U.S. patent application number 09/930774 was filed with the patent office on 2002-01-24 for group 15 containing transition metal catalyst compounds and catalyst systems.
Invention is credited to McConville, David H..
Application Number | 20020010076 09/930774 |
Document ID | / |
Family ID | 23728275 |
Filed Date | 2002-01-24 |
United States Patent
Application |
20020010076 |
Kind Code |
A1 |
McConville, David H. |
January 24, 2002 |
Group 15 containing transition metal catalyst compounds and
catalyst systems
Abstract
The present invention relates to a Group 15 containing metal
catalyst compound having an aryl substituted alkyl leaving group, a
catalyst system and a supported catalyst system thereof.
Inventors: |
McConville, David H.;
(Houston, TX) |
Correspondence
Address: |
Univation Technologies, LLC
Suite 1950
5555 San Felipe
Houston
TX
77056
US
|
Family ID: |
23728275 |
Appl. No.: |
09/930774 |
Filed: |
August 16, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09930774 |
Aug 16, 2001 |
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09435409 |
Nov 8, 1999 |
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6300439 |
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Current U.S.
Class: |
502/103 ;
502/102; 502/113; 502/117 |
Current CPC
Class: |
C08L 2205/02 20130101;
C08F 2500/01 20130101; C08F 10/02 20130101; C08F 4/65916 20130101;
C08F 210/14 20130101; C08F 2500/02 20130101; C08F 2500/04 20130101;
C08L 2666/04 20130101; C08F 2500/26 20130101; C08L 2666/04
20130101; C08F 2/14 20130101; C08F 4/025 20130101; C08F 4/64141
20130101; C08F 4/64148 20130101; C08F 4/65904 20130101; C08L
2314/06 20130101; C08F 2500/12 20130101; C08F 10/00 20130101; C08F
10/00 20130101; C08F 110/02 20130101; C08F 210/16 20130101; C08L
23/0815 20130101; C08F 4/65912 20130101; C08L 23/0815 20130101;
C08F 4/6592 20130101; C08L 23/16 20130101; C08F 10/00 20130101;
Y10S 526/941 20130101; C08F 10/02 20130101; C08F 10/00 20130101;
Y10S 526/901 20130101; C08L 23/16 20130101; C08F 210/16 20130101;
C08F 4/619 20130101; C08F 2410/03 20130101; Y10S 526/943 20130101;
C08F 10/02 20130101 |
Class at
Publication: |
502/103 ;
502/102; 502/113; 502/117 |
International
Class: |
B01J 031/00 |
Claims
We claim:
1. A supported catalyst system comprising a Group 15 containing
metal catalyst compound, an activator and a carrier, wherein the
Group 15 containing metal catalyst compound is represented by the
formulae: 5wherein M is metal; each X is an aryl substituted alkyl
leaving group; y is 0 or 1; n is the oxidation state of M; m is the
formal charge of Y, Z and L or of Y, Z, and L'; L is a Group 15
element; L' is a Group 15 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, a
hydrocarbon group, hydrogen, a halogen, or a heteroatom containing
group; R.sup.4 and R.sup.5 are independently an alkyl group, an
aryl group, a substituted aryl group, a cyclic alkyl group, a
substituted cyclic alkyl group, a cyclic arylalkyl group, a
substituted cyclic arylalkyl group or a 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, hydrogen, an alkyl group,
halogen, heteroatom or a hydrocarbyl group; and R* is absent,
hydrogen, a Group 14 atom containing group, a halogen, or a
heteroatom containing group.
2. The supported catalyst system of claim 1 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.
3. The supported catalyst system of claim 1 wherein R.sup.1 and
R.sup.2 are 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.
4. The supported catalyst system of claim 1 wherein L or L' are
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 bound to a cyclic group and may optionally
be bound to hydrogen, a halogen, a heteroatom, a hydrocarbyl group,
or a heteroatom containing group.
