U.S. patent application number 09/827981 was filed with the patent office on 2002-02-07 for catalyst system and its use in a polymerization process.
Invention is credited to Holtcamp, Matthew W., McConville, David H..
Application Number | 20020016257 09/827981 |
Document ID | / |
Family ID | 23761246 |
Filed Date | 2002-02-07 |
United States Patent
Application |
20020016257 |
Kind Code |
A1 |
McConville, David H. ; et
al. |
February 7, 2002 |
Catalyst system and its use in a polymerization process
Abstract
The present invention relates to a catalyst system of a Group 15
containing metal catalyst compound and a Lewis acid aluminum
containing activator and to a supported catalyst system thereof and
to a process for polymerizing olefin(s) utilizing them.
Inventors: |
McConville, David H.;
(Houston, TX) ; Holtcamp, Matthew W.; (Huffman,
TX) |
Correspondence
Address: |
Univation Technologies, LLC
Suite 1950
5555 San Felipe
Houston
TX
77056
US
|
Family ID: |
23761246 |
Appl. No.: |
09/827981 |
Filed: |
April 6, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09827981 |
Apr 6, 2001 |
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09443551 |
Nov 18, 1999 |
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Current U.S.
Class: |
502/150 ;
502/102; 502/103 |
Current CPC
Class: |
C08F 10/02 20130101;
C08L 2205/02 20130101; C08F 210/16 20130101; C08F 4/64148 20130101;
C08L 2666/04 20130101; C08F 210/14 20130101; C08F 2500/12 20130101;
C08F 2500/01 20130101; C08F 4/025 20130101; C08L 2666/04 20130101;
C08F 4/659 20130101; C08F 2500/02 20130101; C08F 2500/04 20130101;
C08L 23/16 20130101; C08F 2500/26 20130101; C08L 23/0815 20130101;
C08L 23/0815 20130101; C08F 10/02 20130101; C08F 10/02 20130101;
C08F 4/65916 20130101; C08F 210/16 20130101; C08L 23/16 20130101;
C08L 2314/06 20130101; C08F 10/02 20130101; C08F 4/65912
20130101 |
Class at
Publication: |
502/150 ;
502/102; 502/103 |
International
Class: |
B01J 031/00 |
Claims
We claim:
1. A process for polymerizing olefin(s) in the presence of a
catalyst system comprising a Group 15 containing metal catalyst
compound and a Lewis acid aluminum containing activator.
2. The process of claim 1 wherein the Group 15 containing metal
catalyst compound is a Group 15 containing bidentate or tridentate
ligated metal catalyst compound.
3. The process of claim 1 wherein the Group 15 containing metal
catalyst compound is a metal atom bound to at least one substituted
alkyl leaving group having 6 or greater carbon atoms and to at
least two Group 15 atoms, where at least one of the at least two
Group 15 atoms is bound to a Group 15 or 16 atom through a bridging
group.
4. The process of claim 3 wherein the bridging group is selected
from the group consisting of a C.sub.1 to C.sub.20 hydrocarbon
group, a heteroatom containing group, silicon, germanium, tin,
lead, and phosphorus.
5. The process of claim 4 wherein the Group 15 or 16 atom may also
be bound to nothing, a hydrogen, a Group 14 atom containing group,
a halogen, or a heteroatom containing group, and wherein each of
the two Group 15 atoms are also bound to a cyclic group and may
optionally be bound to hydrogen, a halogen, a heteroatom or a
hydrocarbyl group, or a heteroatom containing group.
6. The process of claim 1 wherein the Group 15 containing metal
compound is represented by the formulae: 4wherein M is metal; each
X is a leaving group; y is 0 or 1; n is the oxidation state of M; m
is the formal charge of the YZL or the YZL' ligand; L is a Group 15
or 16 element; L' is a Group 15 or 16 element or Group 14
containing group; Y is a Group 15 element; Z is a Group 15 element;
R.sup.1 and R.sup.2 are independently a C.sub.1 to C.sub.20
hydrocarbon group, a heteroatom containing group having up to
twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus;
R.sup.3 is absent or a hydrocarbon group, hydrogen, a halogen, a
heteroatom containing group; R.sup.4 and R.sup.5 are independently
an alkyl group, an aryl group, substituted aryl group, a cyclic
alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl
group, a substituted cyclic arylalkyl group or multiple ring
system; R.sup.1 and R.sup.2 may be interconnected to each other,
and/or R.sup.4 and R.sup.5 may be interconnected to each other;
R.sup.6 and R.sup.7 are independently absent, or hydrogen, an alkyl
group, halogen, heteroatom or a hydrocarbyl group; and R* is
absent, or is hydrogen, a Group 14 atom containing group, a
halogen, a heteroatom containing group.
7. The process of claim 6 wherein R.sup.4 and R.sup.5 are
represented by the formula: 5wherein R.sup.8 to R.sup.12 are each
independently hydrogen, a C.sub.1 to C.sub.40 alkyl group, a
halide, a heteroatom, a heteroatom containing group containing up
to 40 carbon atoms, preferably a C.sub.1 to C.sub.20 linear or
branched alkyl group, preferably a methyl, ethyl, propyl or butyl
group, any two R groups may form a cyclic group and/or a
heterocyclic group. The cyclic groups may be aromatic.
8. The process of claim 7 wherein R.sup.9, R.sup.10 and R.sup.12
are independently a methyl, ethyl, propyl or butyl group and X is a
substituted alkyl group having greater than 6 carbon atoms.
9. The process of claim 7 wherein R.sup.9, R.sup.10 and R.sup.12
are methyl groups, and R.sup.8 and R.sup.11 are hydrogen and X is a
alkyl substituted with an aryl group.
10. The process of claim 6 wherein L, Y, and Z are independently
nitrogen, R.sup.1 and R.sup.2 are a hydrocarbon radical, R.sup.3 is
hydrogen, and R.sup.6 and R.sup.7 are absent.
11. The process of claim 6 wherein L and Z are independently
nitrogen, L' is a hydrocarbyl radical, and R.sup.6 and R.sup.7 are
absent.
12. The process of claim 1 wherein the catalyst system is supported
on a carrier.
13. The process of claim 1 wherein the process is a continuous gas
phase process.
14. The process of claim 1 wherein the process is a continuous
slurry phase process.
15. The process of claim 1 wherein the olefin(s) is ethylene or
propylene.
