, issued Dec. 14, 1999 to Razavi et al.; U.S. Pat. No.
6,066,588, issued May 23, 2000, to Razavi et al.; U.S. Pat. No.
6,177,529 B1, issued Jan. 23, 2001, to Razavi et al.; U.S. Pat. No.
6,194,343 B1, issued Feb. 27, 2001 to Collins et al.; U.S. Pat. No.
6,211,110 B1, issued Apr. 3, 2001 to Santi et al.; and U.S. Pat.
No. 6,268,518 B1, issued Jul. 31, 2001 to Resconi et al.
[0013] However, in spite of the above advancements, there still
exists a need in the art for catalyst compositions, methods of
making such compositions, methods of polymerization using such
compositions, to polymer compositions, and to articles made from
such polymer compositions.
[0014] There is another need in the art for catalyst compositions,
methods of making such compositions, methods of polymerization
using such compositions, to polymer compositions, and to articles
made from such polymer compositions, which do not suffer from the
disadvantages of the prior art compositions, products and
methods.
[0015] These and other needs in the art will become apparent to
those of skill in the art upon review of this specification,
including its drawings and claims.
SUMMARY OF THE INVENTION
[0016] It is an object of the present invention to provide for
catalyst compositions, methods of making such compositions, methods
of polymerization using such compositions, to polymer compositions,
and to articles made from such polymer compositions.
[0017] It is another object of the present invention to provide for
catalyst compositions, methods of making such compositions, methods
of polymerization using such compositions, to polymer compositions,
and to articles made from such polymer compositions, which do not
suffer from the disadvantages of the prior art compositions,
products and methods.
[0018] These and other objects of the present invention will become
apparent to those of skill in the art upon review of this
specification, including its drawings and claims.
[0019] According to one embodiment of the present invention there
is provided a bridged metallocene compound having the formula:
1
[0020] wherein M is a metal; each X is an atom or group covalently
or ionically bonded to M and may be the same or different; R.sub.1
and R.sub.2 may be the same or each may be different and are
substituted or unsubstituted cyclopentadienyl rings; R.sub.B is a
structural bridge between the cyclopentadienyl rings R.sub.1 and
R.sub.2 and imparts stereorigidity to the rings, and comprises at
least one heteroatom bonded to M, with each of R.sub.1 and R.sub.2
bonded to the same or different heteroatom of R.sub.B which
heteroatom is also bonded to M; Z is the coordination number of M
and is greater than or equal to 4; m is the number of bonds between
M and heteroatoms of R.sub.B and to impart sterorigidity
m.gtoreq.2; because the number of bonds around M cannot exceed its
coordination number m+2.ltoreq.Z; and with R.sub.1, R.sub.2 and
R.sub.B selected to provide a catalyst component that is chiral
with C.sub.1, C.sub.2 or C.sub.S symmetry.
[0021] According to another embodiment of the present invention,
there is provided a method of making a bridged metallocene compound
comprising contacting a metal compound of the formula M(X).sub.2
with a bridged compound R.sub.B of the formula 2
[0022] wherein M, X, R.sub.1, R.sub.2, m and z are as defined
above.
[0023] According to even another embodiment of the present
invention, there is provided a catalyst system comprising an
activated bridged metallocene compound having the formula: 3
[0024] wherein M, X, R.sub.1, R.sub.2, m and z are as defined
above.
[0025] According to still another embodiment of the present
invention, there is provided a method of making a catalyst system
comprising contacting an activator with a bridged metallocene
compound having the formula: 4
[0026] wherein M, X, R.sub.1, R.sub.2, m and z are as defined
above.
[0027] According to yet another embodiment of the present
invention, there is provided a method of forming polyolefins
comprising contacting olefin monomer or mixture of monomers in the
presence of an activated bridged metallocene compound having the
formula: 5
[0028] wherein M, X, R.sub.1, R.sub.2, m and z are as defined
above.