5. The supported catalyst system of claim 1 wherein R.sup.4 and
R.sup.5 are represented by the formula: 6wherein 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, or a heteroatom containing
group containing up to 40 carbon atoms, wherein any two R groups
may form a cyclic group and/or a heterocyclic group, and wherein
the cyclic groups may be aromatic.
6. The supported catalyst system of claim 1 wherein R.sup.9,
R.sup.10 and R.sup.12 are independently a methyl, ethyl, propyl or
butyl group and X is an aryl substituted alkyl group having greater
than 10 carbon atoms.
7. The supported catalyst system of claim 1 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.
8. The supported catalyst system of claim 1 wherein L, Y, and Z are
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.
9. The supported catalyst system of claim 1 wherein L and Z are
independently nitrogen, L' is a hydrocarbyl radical, and R.sup.6
and R.sup.7 are absent.
Description
RELATED APPLICATION DATA
[0001] The present application is a divisional of U.S. patent
application Ser. No. 09/435,409, now issued as U.S. Pat. No.
______.
FIELD OF THE INVENTION
[0002] The present invention relates to a Group 15 containing
transition metal catalyst compounds, a catalysts system thereof and
its use in the polymerization of olefin(s).
BACKGROUND OF THE INVENTION
[0003] Advances in polymerization and catalysis have resulted in
the capability to produce many new polymers having improved
physical and chemical properties useful in a wide variety of
superior products and applications. With the development of new
catalysts the choice of polymerization-type (solution, slurry, high
pressure or gas phase) for producing a particular polymer has been
greatly expanded. Also, advances in polymerization technology have
provided more efficient, highly productive and economically
enhanced processes. Especially illustrative of these advances is
the development of technology utilizing bulky ligand
metallocene-type catalyst systems.
[0004] More recently, developments have lead to the discovery of
anionic, multidentate heteroatom ligands as discussed by the
following articles: (1) Kempe et al., "Aminopyridinato Ligands--New
Directions and Limitations", 80.sup.th Canadian Society for
Chemistry Meeting, Windsor, Ontario, Canada, Jun. 1-4, 1997; (2)
Kempe et al., Inorg. Chem. 1996 vol 35 6742; (3) Jordan et al. of
polyolefin catalysts based on hydroxyquinolines (Bei, X.; Swenson,
D. C.; Jordan, R. F., Organometallics 1997, 16, 3282); (4) Horton,
et. al., "Cationic Alkylzirconium Complexes Based on a Tridentate
Diamide Ligand: New Alkene Polymerization Catalysts",
Organometallics, 1996, 15, 2672-2674 relates to tridentate
zirconium complexes; (5) Baumann, et al., "Synthesis of Titanium
and Zirconium Complexes that Contain the Tridentate Diamido Ligand
[((t-Bu-d.sub.6)N--O--C.sub.6H.sub.4).sub.2O].sup.2-{[NON}.sup.2-)
and the Living Polymerization of 1-Hexene by Activated [NON]ZrMe2",
Journal of the American Chemical Society, Vol. 119, pp. 3830-3831;
(6) Cloke et al., "Zirconium Complexes incorporating the New
Tridentate Diamide Ligand
[(Me.sub.3Si)N{CH.sub.2CH.sub.2N(SiMe.sub.3)}.sub.2].sup.2- -(L);
the Crystal Structure of [Zr(BH.sub.4).sub.2L] and
[ZrCl{CH(SiMe.sub.3).sub.2}L]", J. Chem. Soc. Dalton Trans, pp.