16. The process of claim 1 wherein the olefins are ethylene and at
least one other monomer having from 3 to 20 carbon atoms.
17. The process of claim 1 wherein the catalysts system further
comprises an activator.
18. A supported catalyst system comprising: a Group 15 containing
metal catalyst compound, an activator and a carrier.
19. The supported catalyst system of claim 18 wherein the Group 15
containing metal catalyst compound is a Group 15 containing
bidentate or tridentate ligated metal catalyst compound having a
substituted hydrocarbon leaving group.
20. The supported catalyst system of claim 18 wherein the Group 15
containing metal catalyst compound is contacted with the activator
to form a reaction product that is then contacted with the carrier.
Description
[0001] Furthermore, U.S. Pat. No. 5,576,460 describes a preparation
of arylamine ligands and U.S. Pat. No. 5,889,128 discloses a
process for the living polymerization of olefins using initiators
having a metal atom and a ligand having two group 15 atoms and a
group 16 atom or three group 15 atoms. EP 893 454 A1 also describes
preferably titanium transition metal amide compounds. In addition,
U.S. Pat. No. 5,318,935 discusses amido transition metal compounds
and catalyst systems especially for the producing isotactic
polypropylene. Polymerization catalysts containing bidentate and
tridentate ligands are further discussed in U.S. Pat. No.
5,506,184.
[0002] While all these compounds have been described in the art,
there is still a need for an improved catalyst system.
SUMMARY OF THE INVENTION
[0003] This invention provides for a catalyst system and for its
use in polymerizing process.
[0004] In one embodiment, the invention is directed to a catalyst
system of a Group 15 containing transition metal catalyst compound
and a Lewis acid activator and to its use in the polymerization of
olefin(s).
[0005] In another embodiment, the invention is directed to a
catalyst system of a Group 15 containing bidentate or tridentate
ligated transition metal catalyst compound and a Lewis acid
aluminum containing activator to its use in the polymerization of
olefin(s).
[0006] In another embodiment, the invention is directed to a
catalyst system having a transition metal bound to at least one
leaving group and also bound to at least two Group 15 atoms, at
least one of which is also bound to a Group 15 or 16 atom through
another group, and a Lewis acid aluminum containing activator, and
to its use in the polymerization of olefin(s).
[0007] In still another embodiment, the invention is directed to a
method for supporting the multidentate metal based catalyst system,
and to the supported catalyst system itself.
[0008] In another embodiment, the invention is directed to a
process for polymerizing olefin(s), particularly in a gas phase or
slurry phase process, utilizing any one of the catalyst systems or
supported catalyst systems discussed above.
DETAILED DESCRIPTION OF THE INVENTION
[0009] Introduction
[0010] It has been found that catalyst systems of a Group 15
containing transition metal catalyst compound and a Lewis acid
aluminum containing activators exhibit commercially acceptable
productivity with excellent operability. Also, in particular the
catalyst system of the invention is supportable on a support
material, preferably for use in a slurry or gas phase
polymerization process.
[0011] Group 15 Containing Metal Catalyst Compound and Catalyst
Systems
[0012] In one embodiment, the metal based catalyst compounds of the
invention are Group 15 bidentate or tridentate ligated transition
metal compound having at least one substituted hydrocarbon group,
the preferred Group 15 elements are nitrogen and/or phosphorous,
most preferably nitrogen, and the preferred leaving group is a
substituted alkyl group having greater than 6 carbon atoms,
preferably the alkyl substituted with an aryl group.
[0013] The Group 15 containing metal catalyst compounds of the
invention generally include a transition metal atom bound to at
least one substituted hydrocarbon leaving group and also bound to
at least two Group 15 atoms, at least one of which is also bound to
a Group 15 or 16 atom through another group.
[0014] In one preferred embodiment, at least one of the Group 15
atoms is also bound to a Group 15 or 16 atom through another group,
which may be a hydrocarbon group, preferably a hydrocarbon group
having 1 to 20 carbon atoms, a heteroatom containing group,
preferably silicon, germanium, tin, lead, or phosphorus. In this
embodiment, it is further preferred that the Group 15 or 16 atom be
bound to nothing or a hydrogen, a Group 14 atom containing group, a
halogen, or a heteroatom containing group. Additionally in these
embodiment, it is preferred that each of the two Group 15 atoms are
also bound to a cyclic group that may optionally be bound to
hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a
heteroatom containing group.
[0015] In an embodiment of the invention, the Group 15 containing
metal compound of the invention is represented by the formulae:
1
[0016] wherein M is a metal, preferably a transition metal, more
preferably a Group 4,5 or 6 metal, even more preferably a Group 4
metal, and most preferably hafnium or zirconium; each X is
independently a leaving group, preferably, an anionic leaving
group, and more preferably hydrogen, a hydrocarbyl group, a
heteroatom, and most preferably an alkyl. In a most preferred
embodiment, at least one X is a substituted hydrocarbon group,
preferably a substituted alkyl group having more than 6 carbon
atoms, more preferably an aryl substituted alkyl group and most
preferably a benzyl group.
[0017] y is 0 or 1 (when y is 0 group L' is absent);
[0018] n is the oxidation state of M, preferably +2, +3, +4 or +5
and more preferably +4;
[0019] m is the formal charge of the YZL or the YZL' ligand,
preferably 0, -1, -2 or -3, and more preferably -2;
[0020] L is a Group 15 or 16 element, preferably nitrogen;
[0021] L' is a Group 15 or 16 element or Group 14 containing group,
preferably carbon, silicon or germanium;
[0022] Y is a Group 15 element, preferably nitrogen or phosphorus,
and more preferably nitrogen;
[0023] Z is a Group 15 element, preferably nitrogen or phosphorus,
and more preferably nitrogen;
[0024] R.sup.1 and R.sup.2 are independently a C.sub.1 to C.sub.20
hydrocarbon group, a heteroatom containing group having up to
twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus,
preferably a C.sub.2 to C.sub.20 alkyl, aryl or arylalkyl group,
more preferably a linear, branched or cyclic C.sub.2 to C.sub.20
alkyl group, most preferably a C.sub.2 to C.sub.6 hydrocarbon
group;
[0025] R.sup.3 is absent or a hydrocarbon group, hydrogen, a
halogen, a heteroatom containing group, preferably a linear, cyclic
or branched alkyl group having 1 to 20 carbon atoms, more
preferably R.sup.3 is absent, hydrogen or an alkyl group, and most
preferably hydrogen; R.sup.4 and R.sup.5 are independently an alkyl
group, an aryl group, substituted aryl group, a cyclic alkyl group,
a substituted cyclic alkyl group, a cyclic arylalkyl group, a
substituted cyclic arylalkyl group or multiple ring system,
preferably having up to 20 carbon atoms, more preferably between 3
and 10 carbon atoms, and even more preferably a C.sub.1 to C.sub.20
hydrocarbon group, a C.sub.1 to C.sub.20 aryl group or a C.sub.1 to
C.sub.20 arylalkyl group, or a heteroatom containing group, for
example PR.sub.3, where R is an alkyl group;
[0026] R.sup.1 and R.sup.2 may be interconnected to each other,
and/or R.sup.4 and R.sup.5 may be interconnected to each other;
[0027] R.sup.6 and R.sup.7 are independently absent, or hydrogen,
an alkyl group, halogen, heteroatom or a hydrocarbyl group,
preferably a linear, cyclic or branched alkyl group having 1 to 20
carbon atoms, more preferably absent; and
[0028] R* is absent, or is hydrogen, a Group 14 atom containing
group, a halogen, a heteroatom containing group.