[0029] For all of the above embodiments, various further
embodiments are provided by changing M, X, R.sub.1, R.sub.2, m and
z as described in the detailed description.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The bridged metallocene catalyst component of the present
invention is represented by the following formula EQN. 1: 6
[0031] wherein M is a metal; each X is an atom or group covalently
or ionically bonded to M and may be the same or different; R.sub.1
and R.sub.2 may be the same or each may be different and are
substituted or unsubstituted cyclopentadienyl rings; R.sub.B is a
structural bridge between the cyclopentadienyl rings R.sub.1 and
R.sub.2 and imparts stereorigidity to the rings, and comprises at
least one heteroatom bonded to M, with each of R.sub.1 and R.sub.2
bonded to the same or different heteroatom of R.sub.B which
heteroatom is also bonded to M; Z is the coordination number of M
and is greater than or equal to 4; m is the number of bonds between
M and the heteroatom(s) of R.sub.B and to impart sterorigidity
m.gtoreq.2; because the number of bonds around M cannot exceed its
coordination number m+2.ltoreq.Z; with R.sub.1, R.sub.2 and R.sub.B
selected to provide a catalyst component that is chiral with
C.sub.1, C.sub.2 or C.sub.S symmetry.
[0032] The metal M of the present invention may be any suitable
metal useful as the metal component in metallocene catalysts. As a
non-limiting example, M may be selected from among any metal as is
known in the prior art to be useful as the metal component in
metallocene catalysts.
[0033] M will be selected to have a coordination number Z that is
at least equal to the number of substituents bonded to M, that is,
m number of R.sub.B heteroatom-to-metal bonds plus 2 (for both
X's).
[0034] Preferably, M is selected from among any transition metal.
More preferably, M is selected from among transition metals,
lanthanides and actinides. Even more preferably, M is selected from
transition metals and lanthanides. Still more preferably, M is
selected from among group 3d, 4d or 5d transition metals,
specifically Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt. Yet more
preferably, M is selected from among Fe, Co and Ni. Even still more
preferably, M is selected from among Fe and Co.
[0035] R.sub.1 and R.sub.2 may be the same or each may be different
and may be generally described as being substituted or
unsubstituted cyclopentadienyl rings. As non-limiting examples,
R.sub.1 and R.sub.2 may be selected from among any substituted or
unsubstituted cyclopentadienyl ring as are known in the art to be
useful in metallocene catalysts. Non-limiting examples of
hydrocarbon radicals suitable for use as R.sub.1 and R.sub.2 are
shown in the Examples below.
[0036] Preferably, R.sub.1 and R.sub.2 may be described as a
cyclopentadienyl ring of the form (C.sub.5(R').sub.4), wherein each
R' may be the same or each may be different, and R' is a hydrogen
or a substituted or unsubstituted hydrocarbyl radical having 1-20
carbon atoms.
[0037] Non-limiting examples of hydrocarbyl radicals suitable for
use as R' include unsubstituted and substituted alkyl, alkenyl,
aryl, alkylaryl or arylalkyl radicals. More specific non-limiting
examples of suitable hydrocarbyl radicals include unsubstituted and
substituted methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl,
isobutyl, heptyl, octyl, nonyl, decyl, cetyl, phenyl, methylene,
ethylene, propylene, and other like groups.
[0038] R.sub.B is a structural bridge between the cyclopentadienyl
rings R.sub.1 and R.sub.2 and imparts stereorigidity to the rings,
and comprises n heteroatoms ("HA") bonded to M. Preferably,
n.gtoreq.1, more preferably n.gtoreq.2, and even more preferably
n.gtoreq.3. An example of a suitable structural bridge R.sub.B is
provided in the examples.
[0039] Heteroatoms useful in structural bridge R.sub.B include any
that can be coordinated to the metal M by a "dative" bond, that is,
a bond formed by the donation of a lone pair of electrons from the
heteroatom. Where R.sub.B comprises more than one heteroatom bonded
to M, they may be the same heteroatom or different heteroatoms.
Non-limiting examples of suitable heteroatoms include O, N, S, and
P. Preferably the heteroatoms are selected from among O, N, and P,
and more preferably is N.
[0040] R.sub.1 is bonded to a heteroatom of R.sub.B which
heteroatom is also bonded to M. Likewise, R.sub.2 is also bonded to
a heteroatom of R.sub.B which heteroatom is also bonded to M.
R.sub.1 and R.sub.2 may be bonded to the same heteroatom that is
also bonded to M, or may be bonded to different heteroatoms which
different heteroatoms are also bonded to M.
[0041] According to the present invention, R.sub.1, R.sub.2 and
R.sub.B are selected to provide a catalyst component that is chiral
with C.sub.1, C.sub.2 or C.sub.S symmetry.