25-30, 1995; (7) Clark et al., "Titanium (IV) complexes
incorporating the aminodiamide ligand
[(SiMe.sub.3)N{CH.sub.2CH.sub.2N (SiMe.sub.3)}.sub.2].sup.2-(L);
the X-ray crystal structure of [TiMe.sub.2(L)] and
[TiCl{CH(SiMe.sub.3).sub.2}(L)]", Journal of Organometallic
Chemistry, Vol 50, pp. 333-340, 1995; (8) Scollard et al., "Living
Polymerization of alpha-olefins by Chelating Diamide Complexes of
Titanium", J. Am. Chem. Soc., Vol 118, No. 41, pp. 10008-10009,
1996; and (9) Guerin et al., "Conformationally Rigid Diamide
Complexes: Synthesis and Structure of Titanium (IV) Alkyl
Derivatives", Organometallics, Vol 15, No. 24, pp. 5085-5089,
1996.
[0005] 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.
[0006] While all these compounds have been described in the art,
there is still a need for an improved catalyst compound.
SUMMARY OF THE INVENTION
[0007] This invention provides for an improved catalyst compound, a
catalyst system and for its use in a polymerizing process.
[0008] In one embodiment, the invention is directed to a Group 15
containing transition metal catalyst compound having a substituted
hydrocarbon leaving group, a catalyst system including the Group 15
containing catalyst compound and to their use in the polymerization
of olefin(s).
[0009] In another embodiment, the invention is directed to a Group
15 containing bidentate or tridentate ligated transition metal
catalyst compound, a catalyst system including the bidentate or
tridentate ligated metal catalyst compound and to their use in the
polymerization of olefin(s).
[0010] In another embodiment, the invention is directed to a
catalyst compound having a metal 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, a catalyst system of this transition metal compound
and to their use in the polymerization of olefin(s).
[0011] In still another embodiment, the invention is directed to a
method for supporting the multidentate metal based catalysts
system, and to the supported catalyst system itself.
[0012] 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
supports catalyst systems discussed above.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Introduction
[0014] It has unexpectedly been found that the metal based Group 15
containing catalyst compound having a substituted hydrocarbon
leaving group exhibit much higher catalyst productivity as compared
to the same compounds having halogen or simple alkyl leaving
groups. As a result of this discovery it is now possible to provide
a highly active polymerization with commercially acceptable level
of productivity. Furthermore, it has also been discovered that
these Group 15 containing metal catalyst compounds of the invention
provide for an improved supported catalysts system, particularly
for use in slurry phase or gas phase polymerizations.
[0015] Group 15 containing Metal Catalyst Compound and Catalyst
Systems
[0016] 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.
[0017] 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.
[0018] 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.
[0019] In an embodiment of the invention, the Group 15 containing
metal compound of the invention is represented by the formulae:
1
[0020] 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 or a halogen, and most preferably an alkyl; and at least
one X is a substituted hydrocarbon group, preferably a substituted
alkyl group having more than 6 carbon atoms, most preferably an
aryl substituted alkyl group. The most preferred aryl substituted
alkyl group is benzyl.
[0021] y is 0 or 1 (when y is 0 group L' is absent);
[0022] n is the oxidation state of M, preferably +2, +3, +4 or +5
and more preferably +4;
[0023] m is the formal charge of the YZL or the YZL' ligand,
preferably 0, -1, -2 or -3, and more preferably -2;
[0024] L is a Group 15 or 16 element, preferably nitrogen;
[0025] L' is a Group 15 or 16 element or Group 14 containing group,
preferably carbon, silicon or germanium;
[0026] Y is a Group 15 element, preferably nitrogen or phosphorus,
and more preferably nitrogen;
[0027] Z is a Group 15 element, preferably nitrogen or phosphorus,
and more preferably nitrogen;
[0028] 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;
[0029] 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;
[0030] 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;
[0031] 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;
[0032] 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
[0033] R* is absent, or is hydrogen, a Group 14 atom containing
group, a halogen, a heteroatom containing group.
[0034] 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.
[0035] 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
R.sup.5 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.
[0036] 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.
[0037] In a preferred embodiment R.sup.4 and R.sup.5 are
independently a group represented by the following formula: 2
[0038] 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.
[0039] In a particularly preferred embodiment R.sup.4 and R.sup.5
are both a group represented by the following formula: 3
[0040] 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.