[0029] By "formal charge of the YZL or YZL' ligand", it is meant
the charge of the entire ligand absent the metal and the leaving
groups X.
[0030] By "R.sup.1 and R.sup.2 may also be interconnected" it is
meant that R.sup.1 and R.sup.2 may be directly bound to each other
or may be bound to each other through other groups. By "R.sup.4 and
RS may also be interconnected" it is meant that R.sup.4 and R.sup.5
may be directly bound to each other or may be bound to each other
through other groups.
[0031] An alkyl group may be a linear, branched alkyl radicals, or
alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl
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 combination thereof. An arylalkyl group is defined to
be a substituted aryl group.
[0032] In a preferred embodiment R.sup.4 and R.sup.5 are
independently a group represented by the following formula: 2
[0033] wherein R.sup.8 to R.sup.12 are each independently hydrogen,
a C.sub.1 to C.sub.40 alkyl group, a halide, a heteroatom, a
heteroatom containing group containing up to 40 carbon atoms,
preferably a C.sub.1 to C.sub.20 linear or branched alkyl group,
preferably a methyl, ethyl, propyl or butyl group, any two R groups
may form a cyclic group and/or a heterocyclic group. The cyclic
groups may be aromatic. In a preferred embodiment R.sup.9, R.sup.10
and R.sup.12 are independently a methyl, ethyl, propyl or butyl
group (including all isomers), in a preferred embodiment R.sup.9,
R.sup.10 and R.sup.12 are methyl groups, and R.sup.8 and R.sup.11
are hydrogen.
[0034] In a particularly preferred embodiment R.sup.4 and R.sup.5
are both a group represented by the following formula: 3
[0035] In this embodiment, M is hafnium or zirconium; each of L, Y,
and Z is nitrogen; each of R.sup.1 and R.sup.2 is a hydrocarbyl
group, preferably --CH.sub.2--CH.sub.2--; R.sup.3 is hydrogen; and
R.sup.6 and R.sup.7 are absent.
[0036] The Group 15 containing metal catalyst compounds of the
invention are prepared by methods known in the art, such as those
disclosed in EP 0 893 454 A1, U.S. Pat. No. 5,889,128 and the
references cited in U.S. Pat. No. 5,889,128 which are all herein
incorporated by reference. U.S. application Ser. No. 09/312,878,
filed May 17, 1999, discloses a gas or slurry phase polymerization
process using a supported bisamide catalyst, which is also
incorporated herein by reference. A preferred direct synthesis of
these compounds comprises reacting the neutral ligand, (see for
example YZL or YZL' of Formula I or II) with MX.sub.n, n is the
oxidation state of the metal, each X is an anionic group, such as
halide, in a non-coordinating or weakly coordinating solvent, such
as ether, toluene, xylene, benzene, methylene chloride, and/or
hexane or other solvent having a boiling point above 60.degree. C.,
at about 20.degree. C. to about 150.degree. C. (preferably
20.degree. C. to 100.degree. C.), preferably for 24 hours or more,
then treating the mixture with an excess (such as four or more
equivalents) of an alkylating agent, such as methyl magnesium
bromide in ether. The magnesium salts are removed by filtration,
and the metal complex isolated by standard techniques.
[0037] In one embodiment the Group 15 containing metal catalyst
compound is prepared by a method comprising reacting a neutral
ligand, (see for example YZL or YZL' of formula 1 or 2) with a
compound represented by the formula MX, (where n is the oxidation
state of M, M is a transition metal, and each X is an anionic
leaving group) in a non-coordinating or weakly coordinating
solvent, at about 20.degree. C. or above, preferably at about
20.degree. C. to about 100.degree. C., then treating the mixture
with an excess of an alkylating agent, then recovering the metal
complex. In a preferred embodiment the solvent has a boiling point
above 60.degree. C., such as toluene, xylene, benzene, and/or
hexane. In another embodiment the solvent comprises ether and/or
methylene chloride, either being preferable.
[0038] Activator and Activation Methods
[0039] The above described Group 15 containing metal catalyst
compounds are typically activated in various ways to yield catalyst
compounds having a vacant coordination site that will coordinate,
insert, and polymerize olefin(s).
[0040] The preferred activator is a Lewis acid compound, more
preferably an aluminum based Lewis acid compound, and most
preferably a neutral, aluminum based Lewis acid compound having at
least one, preferably two, halogenated aryl ligands and one or two
additional monoanionic ligands not including halogenated aryl
ligands.
[0041] The Lewis acid compounds of the invention include those
olefin catalyst activator Lewis acids based on aluminum and having
at least one bulky, electron-withdrawing ancillary ligand such as
the halogenated aryl ligands of tris(perfluorophenyl)borane or
tris(perfluoronaphthyl)borane. These bulky ancillary ligands are
those sufficient to allow the Lewis acids to function as
electronically stabilizing, compatible non-coordinating anions.
Stable ionic complexes are achieved when the anions will not be a
suitable ligand donor to the strongly Lewis acidic cationic Group
15 containing transition metal cations used in insertion
polymerization, i.e., inhibit ligand transfer that would neutralize
the cations and render them inactive for polymerization.