[0042] Each X may be any atom or group as are known to be utilized
with metallocene catalysts, and is generally covalently or
ionically bonded to M. Each X may be the same or different,
although commonly each X is the same. As a non-limiting example, X
may be selected from among halide, sulphate, nitrate, thiolate,
thiocarboxylate, BF.sub.4.sup.-, PF.sub.6.sup.-, hydride,
hydrocarbyloxide, carboxylate, substituted or unsubstituted
hydrocarbyl, and heterohydrocarbyl. Non-limiting examples of such
atoms or groups are chloride, bromide, methyl, ethyl, propyl,
butyl, octyl decyl, phenyl, benzyl, methoxide, ethoxide,
isopropoxide, toxylate, triflate, formate, acetate, phenoxide and
benzoate. Preferably, X is a halide or a C.sub.1 to C.sub.20
hydrocarbyl. More preferably, X is chloride.
[0043] The bridged metallocene catalyst component is generally made
by contacting a bridge intermediate with a compound of the form
M(X).sub.2. More details are provided in the Examples.
[0044] The present invention further includes a catalyst system
comprising one or more of the above described bridged metallocene
catalyst components and one or more activators and/or cocatalysts
(as described in greater detail below) or the reaction product of
an activator and/or cocatalyst, such as for example
methylaluminoxane (MAO) and optionally an alkylation/scavenging
agent such as trialkylaluminum compound (TEAL). The above described
metallocene catalyst components may also be supported as is known
in the metallocene art. Typical supports may be any support such as
talc, an inorganic oxide, clay, and clay minerals, ion-exchanged
layered compounds, diatomaceous earth, silicates, zeolites or a
resinous support material such as a polyolefin. Specific inorganic
oxides include silica and alumina, used alone or in combination
with other inorganic oxides such as magnesia, titania, zirconia and
the like. Non-metallocene transition metal compounds, such as
titanium tetrachloride, are also incorporated into the supported
catalyst component. The inorganic oxides used as support are
characterized as having an average particle size ranging from
30-600 microns, desirably from 30-100 microns, a surface area of
50-1,000 square meters per gram, desirably from 100-400 square
meters per gram, a pore volume of 0.5-3.5 cc/g, desirably from
about 0.5-2 cc/g.
[0045] The bridged metallocenes of the present invention may be
used in combination with some form of activator in order to create
an active catalyst system. The term "activator" is defined herein
to be any compound or component, or combination of compounds or
components, capable of enhancing the ability of one or more
metallocenes to polymerize olefins to polyolefins. Alklyalumoxanes
such as methylalumoxane (MAO) are commonly used as metallocene
activators. Generally alkylalumoxanes contain about 5 to 40 of the
repeating units.
1 7 AIR.sub.2 for linear species and 8 for cyclic species
[0046] where R is a C1-C8 alkyl including mixed alkyls.
Particularly desirable are the compounds in which R is methyl.
Alumoxane solutions, particularly methylalumoxane solutions, may be
obtained from commercial vendors as solutions having various
concentrations. There are a variety of methods for preparing
alumoxane, non-limiting examples of which are described in U.S.
Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,
4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,
5,248,801, 5,235,081, 5,103,031 and EP-A-0 561 476, EP 0 279 586,
EP-A-0 594 218 and WO 94/10180, each fully incorporated herein by
reference. (As used herein unless otherwise stated "solution"
refers to any mixture including suspensions.) Ionizing activators
may also be used to activate the bridged metallocenes. These
activators are neutral or ionic, or are compounds such as
tri(n-butyl)ammonium tetrakis(pentaflurophenyl)borate, which ionize
the neutral metallocene compound. Such ionizing compounds may
contain an active proton, or some other cation associated with, but
not coordinated or only loosely coordinated to, the remaining ion
of the ionizing compound. Combinations of activators may also be
used, for example, alumoxane and ionizing activators in
combinations, see for example, WO 94/07928.
[0047] Descriptions of ionic catalysts for coordination
polymerization comprised of metallocene cations activated by
non-coordinating anions appear in the early work in EP-A-0 277 003,
EP-A-0 277 004 and U.S. Pat. No. 5,198,401 and WO-A-92/00333
(incorporated herein by reference). These teach a desirable method
of preparation wherein metallocenes (bis Cp and monoCp) are
protanated by an anion precursor such that an alkyl/hydride group
is abstracted from a transition metal to make it both cationic and
charge-balanced by the non-coordinating anion. Suitable ionic salts
include tetrakis-substituted borate or aluminum salts having
fluorided aryl-constituents such as phenyl, biphenyl and
napthyl.