[0041] In a particularly preferred embodiment the Group 15
containing metal compound is represented by the formula: 4
[0042] Ph equals phenyl and M is a transition metal, preferably
hafnium or zirconium.
[0043] 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.
[0044] 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.sub.n (where n is the
oxidation state of M, M is a transition metal, and each X is an
anionic substituted hydrocarbon 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.
[0045] Activator and Activation Methods
[0046] 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).
[0047] For the purposes of this patent specification and appended
claims, the term "activator" is defined to be any compound or
component or method which can activate any of the Group 15
containing bidentate or tridentate ligated metal catalyst compounds
of the invention as described above. Non-limiting activators, for
example may include a Lewis acid or a non-coordinating ionic
activator or ionizing activator or any other compound including
Lewis bases, aluminum alkyls, conventional-type cocatalysts and
combinations thereof that can convert a neutral Group 15 containing
metal catalyst compound to a catalytically active Group 15
containing metal cation. It is within the scope of this invention
to use alumoxane or modified alumoxane as an activator, and/or to
also use ionizing activators, neutral or ionic, such as tri
(n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a
trisperfluorophenyl boron metalloid precursor or a
trisperfluoronaphtyl boron metalloid precursor, polyhalogenated
heteroborane anions (WO 98/43983) or combination thereof, that
would ionize the neutral catalyst compound. While most of the
publications discussed herein refer to a bulky ligand
metallocene-type catalyst, it contemplated that the activators and
activation methods utilized for these bully-ligand metallocene-type
catalyst compounds are applicable to the Group 15 containing metal
catalyst compounds of this invention.
[0048] In one embodiment, an activation method using ionizing ionic
compounds not containing an active proton but capable of producing
both a catalyst cation and a non-coordinating anion are also
contemplated, and are described in EP-A-0 426 637, EP-A-0 573 403
and U.S. Pat. No. 5,387,568, which are all herein incorporated by
reference.
[0049] There are a variety of methods for preparing alumoxane and
modified alumoxanes, 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, 5,157,137, 5,103,031, 5,391,793,
5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177,
5,854,166, 5,856,256 and 5,939,346 and European publications EP-A-0
561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and
PCT publication WO 94/10180, all of which are herein fully
incorporated by reference.
[0050] Organoaluminum compounds as activators include
trimethylaluminum, triethylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, tri-n-octylaluminum and the like.
[0051] Ionizing compounds may contain an active proton, or some
other cation associated with but not coordinated to or only loosely
coordinated to the remaining ion of the ionizing compound. Such
compounds and the like are described in European publications
EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944,
EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,
5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124
and U.S. patent application Ser. No. 08/285,380, filed Aug. 3,
1994, all of which are herein fully incorporated by reference.
[0052] Other activators include those described in PCT publication
WO 98/07515 such as tris (2,2',2"-nonafluorobiphenyl)
fluoroaluminate, which publication is fully incorporated herein by
reference. Combinations of activators are also contemplated by the
invention, for example, alumoxanes and ionizing activators in
combinations, see for example, EP-B1 0 573 120, PCT publications WO
94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410
all of which are herein fully incorporated by reference. WO
98/09996 incorporated herein by reference describes activating
catalyst compounds with perchlorates, periodates and iodates
including their hydrates. WO 98/30602 and WO 98/30603 incorporated
by reference describe the use of lithium
(2,2'-bisphenyl-ditrimethylsilicate).cndot.4THF as an activator for
a catalyst compound. WO 99/18135 incorporated herein by reference
describes the use of organo-boron-aluminum activators. EP-B1-0 781
299 describes using a silylium salt in combination with a
non-coordinating compatible anion. Also, methods of activation such
as using radiation (see EP-B1-0 615 981 herein incorporated by
reference), electrochemical oxidation, and the like are also
contemplated as activating methods for the purposes of rendering
the neutral catalyst compound or precursor to a catalyst cation
capable of polymerizing olefins. Other activators or methods for
activating a catalyst compound are described in for example, U.S.
Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO
99/42467
(diotadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazoli-
de), which are herein incorporated by reference.
[0053] In another embodiment, the invention provides for one or
more Group 15 containing metal catalyst compounds used in
combination with one or more activators discussed above.
[0054] 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.
[0055] Supports, Carriers and General Supporting Techniques
[0056] The above described Group 15 containing metal catalyst
compounds and catalyst systems 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
or catalyst system 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.
[0057] The terms "support" or "carrier" are used interchangeably
and are any support material, preferably a porous support material,
including inorganic or organic support materials. Non-limiting
examples of inorganic support materials include inorganic oxides
and inorganic chlorides. Other carriers include resinous support
materials such as polystyrene, functionalized or crosslinked
organic supports, such as polystyrene divinyl benzene polyolefins
or polymeric compounds or any other organic or inorganic support
material and the like, or mixtures thereof.
[0058] The preferred carriers are inorganic oxides that include
those Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred
supports include silica, alumina, silica-alumina, and mixtures
thereof. Other useful supports include magnesia, titania, zirconia,
magnesium chloride, montmorillonite (EP-B1 0 511 665),
phyllosilicate, zeolites, talc, clays and the like. Also,
combinations of these support materials may be used, for example,
silica-chromium, silica-alumina, silica-titania and the like.
Additional support materials may include those porous acrylic
polymers described in EP 0 767 184 B1, which is incorporated herein
by reference.
[0059] It is preferred that the 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..
[0060] Examples of supporting catalyst systems again replacing the
bulky ligand metallocene-type catalyst compound with the Group 15
containing metal catalyst compounds of the invention are described
in U.S. Pat. Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821,
4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925,
5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704,
5,629,253, 5,639,835, 5,625,015, 5,643,847, 5,665,665, 5,698,487,
5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032,
5,770,664, 5,846,895 and 5,939,348 and U.S. application Ser. Nos.
271,598 filed Jul. 7, 1994 and 788,736 filed Jan. 23, 1997 and PCT
publications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297,
and EP-B1-0 685 494 all of which are herein fully incorporated by
reference.
[0061] There are various other methods in the art for supporting a
polymerization catalyst compound or catalyst system of the
invention. For example, the Group 15 containing metal catalyst
compounds of the invention may contain a polymer bound ligand as
described in U.S. Pat. Nos. 5,473,202 and 5,770,755, which is
herein fully incorporated by reference; the Group 15 containing
metal catalyst compounds of the invention may be spray dried as
described in U.S. Pat. No. 5,648,310, which is herein fully
incorporated by reference; the support used with the Group 15
containing metal catalyst compounds of the invention is
functionalized as described in European publication EP-A-0 802 203,
which is herein fully incorporated by reference, or at least one
substituent or leaving group is selected as described in U.S. Pat.
No. 5,688,880, which is herein fully incorporated by reference.
[0062] In a preferred embodiment, the invention provides for a
Group 15 containing metal catalyst system that includes an
antistatic agent or 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.
[0063] 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.
[0064] 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 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 an 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 activator of the invention. 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 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 activator solution or the
Group 15 containing metal catalyst compound solution and 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.
[0065] 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).
[0066] The most preferred methods for supporting the Group 15 metal
compounds of the invention are described in U.S. application Ser.
No. 09/312,878, filed May 17, 1999, which is fully incorporated
herein by reference.
[0067] The mole ratio of the metal of the activator component to
the metal of the supported Group 15 containing metal catalyst
compound are in the range of between 0.3:1 to 1000:1, preferably
20:1 to 800:1, and most preferably 50:1 to 500:1. Where the
activator is an ionizing activator such as those based on the anion
tetrakis(penta-fluorophenyl)boron, 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.
[0068] 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 a supported Group 15 containing metal 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.
[0069] Polymerization Process
[0070] 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.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 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.
[0075] 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.
[0076] 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.
[0077] 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.)