[0042] The Lewis acids fitting this description can be described by
the following formula:
R.sub.nAl(ArHal).sub.3-n, (V)
[0043] where R is a monoanionic ligand and ArHal is a halogenated
C.sub.6 aromatic or higher carbon number polycyclic aromatic
hydrocarbon or aromatic ring assembly in which two or more rings
(or fused ring systems) are joined directly to one another or
together, and n=1 to 2, preferably n=1.
[0044] In one embodiment, at least one (ArHal) is a halogenated Cg
aromatic or higher, preferably a fluorinated naphtyl. Suitable
non-limiting R ligands include: substituted or unsubstituted
C.sub.1 to C.sub.30 hydrocarbyl aliphatic or aromatic groups,
substituted meaning that at least one hydrogen on a carbon atom is
replaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl or
halocarbyl substituted organometalloid, dialkylamido, alkoxy,
siloxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,
alkylphosphido or other anionic substituent; fluoride; bulky
alkoxides, where bulky refers to C.sub.4 and higher number
hydrocarbyl groups, e.g., up to about C.sub.20, such as
tert-butoxide and 2,6-dimethyl-phenoxide, and
2,6-di(tert-butyl)phenoxide- ; --SR; --NR.sub.2, and --PR.sub.2,
where each R is independently a substituted or unsubstituted
hydrocarbyl as defined above; and, C.sub.1 to C.sub.30 hydrocarbyl
substituted organometalloid, such as trimethylsilyl.
[0045] Examples of ArHal include the phenyl, napthyl and
anthracenyl radicals of U.S. Pat. No. 5,198,401 and the biphenyl
radicals of WO 97/29845 when halogenated. The use of the terms
halogenated or halogenation means for the purposes of this
application that at least one third of hydrogen atoms on carbon
atoms of the aryl-substituted aromatic ligands are replaced by
halogen atoms, and more preferred that the aromatic ligands be
perhalogenated. Fluorine is the most preferred halogen.
[0046] Other activators or methods of activation are contemplated
for use with the aluminum based Lewis acid activators. For example
other activators include: alumoxane, modified alumoxane, tri
(n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a
trisperfluorophenyl boron metalloid precursor or a
trisperfluoronaphtyl boron metalloid precursor, polyhalogenated
heteroborane anions, trimethylaluminum, triethylaluminum,
triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tris
(2,2',2"-nonafluorobiphenyl) fluoroaluminate, perchlorates,
periodates, iodates and hydrates,
(2,2'-bisphenyl-ditrimethylsilicate).cndot.4THF and
organo-boron-aluminum compound, silylium salts and
dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)-benzimidazol-
ide.
[0047] It is further contemplated by the invention that other
catalysts including bulky ligand metallocene-type catalyst
compounds and/or conventional-type catalyst compounds can be
combined with the Group 15 containing metal catalyst compounds of
this invention.
[0048] Supports, Carriers and General Supporting Techniques
[0049] The above described catalyst systems of a Group 15
containing metal catalyst compound and a Lewis acid aluminum
containing activator may be combined with one or more support
materials or carriers using one of the support methods well known
in the art or as described below. For example, in a most preferred
embodiment, a Group 15 containing metal catalyst compound and Lewis
acid activator is in a supported form, for example deposited on,
contacted with, vaporized with, bonded to, or incorporated within,
adsorbed or absorbed in, or on, a support or carrier.
[0050] The R group in formula (V) above, or ligand, may also be a
covalently bonded to a support material, preferably a
metal/metalloid oxide or polymeric support. Lewis base-containing
support materials or substrates will react with the Lewis acid
activators to form a support bonded Lewis acid compound, a
supported activator, where one R group of R.sub.nAl(ArHal).sub.3,
is covalently bonded to the support material. For example, where
the support material is silica, the Lewis base hydroxyl groups of
the silica is where this method of bonding at one of the aluminum
coordination sites occurs.
[0051] In a preferred embodiment, the support material is a metal
or metalloid oxide, preferably having surface hydroxyl groups
exhibiting a pK.sub.a equal to or less than that observed for
amorphous silica, i.e., pK.sub.a less than or equal to about
11.
[0052] While not wishing to be bound to any particular theory, it
is believed that the covalently bound anionic activator, the Lewis
acid, is believed to form initially a dative complex with a silanol
group, for example of silica (which acts as a Lewis base), thus
forming a formally dipolar (zwitterionic) Bronsted acid structure
bound to the metal/metalloid of the metal oxide support.
Thereafter, the proton of the Bronsted acid appears to protonate an
R'-group of the Lewis acid, abstracting it, at which time the Lewis
acid becomes covalently bonded to the oxygen atom. The replacement
R group of the Lewis acid then becomes R'--O--, where R' is a
suitable support material or substrate, for example, silica or
hydroxyl group-containing polymeric support. Any support material
that contain surface hydroxyl groups are suitable for use in this
particular supporting method. Other support material include glass
beads.
[0053] In one embodiment where the support material is a metal
oxide composition, these compositions may additionally contain
oxides of other metals, such as those of Al, K, Mg, Na, Si, Ti and
Zr and should preferably be treated by thermal and/or chemical
means to remove water and free oxygen. Typically such treatment is
in a vacuum in a heated oven, in a heated fluidized bed or with
dehydrating agents such as organo silanes, siloxanes, alkyl
aluminum compounds, etc. The level of treatment should be such that
as much retained moisture and oxygen as is possible is removed, but
that a chemically significant amount of hydroxyl functionality is
retained. Thus calcining at up to 800.degree. C. or more up to a
point prior to decomposition of the support material, for several
hours is permissible, and if higher loading of supported anionic
activator is desired, lower calcining temperatures for lesser times
will be suitable. Where the metal oxide is silica, loadings to
achieve from less than 0.1 mmol to 3.0 mmol activator/g SiO.sub.2
are typically suitable and can be achieved, for example, by varying
the temperature of calcining from 200 to 800+.degree. C. See
Zhuralev, et al, Langmuir 1987, Vol. 3, 316 where correlation
between calcining temperature and times and hydroxyl contents of
silica's of varying surface areas is described.
[0054] The tailoring of hydroxyl groups available as attachment
sites can also be accomplished by the pre-treatment, prior to
addition of the Lewis acid, with a less than stoichiometric amount
of the chemical dehydrating agents. Preferably those used will be
used sparingly and will be those having a single ligand reactive
with the silanol groups (e.g., (CH.sub.3).sub.3SiCl), or otherwise
hydrolyzable, so as to minimize interference with the reaction of
the transition metal catalyst compounds with the bound activator.