[0048] The term "noncoordinating anion" ("NCA") means an anion
which either does not coordinate to said cation or which is only
weakly coordinated to said cation thereby remaining sufficiently
labile to be displaced by a neutral Lewis base. "Compatible"
noncoordinating anions are those which are not degraded to
neutrality when the initially formed complex decomposes. Further,
the anion will not transfer an anionic substituent or fragment to
the cation so as to cause it to form a neutral four coordinate
metallocene compound and a neutral by-product from the anion.
[0049] The use of ionizing ionic compounds not containing an active
proton but capable of producing both the active metallocene cation
and a noncoordinating anion is also known. See, for example, EP-A-0
426 637 and EP-A-0 573 403 (incorporated herein by reference). An
additional method of making the ionic catalysts uses ionizing anion
precursors which are initially neutral Lewis acids but form the
cation and anion upon ionizing reaction with the metallocene
compounds, for example the use of tris(pentafluorophenyl) borane,
see EP-A-0 520 732 (incorporated herein by reference). Ionic
catalysts for addition polymerization can also be prepared by
oxidation of the metal centers of transition metal compounds by
anion precursors containing metallic oxidizing groups along with
the anion groups, see EP-A-0 495 375 (incorporated herein by
reference).
[0050] Where the metal ligands include halogen moieties (for
example, bis-cyclopentadienyl zirconium dichloride) which are not
capable of ionizing abstraction under standard conditions, they can
be converted via known alkylation reactions with organometallic
compounds such as lithium or aluminum hydrides or alkyls,
alkylalumoxanes, Grignard reagents, etc. See EP-A-O 500 944 and
EP-Al-0 570 982 (incorporated herein by reference) for in situ
processes describing the reaction of alkyl aluminum compounds with
dihalo-substituted metallocene compounds prior to or with the
addition of activating anionic compounds.
[0051] Desirable methods for supporting ionic catalysts comprising
metallocene cations and NCA are described in U.S. Pat. No.
5,643,847, U.S. patent application No. 09184358, filed Nov. 2, 1998
and U.S. patent application No. 09184389, filed Nov. 2, 1998 (all
fully incorporated herein by reference). When using the support
composition, these NCA support methods generally comprise using
neutral anion precursors that are sufficiently strong Lewis acids
to react with the hydroxyl reactive functionalities present on the
silica surface such that the Lewis acid becomes covalently
bound.
[0052] Additionally, when the activator for the metallocene
supported catalyst composition is a NCA, desirably the NCA is first
added to the support composition followed by the addition of the
bridged metallocene catalyst. When the activator is MAO, desirably
the MAO and bridged metallocene catalyst are dissolved together in
solution. The support is then contacted with the MAO/metallocene
catalyst solution. Other methods and order of addition will be
apparent to those skilled in the art.
[0053] The catalysts of the present invention can be used for the
polymerization of any type of .alpha.-olefins or the
copolymerization any mixture of .alpha.-olefins. For example, the
present catalyst is useful for catalyzing ethylene, propylene,
butylene, pentene, hexene, 4-methylpentene and other
.alpha.-alkenes having at least 2 carbon atoms, and also for
mixtures thereof. Preferably, the catalysts of the present
invention are utilized for the polymerization of propylene to
produce polypropylene, most preferably high crystallinity
polypropylene.
[0054] The polymerization and, where applicable, pre-polymerization
conditions are well known in the art and need not be described in
too much detail here. In general, polymerization is accomplished by
contacting together either .alpha.-olefin monomer or mixture of
.alpha.-olefins in the presence of the above described catalyst
system under polymerization conditions.
[0055] The invention having been generally described, the following
examples are given as particular embodiments of the invention and
to demonstrate the practice and advantages thereof. It is
understood that the exaples are given by way of illustration and
are not intended to limit the specification or the claims to follow
in any manner.
EXAMPLES
[0056] These examples are provided merely to illustrate a few
embodiments of the present invention, and are not intended to and
do not limit the specification or scope of the claims.