[0078] 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).
[0079] 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.
[0080] 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.
[0081] 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).
[0082] 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.
[0083] 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.
[0084] 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).
[0085] 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
[0086] A preferred process of the invention is where the process,
preferably a slurry or gas phase process is operated in the
presence of Group 15 containing metal 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 preferred 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.
[0087] In an embodiment, the method of the invention provides for
injecting an unsupported Group 15 containing metal catalyst system
into a reactor, particularly a gas phase reactor. In one embodiment
the Group 15 containing metal polymerization catalyst 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 Group 15
containing metal catalyst compound is used the mole ratio of the
metal of the 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.
[0088] Polymer Products
[0089] 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.
[0090] 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.
[0091] 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.
[0092] 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.
[0093] 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%.
[0094] 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%.
[0095] The polymers of the present invention in one embodiment have
a melt index (MI) or (I.sub.2) 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.
[0096] 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.
[0097] 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.
[0098] 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.
[0099] 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).
[0100] 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.
[0101] 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
[0102] In order to provide a better understanding of the present
invention including representative advantages thereof, the
following examples are offered.
Example 1
Preparation of
[(2,4,6-Me.sub.3C.sub.6H.sub.2)NHCH.sub.2CH.sub.2].sub.2 (NH
ligand)
[0103] A 2 L one-armed Schlenk flask was charged with a magnetic
stir bar, dietbylenetriamine (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.degree. 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 (3 **** 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.degree. 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).
Comparative Example 2
Preparation of
{[(2,4,6-Me.sub.3C.sub.6H.sub.2)NCH.sub.2CH.sub.2].sub.2NH}-
ZrCl.sub.2 (ZrCl.sub.2--HN3)
[0104] 5.480 g of Zr(NMe.sub.2).sub.4 (20.48 mmol) was dissolved in
50 mL of pentane in a 250 mL round bottom flask. 6.656 g of
[(2,4,6-Me.sub.3C.sub.6H.sub.2)NHCH.sub.2CH.sub.2].sub.2NH (20.48
mmol) was added as a pentane solution (50 mL) and the solution
stirred for 2 hours. The mixed amide
{[(2,4,6-Me.sub.3C.sub.6H.sub.2)NCH.sub.2CH.sub.2]-
.sub.2NH}Zr(NMe.sub.2).sub.2 was identified by proton NMR but was
not isolated. .sup.1H NMR (C.sub.6D.sub.6) .delta. 6.94 (m, 4),
3.33 (m, 2), 3.05 (s, 6), 3.00 (m, 2), 2.59 (m, 4), 2.45 (s, 6),
2.43 (s, 6), 2.27 (s, 6), 2.20 (s, 6), 1.80 (m, 1). The solvent was
removed under vacuum. The residues were dissolved in toluene and
6.0 g of ClSiMe.sub.3 (55 mmol) added in one portion. The solution
was stirred for 24 hours. The solvent was removed under vacuum and
the solids suspended in pentane. The solid was collected by
filtration and wash with pentane (5.528 g, 54% yield). The
dichloride {[(2,4,6-Me.sub.3C.sub.6H.sub.2)
NCH.sub.2CH.sub.2].sub.2N- H}ZrCl.sub.2 was identified by proton
NMR. .sup.1H NMR (C.sub.6D.sub.6) .delta. 6.88 (s, 2), 6.81 (s, 2),
3.32 (m, 2), 2.86 (m, 2), 2.49 (s, 6), 2.47 (m, 4), 2.39 (s, 6),
2.12 (s, 6), NH was obscured.
Comparative Example 3
Preparation of
{[(2,4,6-Me.sub.3C.sub.6H.sub.2)NH.sub.2C.sub.2].sub.2NH}Hf-
Cl.sub.2 (HfCl.sub.2--HN3)
[0105] 3.075 g of Hf(NMe.sub.2).sub.4 (8.66 mmol) was dissolved in
100 mL of pentane in a 250 mL round bottom flask. 2.942 g of
[(2,4,6-Me.sub.3C.sub.6H.sub.2)NHCH.sub.2CH.sub.2].sub.2NH (8.66
mmol) was added as a solid and the solution stirred for 2 hours.