If calcining temperatures below 400.degree. C. are employed,
difunctional coupling agents (e.g., (CH.sub.3).sub.2SiCl.su- b.2)
may be employed to cap hydrogen bonded pairs of silanol groups
which are present under the less severe calcining conditions. See
for example, "Investigation of Quantitative SiOH Determination by
the Silane Treatment of Disperse Silica", Gorski, et al, Journ. of
Colloid and Interface Science, Vol. 126, No. 2, Dec. 1988, for
discussion of the effect of silane coupling agents for silica
polymeric fillers that will also be effective for modification of
silanol groups on the catalyst supports of this invention.
Similarly, use of the Lewis acid in excess of the stoichiometric
amount needed for reaction with the transition metal compounds will
serve to neutralize excess silanol groups without significant
detrimental effect for catalyst preparation or subsequent
polymerization.
[0055] Polymeric supports are preferably
hydroxyl-functional-group-contain- ing polymeric substrates, but
functional groups may be any of the primary alkyl amines, secondary
alkyl amines, and others, where the groups are structurally
incorporated in a polymeric chain and capable of a acid-base
reaction with the Lewis acid such that a ligand filling one
coordination site of the aluminum is protonated and replaced by the
polymer incorporated functionality. See, for example, the
functional group containing polymers of U.S. Pat. No. 5,288,677,
which is herein incorporated by reference.
[0056] Other supports include silica, alumina, silica-alumina,
magnesia, titania, zirconia, magnesium chloride, montmorillonite,
phyllosilicate, zeolites, talc, clays, silica-chromium,
silica-alumina, silica-titania, porous acrylic polymers.
[0057] In one embodiment, the support material or carrier, most
preferably an inorganic oxide has a surface area in the range of
from about 10 to about 100 m.sup.2/g, pore volume in the range of
from about 0.1 to about 4.0 cc/g and average particle size in the
range of from about 5 to about 500 .mu.m. More preferably, the
surface area of the carrier is in the range of from about 50 to
about 500 m.sup.2/g, pore volume of from about 0.5 to about 3.5
cc/g and average particle size of from about 10 to about 200 .mu.m.
Most preferably the surface area of the carrier is in the range is
from about 100 to about 400 m.sup.2/g, pore volume from about 0.8
to about 5.0 cc/g and average particle size is from about 5 to
about 100 .mu.m. The average pore size of the carrier of the
invention typically has pore size in the range of from 10 to 1000
.ANG., preferably 50 to about 500 .ANG., and most preferably 75 to
about 450 .ANG..
[0058] There are various other methods in the art for supporting a
polymerization catalyst compound or catalyst system of the
invention.
[0059] In a preferred embodiment, the invention provides for a
Group 15 containing metal catalyst system includes a surface
modifier that is used in the preparation of the supported catalyst
system as described in PCT publication WO 96/11960, which is herein
fully incorporated by reference. The catalyst systems of the
invention can be prepared in the presence of an olefin, for example
hexene-1.
[0060] In a preferred embodiment, the Group 15 containing metal
catalyst system can be combined with a carboxylic acid salt of a
metal ester, for example aluminum carboxylates such as aluminum
mono, di- and tri-stearates, aluminum octoates, oleates and
cyclohexylbutyrates, as described in U.S. application Ser. No.
09/113,216, filed Jul. 10, 1998.
[0061] A preferred method for producing a supported Group 15
containing metal catalyst system is described below and is
described in U.S. application Ser. Nos. 265,533, filed Jun. 24,
1994 and Ser. No. 265,532, filed Jun. 24, 1994 and PCT publications
WO 96/00245 and WO 96/00243 both published Jan. 4, 1996, all of
which are herein fully incorporated by reference. In this preferred
method, the Group 15 containing metal catalyst compound is slurried
in a liquid to form a solution and a separate solution is formed
containing a Lewis acid activator and a liquid. The liquid may be
any compatible solvent or other liquid capable of forming a
solution or the like with the Group 15 containing metal catalyst
compounds and/or Lewis acid activator. In the most preferred
embodiment the liquid is a cyclic aliphatic or aromatic
hydrocarbon, most preferably toluene. The Group 15 containing metal
catalyst compounds and Lewis acid activator solutions are mixed
together and added to a porous support such that the total volume
of Group 15 containing metal catalyst compound solution and the
Lewis acid activator solution or the Group 15 containing metal
catalyst compound solution and Lewis acid activator solution is
less than four times the pore volume of the porous support, more
preferably less than three times, even more preferably less than
two times; preferred ranges being from 1.1 times to 3.5 times range
and most preferably in the 1.2 to 3 times range.
[0062] Procedures for measuring the total pore volume of a porous
support are well known in the art. Details of one of these
procedures is discussed in Volume 1, Experimental Methods in
Catalytic Research (Academic Press, 1968) (specifically see pages
67-96). This preferred procedure involves the use of a classical
BET apparatus for nitrogen absorption. Another method well known in
the art is described in Innes, Total Porosity and Particle Density
of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical
Chemistry 332-334 (March, 1956).
[0063] The mole ratio of the metal of the activator component to
the metal component of the Group 15 containing metal catalyst
compound is preferably in the range of between 0.3:1 to 3:1.
[0064] In one embodiment of the invention, olefin(s), preferably
C.sub.2 to C.sub.30 olefin(s) or alpha-olefin(s), preferably
ethylene or propylene or combinations thereof are prepolymerized in
the presence of the catalyst system of the invention prior to the
main polymerization. The prepolymerization can be carried out
batchwise or continuously in gas, solution or slurry phase
including at elevated pressures. The prepolymerization can take
place with any olefin monomer or combination and/or in the presence
of any molecular weight controlling agent such as hydrogen. For
examples of prepolymerization procedures, see U.S. Pat. Nos.
4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578
and European publication EP-B-0279 863 and PCT Publication WO
97/44371 all of which are herein fully incorporated by
reference.
[0065] Polymerization Process
[0066] The catalyst systems, supported catalyst systems or
compositions of the invention described above are suitable for use
in any prepolymerization and/or polymerization process over a wide
range of temperatures and pressures. The temperatures may be in the
range of from -60.degree. C. to about 280.degree. C., preferably
from 50.degree. C. to about 200.degree. C., and the pressures
employed may be in the range from 1 atmosphere to about 500
atmospheres or higher.