[0057] In these examples, all manipulations of
air/moisture-sensitive materials were performed on a conventional
vacuum/inert atmosphere line using standard Schlenk line
techniques.
Example 1
[0058] The procedure as described in WO 99/12981 was utilized for
synthesis of ligand intermediate A of the formula as shown below:
9
[0059] 2,6-diisopropylaniline (3.46 ml, 18.4 mmol) was added
dropwise to a solution of 2,6-diacetylpyridine (1.5 g, 9.2 mmol) in
absolute ethanol (25 ml) A few drops of glacial acetic acid was
added and the solution was refluxed for 48 h. Concentration of the
solution to half volume and cooling to -78.degree. C. gave
intermediate A as pale yellow crystals (80%). Calcd for C33H43N3:
C, 82.3; H 8.9; N 8.7; Found; C, 81.9; H 8.5; 8.7%. FABMS: M+(481).
1H NMR (CDCl3): 8.6-7.9 [m, 3H, C5H3N], 7.2-6.9 [m, 6H,
C6(CHMe2)H3], 2.73[sept, 4H, CHMe2], 2.26[s, 6H, C5H3N(CMeNAr)2]
and 1.16 [m, 24H, CHMe2]. FABMS is fast atom bombardment mass
spectrometry.
Example 2
[0060] 250 mg, 1.09 eq. of Intermediate A, and 95 mg of FeCl2.4H2O
was weighed into a 10 ml Schlenk flask containing a stirbar. The
flask was placed on a Schlenk manifold, backfilled 3 times with
argon, and 10 ml of THF were added while stirring. After 2 h, the
THF was removed under vacuum. The resulting deep blue solid
(formula below), was washed twice with ether and dried under
vacuum. 10
Example 3
[0061] This example shows creation of a ligand having C2/Class A
symmetry. The same general synthesis is followed from Example 1,
with the exception that the 2,6-diisopropylaniline is replaced with
indene.
[0062] Indene (18.4 mmol) is added to a solution of
2,6-diacetylpyridine (9.2 mmol) in absolute. A few drops of glacial
acetic acid is added and the solution is refluxed for 48 h.
Concentration of the solution to half volume and cooling to room
temperature and filtered to give the intermediate shown below.
11
Example 4
[0063] A catalyst from the ligand of Example 3 (Intermediate with
symmetry C2/Class A) is synthesized by using the same general
synthesis as in Example 2, to provide the catalyst component shown
below. 12
Example 5
[0064] This example shows creation of a ligand having C2/Class B
symmetry. The first part of the synthesis for this ligand is
different from that of Example 1 above. The first part of the
synthesis starts with the reduction of the diacetylpyridine to a
diamine by using the Leuckart-Wallach reaction. In scheme 1 below,
a general reaction is shown for the reduction of a carbonyl to an
amine.
[0065] Scheme 1. Reduction of a carbonyl compounds to amines
(Leuckart-Wallach Reaction): 13
Example 6
[0066] This example illustrates the reduction of a carbonyl to an
amine, specifically, the synthesis of 1-phenylethylamine (Vogel's
Practical Organic Chemistry including qualitative organic analysis,
4.sup.th Ed, Furniss, B. S., et al., School of Chemistry Thames
Polytechnic Longman Scientific and Technical, 1978).