The mixed amide
{[(2,4,6-Me.sub.3C.sub.6H.sub.2)NCH.sub.2CH.sub.2].sub.2NH}Hf(NMe.s-
ub.2).sub.2 was identified by proton NMR but was not isolated.
.sup.1H NMR (C.sub.6D.sub.6) .delta. 6.95 (s, 4), 3.40 (m, 2), 3.08
(s, 6), 3.04 (m, 2), 2.52 (m, 4), 2.49 (s, 6), 2.47 (s, 6), 2.32
(s, 6), 2.20 (s, 6), 1.72 (m, 1). The solvent was removed under
vacuum. The residues were dissolved in toluene and 2.825 g of
ClSiMe.sub.3 (26.0 mmol) added in one portion. The solution was
stirred for 24 hours. The solvent was removed under vacuum and the
solids suspended in pentane. The solid was collected by filtration
and wash with pentane (4.870 g, 96% yield). The dichloride
{[(2,4,6-Me.sub.3C.sub.6H.sub.2)
NCH.sub.2CH.sub.2].sub.2NH}HfCl.sub.2 was identified by proton NMR.
.sup.1H NMR (C.sub.6D.sub.6) .delta. 6.89 (s, 2), 6.84 (s, 2), 3.40
(m, 2), 2.95 (m, 2), 2.51 (s, 6), 2.45 (s, 6), 2.40 (m, 4), 2.14
(s, 6), NH was obscured.
Example 4
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--HN3)
[0106] A 500 mL round bottom flask was charged with a magnetic stir
bar, tetrabenzyl zirconium (Boulder Scientific) (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) .delta. 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 5
Preparation of
{[(2,4,6-Me.sub.3C.sub.6H.sub.2)NCH.sub.2CH.sub.2].sub.2NH}-
Hf(CH.sub.2Ph).sub.2 (Hf-HN3)
[0107] 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)
.delta. 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.
Comparative Example 6
Preparation of Catalyst A
[0108] To 2.051 g of MAO (6.836 g of a 30 weight percent solution
in toluene, available from Albemarle Corporation, Baton Rouge, La.)
and 7.285 g of toluene in a 100 mL round bottom flask was added
0.145 g of ZrCl.sub.2--HN3 of Comparative Example 2. The solution
was stirred for 15 minutes. 5.070 g of silica (Davison 948,
calcined at 600.degree. C. available from W.R. Grace, Davison
Division, Baltimore, Md.) was added followed by mixing. The mixture
was dried overnight under vacuum affording 7.011 g of finished
catalyst with a loading of 0.36 weight percent zirconium and an
Al/Zr ratio of 122:1.
Example 7
Preparation of Catalyst B
[0109] To 0.801 g of MAO (2.670 g of a 30 weight percent solution
in toluene, available from Albemarle Corporation, Baton Rouge, La.)
and 4.679 g of toluene in a 100 mL round bottom flask was added
0.070 g of Zr--HN3 of Example 4. The solution was stirred for 15
minutes. 2.130 g of silica (Davison 948, calcined at 600.degree.
C., available from W.R. Grace, Davison Division, Baltimore, Md.)
was added followed by mixing. The mixture was dried overnight under
vacuum affording 2.899 g of finished catalyst with a loading of
0.35 weight percent zirconium and an Al/Zr ratio of 120:1.