[0067] Polymerization processes include solution, gas phase, slurry
phase and a high pressure process or a combination thereof.
Particularly preferred is a gas phase or slurry phase
polymerization of one or more olefins at least one of which is
ethylene or propylene.
[0068] In one embodiment, the process of this invention is directed
toward a solution, high pressure, slurry or gas phase
polymerization process of one or more olefin monomers having from 2
to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more
preferably 2 to 8 carbon atoms. The invention is particularly well
suited to the polymerization of two or more olefin monomers of
ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1,
hexene-1, octene-1 and decene-1.
[0069] Other monomers useful in the process 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, isobutylene,
isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted
styrene, ethylidene norbornene, dicyclopentadiene and
cyclopentene.
[0070] In the most preferred embodiment of the process of the
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, preferably from 4 to 12 carbon atoms, and
most preferably from 4 to 8 carbon atoms, is polymerized in a gas
phase process.
[0071] In another embodiment of the process of the invention,
ethylene or propylene is polymerized with at least two different
comonomers, optionally one of which may be a diene, to form a
terpolymer.
[0072] In one embodiment, the invention is directed to a
polymerization process, particularly a gas phase or slurry phase
process, for polymerizing propylene alone or with one or more other
monomers including ethylene, and/or other olefins having from 4 to
12 carbon atoms.
[0073] 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 and recycled back into the reactor.
Simultaneously, polymer product is withdrawn from the reactor and
fresh monomer is added to replace the polymerized monomer. (See for
example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036,
5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661
and 5,668,228, all of which are fully incorporated herein by
reference.)
[0074] The reactor pressure in a gas phase process may vary from
about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably
in the range of from about 200 psig (1379 kPa) to about 400 psig
(2759 kPa), more preferably in the range of from about 250 psig
(1724 kPa) to about 350 psig (2414 kPa).
[0075] The reactor temperature in a gas phase process may vary from
about 30.degree. C. to about 120.degree. C., preferably from about
60.degree. C. to about 115.degree. C., more preferably in the range
of from about 70.degree. C. to 110.degree. C., and most preferably
in the range of from about 70.degree. C. to about 95.degree. C.
[0076] Other gas phase processes contemplated by the process of the
invention include series or multistage polymerization processes.
Also gas phase processes contemplated by the invention include
those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and
5,677,375, and European publications EP-A-0 794 200 EP-B1-0 649
992, EP-A-0 802 202 and EP-B-634 421 all of which are herein fully
incorporated by reference.
[0077] In a preferred embodiment, the reactor utilized in the
present invention is capable and the process of the invention is
producing greater than 500 lbs of polymer per hour (227 Kg/hr) to
about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer,
preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably
greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably
greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably
greater than 35,000 lbs/hr (15,900 Kg/hr), still even more
preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most
preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater
than 100,000 lbs/hr (45,500 Kg/hr).
[0078] A slurry polymerization process generally uses pressures in
the range of from about 1 to about 50 atmospheres and even greater
and temperatures in the range of 0.degree. C. to about 120.degree.
C. In a slurry polymerization, a suspension of solid, particulate
polymer is formed in a liquid polymerization diluent medium to
which ethylene and comonomers and often hydrogen along with
catalyst are added. The suspension including diluent is
intermittently or continuously removed from the reactor where the
volatile components are separated from the polymer and recycled,
optionally after a distillation, to the reactor. The liquid diluent
employed in the polymerization medium is typically an alkane having
from 3 to 7 carbon atoms, preferably a branched alkane. The medium
employed should be liquid under the conditions of polymerization
and relatively inert. When a propane medium is used the process
must be operated above the reaction diluent critical temperature
and pressure. Preferably, a hexane or an isobutane medium is
employed.
[0079] A preferred polymerization technique of the invention is
referred to as a particle form polymerization, or a slurry process
where the temperature is kept below the temperature at which the
polymer goes into solution. Such technique is well known in the
art, and described in for instance U.S. Pat. No. 3,248,179 which is
fully incorporated herein by reference. Other slurry processes
include those employing a loop reactor and those utilizing a
plurality of stirred reactors in series, parallel, or combinations
thereof. Non-limiting examples of slurry processes include
continuous loop or stirred tank processes. Also, other examples of
slurry processes are described in U.S. Pat. No. 4,613,484, which is
herein fully incorporated by reference.
[0080] In an embodiment the reactor used in the slurry process of
the invention is capable of and the process of the invention is
producing greater than 2000 lbs of polymer per hour (907 Kg/hr),
more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most
preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another
embodiment the slurry reactor used in the process of the invention
is producing greater than 15,000 lbs of polymer per hour (6804
Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to
about 100,000 lbs/hr (45,500 Kg/hr).
[0081] Examples of solution processes are described in U.S. Pat.
Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO
99/32525, which are fully incorporated herein by reference
[0082] A process of the invention is where the process, preferably
a slurry or gas phase process is operated in the presence of the
catalyst system of the invention and in the absence of or
essentially free of any scavengers, such as triethylaluminum,
trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and
diethyl aluminum chloride, dibutyl zinc and the like. This process
is described in PCT publication WO 96/08520 and U.S. Pat. Nos.
5,712,352 and 5,763,543, which are herein fully incorporated by
reference.
[0083] In an embodiment, the method of the invention provides for
injecting an unsupported metal catalyst system of the invention
into a reactor, particularly a gas phase reactor. In one embodiment
the catalyst system is used in the unsupported form, preferably in
a liquid form such as described in U.S. Pat. Nos. 5,317,036 and
5,693,727 and European publication EP-A-0 593 083, all of which are
herein incorporated by reference. The polymerization catalyst in
liquid form can be fed with an activator together or separately to
a reactor using the injection methods described in PCT publication
WO 97/46599, which is fully incorporated herein by reference. Where
an unsupported catalyst system is used the mole ratio of the metal
of the Lewis acid activator component to the metal of the Group 15
containing metal catalyst compound is in the range of between 0.3:1
to 10,000: 1, preferably 100:1 to 5000: 1, and most preferably
500:1 to 2000:1.
[0084] Polymer Products
[0085] The polymers produced by the process of the invention can be
used in a wide variety of products and end-use applications. The
polymers produced by the process of the invention include linear
low density polyethylene, elastomers, plastomers, high density
polyethylenes, medium density polyethylenes, low density
polyethylenes, polypropylene and polypropylene copolymers.