[0067] 126 g (2.0 mol) of ammonium formate, 72 g (0.6 mol) of
acetophenone and a few chips of porous porcelain were added to a
250 ml flask fitted with a Claisen still-head carrying a short
fractionating column; a thermometer expending nearly to the bottom
of the flask was inserted, and a short condenser was set for
downward distillation to the side arm. The flask was heated (either
with a heating mantle or in an air batch); the mixture first melted
to two layers and distillation occurs. The mixture becomes
homogeneous at 150-155 C. and reaction took place with slight
frothing. Heating was continued, until the temperature reached 185
C. (about 2 hours); acetophenone, water and ammonium carbonate
distill. The heating was stopped at 185 C., the upper layer of
acetophenone was separated from the distillate and returned without
drying to the flask. The mixture was heated for 3 hours at 180-185
C. and allowed to cool; the acetophone may be recovered from the
distillate by extraction with 20 ml portions of toluene. The
reaction mixture is transferred to a 250 ml separatory funnel and
shake it with two 75 ml portions of water to remove formamide and
ammonium formate. The crude (1-phenylethyl)formamide is transferred
into the original reaction flask; the aqeous layer was extracted
with two 20 ml portions of toluene, the toluene extracts were
transferred to the flask, 75 ml of concentrated hydrochloric acid
and a few chips of porous porcelain were added. The mixture was
heated cautiously until about 40 ml of toluene was collected, and
boiled gently under reflux for a further 40 minutes; hydrolysis
proceeded rapidly to 1-phenylethylamine hydrochloride except for a
small layer of unchanged acetophenone. The reaction mixture was
allowed to cool, and the acetopenone was removed by extraction with
four 20 ml portions of toluene. The aqueous acid solution was
transferred to a 500 ml round-bottom flask equipped for stream
distillation, a solution of 62.5 g of sodium hydroxide was
cautiously added to 125 ml water, and steam distilled: the
distillation flask was heated so that the volume remained nearly
constant. Most of the amine is contained in the first 500 ml of
distillate; the operation was stopped when the distillate was only
faintly alkaline. The distillate was extracted with five 25, ml
portions of toluene, the extract was dried with sodium hydroxide
pellets and fractionally distilled. Toluene distilled over at 111
C., followed by the phylethylamine. The latter was collected as a
fraction of b.p. 180-190 C. (the bulk of the product distiled at
184-186 C. (3); the yield was 43 g (59%).
Example 7
[0068] The reduction of 2,6-diacetylpiridine to the diamine is
provided using a similar synthetic procedure as described in
Example 6 above.
Example 8
[0069] The diamine as obtained in Example 7 is then reacted with a
ketone as shown in the following reaction formula. 14
Example 9
[0070] The catalyst synthesis procedure to produce a catalyst with
symmetry C2/Class B is the same procedure as the one described in
WO 98/30612 (with the exception of different R' and R groups), and
is shown in the following reaction formula: 15
Example 10
[0071] This example provides a catalyst with symmetry C2/Class B by
reacting the ligand of Example 9 with the desired metal.
[0072] The ligand (1.05 eq.) of Example 9 and the metal salt in its
hydrated or anhydrous form are added together in a Schlenk flask
under inert atmosphere and then charged with THF. The mixture is
stirred for several hours or until no detectable unreacted salts
are observed. The mixture is filtered in air and the solids are
washed with Et2O and dried under vacuum. 16
Example 11
[0073] To synthesize a structure with a C2/Class C symmetry, a
similar procedure as the one used for the C2/Class B symmetry is
used. The exception is that only one acetyl group is reduced on the
2,6-diacetylanaline. The general procedure for this synthesis is
shown in the formula below where only one of the acetyls is reduced
to the amine. 17
Example 12
[0074] In this example, the amine of Example 11 is reacted with a
ketone to provide the R group double bond to the nitrogen. 18
Example 13
[0075] In this Example, an amine is reacted with the mono-acetyl
intermediate of Example 12 to provide the R group with a single
bond to the nitrogen as shown in the formula below. 19
Example 14
[0076] A catalyst is then synthesized according to the procedure
described in Example 10.
[0077] Simply by using different R groups bonded to the nitrogen
atoms with a single bond, a double bond, or with one single bond
and one double bond, th esymmetries for C.sub.1 and C.sub.S may
also be obtained. Some examples for the different symmetries is
summarized in Table 1 for the structure of EQN. 1.
2TABLE 1 Examples of Symmetries Symmetry R1 R2 C2/Class A 20 21
C2/Class B 22 23 C2/Class C 24 25 Cs/Class A 26 27 Cs/Class B 28 29
Cs/Class C 30 31 Cs/Class D 32 33 C1/Class A 34 35 C1/Class B 36 37
C1/Class C 38 39 C1/Class D 40 41
[0078] Any patents, patent applications, articles, books,
treatises, and any other publications cited herein, are hereby
incorporated by reference for all that they teach or suggest.
[0079] While the illustrative embodiments of the invention have
been described with particularity, it will be understood that
various other modifications will be apparent to and can be readily
made by those skilled in the art without departing from the spirit
and scope of the invention. Accordingly, it is not intended that
the scope of the claims appended hereto be limited to the examples
and descriptions set forth herein but rather that the claims be
construed as encompassing all the features of patentable novelty
which reside in the present invention, including all features which
would be treated as equivalents thereof by those skilled in the art
to which this invention pertains.
* * * * *