Comparative Example 8
Preparation of Catalyst C
[0110] To 0.858 g of MAO (2.640 g of a 30 weight percent solution
in toluene, available from Albemarle Corporation, Baton Rouge, La.)
and 2.860 g of toluene in a 100 mL round bottom flask was added
0.067 g of HfCl.sub.2--HN3 of Comparative Example 3. The solution
was stirred for 15 minutes. 2.140 g of silica (Davison 948,
calcined at 600.degree. C., available from W.R. Grace, Davison
Division, Baltimore, Md.) was added followed by mixing. The mixture
was dried overnight under vacuum affording 2.901 g of finished
catalyst with a loading of 0.68 weight percent hafnium and an Al/Hf
ratio of 129:1.
Example 9
Preparation of Catalyst D
[0111] To 0.792 g of MAO (2.640 g of a 30 weight percent solution
in toluene, available from Albemarle Corporation, Baton Rouge, La.)
and 2.830 g of toluene in a 100 mL round bottom flask was added
0.080 g of Hf--HN3 of Example 5. The solution was stirred for 15
minutes. 2.130 g of silica (Davison 948, calcined at 600.degree.
C., available from W.R. Grace, Davison Division, Baltimore, Md.)
was added followed by mixing. The mixture was dried overnight under
vacuum affording 2.908 g of finished catalyst with a loading of
0.68 weight percent hafnium and an Al/Hf ratio of 119:1.
Comparative Example 10
Slurry-Phase Ethylene Polymerization with Catalyst A
[0112] 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 A was added with ethylene pressure and the
reactor was pressurized with 143 psi (986 kPa) of ethylene. The
polymerization was continued for 40 minutes while maintaining the
reactor at 90.degree. C. and 143 psi (986 kPa) by constant ethylene
flow. The reaction was stopped by rapid cooling and vented. 10.5 g
of polyethylene was obtained (Flow Index (FI) no flow, activity=209
g polyethylene/mmol catalyst.cndot.atm.cndot.h).
Example 11
Slurry-Phase Ethylene Polymerization with Catalyst B
[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)
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. 0.100 g of
finished catalyst B was added with ethylene pressure and the
reactor was pressurized with 144 psi (993 kPa) of ethylene. The
polymerization was continued for 30 minutes while maintaining the
reactor at 90.degree. C. and 144 psi (993 kPa) by constant ethylene
flow. The reaction was stopped by rapid cooling and vented. 11.8 g
of polyethylene was obtained (Fl=no flow, activity=641 g
polyethylene/mmol catalyst.cndot.atm.cndot.h).
Comparative Example 12
Slurry-Phase Ethylene Polymerization with Catalyst C
[0114] 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 C was added with ethylene pressure and the
reactor was pressurized with 113 psi (779 kPa) of ethylene. The
polymerization was continued for 40 minutes while maintaining the
reactor at 90.degree. C. and 113 psi (779 kPa) by constant ethylene
flow. The reaction was stopped by rapid cooling and vented. 11.9 g
of polyethylene was obtained (Fl=no flow, activity=311 g
polyethylene/mmol catalyst.cndot.atm.cndot.h).
Example 13
Slurry-Phase Ethylene Polymerization with Catalyst D
[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 D was added with ethylene pressure and the
reactor was pressurized with 130 psi (896 kPa) of ethylene. The
polymerization was continued for 30 minutes while maintaining the
reactor at 90.degree. C. and 130 psi (896 kPa) by constant ethylene
flow. The reaction was stopped by rapid cooling and vented. 29.1 g
of polyethylene was obtained (Fl=no flow, activity=881 g
polyethylene/mmol catalyst.cndot.atm.cndot.h).
[0116] From the data presented above under similar conditions the
Group 15 containing metal catalyst compound having the substituted
hydrocarbon leaving group, preferably the alkyl substituted with an
aryl group of the invention has a much higher productivity than the
same compound having a halogen.
[0117] 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 Group 15 containing
catalyst compositions of the invention can be used. Also it is
contemplated that a Group 15 containing metal catalyst compound
having a substituted alkyl leaving group of the invention can be
used with a Group 15 containing metal catalyst compound having
halogen leaving groups. For this reason, then, reference should be
made solely to the appended claims for purposes of determining the
true scope of the present invention.
* * * * *