[0086] The polymers, typically ethylene based polymers, have a
density in the range of from 0.86 g/cc to 0.97 g/cc, preferably in
the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the
range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the
range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in
the range from 0.910 g/cc to 0.940 g/cc, and most preferably
greater than 0.915 g/cc, preferably greater than 0.920 g/cc, and
most preferably greater than 0.925 g/cc. Density is measured in
accordance with ASTM-D-1238.
[0087] The polymers produced by the process of the invention
typically have a molecular weight distribution, a weight average
molecular weight to number average molecular weight
(M.sub.w/M.sub.n) of greater than 1.5 to about 15, particularly
greater than 2 to about 10, more preferably greater than about 2.2
to less than about 8, and most preferably from 2.5 to 8.
[0088] Also, the polymers of the invention typically have a narrow
composition distribution as measured by Composition Distribution
Breadth Index (CDBI). Further details of determining the CDBI of a
copolymer are known to those skilled in the art. See, for example,
PCT Patent Application WO 93/03093, published Feb. 18, 1993, which
is fully incorporated herein by reference.
[0089] The polymers of the invention in one embodiment have CDBI's
generally in the range of greater than 50% to 100%, preferably 99%,
preferably in the range of 55% to 85%, and more preferably 60% to
80%, even more preferably greater than 60%, still even more
preferably greater than 65%.
[0090] In another embodiment, polymers produced using a catalyst
system of the invention have a CDBI less than 50%, more preferably
less than 40%, and most preferably less than 30%.
[0091] The polymers of the present invention in one embodiment have
a melt index (MI) or (12) as measured by ASTM-D-1238-E in the range
from no measurable flow to 1000 dg/min, more preferably from about
0.01 dg/min to about 100 dg/min, even more preferably from about
0.1 dg/min to about 50 dg/min, and most preferably from about 0.1
dg/min to about 10 dg/min.
[0092] The polymers of the invention in an embodiment have a melt
index ratio (I.sub.21/I.sub.2) ( I.sub.21 is measured by
ASTM-D-1238-F) of from 10 to less than 25, more preferably from
about 15 to less than 25.
[0093] The polymers of the invention in a preferred embodiment have
a melt index ratio (I.sub.21/I.sub.2) (I.sub.21 is measured by
ASTM-D-1238-F) of from preferably greater than 25, more preferably
greater than 30, even more preferably greater that 40, still even
more preferably greater than 50 and most preferably greater than
65. In an embodiment, the polymer of the invention may have a
narrow molecular weight distribution and a broad composition
distribution or vice-versa, and may be those polymers described in
U.S. Pat. No. 5,798,427 incorporated herein by reference.
[0094] In yet another embodiment, propylene based polymers are
produced in the process of the invention. These polymers include
atactic polypropylene, isotactic polypropylene, hemi-isotactic and
syndiotactic polypropylene. Other propylene polymers include
propylene block or impact copolymers. Propylene polymers of these
types are well known in the art see for example U.S. Pat. Nos.
4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117, all of
which are herein incorporated by reference.
[0095] The Group 15 containing metal compound, when used alone,
produces a high weight average molecular weight M.sub.w polymer
(such as for example above 100,000, preferably above 150,000,
preferably above 200,000, preferably above 250,000, more preferably
above 300,000).
[0096] The polymers of the invention may be blended and/or
coextruded with any other polymer. Non-limiting examples of other
polymers include linear low density polyethylenes, elastomers,
plastomers, high pressure low density polyethylene, high density
polyethylenes, polypropylenes and the like.
[0097] Polymers produced by the process of the invention and blends
thereof are useful in such forming operations as film, sheet, 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,
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, pipe, 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.
EXAMPLES
[0098] In order to provide a better understanding of the present
invention including representative advantages thereof, the
following examples are offered.
[0099] Synthesis of Al(C.sub.6F.sub.5).sub.3.cndot.toluene was
prepared in accordance with method of described in EP 0 694 548 A1,
which is fully incorporated by reference.
Example 1
[0100] Preparation of
[(2,4,6-Me.sub.3C.sub.6H.sub.2)NHCH.sub.2CH.sub.2].s- ub.2NH Ligand
(HN3)
[0101] A 2 L one-armed Schlenk flask was charged with a magnetic
stir bar, diethylenetriamine (23.450 g, 0.227 mol),
2-bromomesitylene (90.51 g, 0.455 mol),
tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14 mmol),
racemic-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (racemic BINAP)
(2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol),
and toluene (800 mL) under dry, oxygen-free nitrogen. The reaction
mixture was stirred and heated to 100 C. After 18 h the reaction
was complete, as judged by proton NMR spectroscopy. All remaining
manipulations can be performed in air. All solvent was removed
under vacuum and the residues dissolved in diethyl ether (1 L). The
ether was washed with water (three times with 250 mL) followed by
saturated aqueous NaCl (180 g in 500 mL) and dried over magnesium
sulfate (30 g). Removal of the ether in vacuo yielded a red oil
which was dried at 70 C for 12 h under vacuum (yield: 71.10 g,
92%). .sup.1H NMR (C.sub.6D.sub.6) .delta. 6.83 (s, 4), 3.39 (br s,
2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br
s, 1).
Example 2
[0102] Preparation of {[(2,4 6-Me.sub.3C.sub.6H.sub.2
NCH.sub.2CH.sub.2].sub.2NH}Zr(CH.sub.2Ph).sub.2 (Zr--HN.sub.3)
[0103] A 500 mL round bottom flask was charged with a magnetic stir
bar, tetrabenzyl zirconium (Boulder Scientific, Mead, Colo.)
(41.729 g, 91.56 mmol), and 300 mL of toluene under dry,
oxygen-free nitrogen. Solid HN3 ligand above (32.773 g, 96.52 mmol)
was added with stirring over 1 minute (the desired compound
precipitates). The volume of the slurry was reduced to 100 mL and
300 mL of pentane added with stirring. The solid yellow-orange
product was collected by filtration and dried under vacuum (44.811
g, 80% yield). .sup.1H NMR (C.sub.6D.sub.6) 67 7.22-6.81 (m, 12),
5.90 (d, 2), 3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4),
2.43 (s, 6), 2.41 (s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 (s,
2).
Example 3
[0104] Preparation of
{[(2,4,6-Me.sub.3C.sub.6H.sub.2)NCH.sub.2CH.sub.2].s-
ub.2NH}Hf(CH.sub.2Ph).sub.2 (Hf--HN3)
[0105] A 250 mL round bottom flask was charged with a magnetic stir
bar, tetrabenzyl hafnium (4.063 g, 7.482 mmol), and 150 mL of
toluene under dry, oxygen-free nitrogen. Solid triamine ligand
above (2.545 g, 7.495 mmol) was added with stirring over 1 minute
(the desired compound precipitates). The volume of the slurry was
reduced to 30 mL and 120 mL of pentane added with stirring. The
solid pale yellow product was collected by filtration and dried
under vacuum (4.562 g, 87% yield). .sup.1H NMR (C.sub.6D.sub.6) 67
7.21-6.79 (m, 12), 6.16 (d, 2), 3.39 (m, 2), 3.14 (m, 2), 2.65 (s,
6), 2.40 (s, 6), 2.35 (m, 2), 2.23 (m, 2), 2.19 (s, 6) 1.60 (s, 2),
1.26 (s, 2), NH obscured.
Example 4
[0106] Preparation of Silica Bound Aluminum
(Si--O--Al(C.sub.6E.sub.5).sub- .2)
[0107] A sample of 40.686 g of silica (Davison 948, calcined at
600C, available from W.R. Grace, Davison Division, Baltimore, Md.)
was slurried in 300 mL of toluene in a 500 mL round bottom flask.
Solid Al(C.sub.6F.sub.5).sub.3.cndot.toluene (15.470 g, 24.90 mmol)
was added and the mixture stirred for 30 minutes. The mixture was
allowed to stand for 18 hours. The silica bound aluminum was
isolated by filtration and dried for 6 hours under vacuum with a
yield of 49.211 g.
Example 5
[0108] Preparation of Catalyst A
[0109] To 1.000 g of silica bound aluminum (from Example 4 above)
in 20 mL of toluene was added Zr--HN3 (0.076 g, 0.124 mmol) in 5 mL
of toluene. The mixture was stirred for 30 minutes. The silica
turned orange-red from colorless. The silica was isolated by
filtration and dried under vacuum for 6 hours with a yield of 1.051
g. The final transition metal loading was 116 .mu.mol/g, transition
metal to silica bound aluminum.
Example 6
[0110] Preparation of Catalyst B
[0111] To 1.000 g of silica bound aluminum (from Example 4 above)
in 20 mL of toluene was added Hf--HN3 (0.087 g, 0.125 mmol) in 5 mL
of toluene. The mixture was stirred for 30 minutes. The silica
turned orange-red from colorless. The silica was isolated by
filtration and dried under vacuum for 6 hours with a yield of 1.059
g. The final transition metal loading was 115 .mu.mol/g, transition
metal to silica bound aluminum.
Example 7
[0112] Slurry-Phase Ethylene-Hexene Polymerization with Catalyst
A
[0113] Polymerization was performed in the slurry-phase in a
1-liter autoclave reactor equipped with a mechanical stirrer, an
external water jacket for temperature control, a septum inlet and
vent line, and a regulated supply of dry nitrogen and ethylene. The
reactor was dried and degassed at 160.degree. C. Isobutane (400 mL)
is added as a diluent, 35 mL of 1-hexene, and 0.7 mL of a 25 weight
percent trioctyl aluminum in hexane is added as a scavenger using a
gas tight syringe. The reactor was heated to 60.degree. C. 0.100 g
of finished Catalyst A was added with ethylene pressure and the
reactor was pressurized with 78 psi (538 kPa) of ethylene. The
polymerization was continued for 30 minutes while maintaining the
reactor at 60.degree. C. and 78 psi (538 kPa) by constant ethylene
flow. The reaction was stopped by rapid cooling and vented. 70.0 g
of copolymer was obtained (Flow Index (FI)=no flow, activity=2320 g
polyethylene/mmol catalyst.cndot.atm.cndot.h, 10.5 weight percent
1-hexene incorporation).
Example 8
[0114] Slurry-Phase Ethylene Polymerization with Catalyst B
[0115] Polymerization was performed in the slurry-phase in a
1-liter autoclave reactor equipped with a mechanical stirrer, an
external water jacket for temperature control, a septum inlet and
vent line, and a regulated supply of dry nitrogen and ethylene. The
reactor was dried and degassed at 160.degree. C. Isobutane (400 mL)
was added as a diluent and 0.7 mL of a 25 weight percent trioctyl
aluminum solution in hexane was added as a scavenger using a gas
tight syringe. The reactor was heated to 90.degree. C. 0.200 g of
finished Catalyst B was added with ethylene pressure and the
reactor was pressurized with 134 psi (924 kPa) of ethylene. The
polymerization was continued for 30 minutes while maintaining the
reactor at 90.degree. C. and 134 psi (924 kPa) by constant ethylene
flow. The reaction was stopped by rapid cooling and vented. 37.4 g
of polyethylene was obtained (FI=no flow, activity=364 g
polyethylene/mmol catalyst.cndot.atm.cndot.rh).
Example 9
[0116] Slurry-Phase Ethylene-Hexene Polymerization with Catalyst
B
[0117] Polymerization was performed in the slurry-phase in a
1-liter autoclave reactor equipped with a mechanical stirrer, an
external water jacket for temperature control, a septum inlet and
vent line, and a regulated supply of dry nitrogen and ethylene. The
reactor was dried and degassed at 160.degree. C. Isobutane (400 mL)
is added as a diluent, 35 mL of 1-hexene, and 0.7 mL of a 25 weight
percent trioctyl aluminum in hexane is added as a scavenger using a
gas tight syringe. The reactor was heated to 90.degree. C. 0.100 g
of finished catalyst B was added with ethylene pressure and the
reactor was pressurized with 113 psi (889 kPa) of ethylene. The
polymerization was continued for 25 minutes while maintaining the
reactor at 90.degree. C. and 113 psi (889 kPa) by constant ethylene
flow. The reaction was stopped by rapid cooling and vented. 68.0 g
of polyethylene was obtained (FI=no flow, activity=1650 g
polyethylene/mmol catalyst.cndot.atm.cndot.h).
[0118] 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 variations not necessarily illustrated herein. For
example, it is contemplated that two or more supported Group 15
containing catalyst compositions of the invention can be used in a
single or in multiple polymerization reactor configurations. For
this reason, then, reference should be made solely to the appended
claims for purposes of determining the true scope of the present
invention.
* * * * *