U.S. patent application number 09/827587 was filed with the patent office on 2001-10-18 for mixed catalyst compounds, catalyst systems and thier use in a polymerization process.
Invention is credited to Loveday, Donald R., McConville, David H..
Application Number | 20010031695 09/827587 |
Document ID | / |
Family ID | 23699503 |
Filed Date | 2001-10-18 |
United States Patent
Application |
20010031695 |
Kind Code |
A1 |
Loveday, Donald R. ; et
al. |
October 18, 2001 |
Mixed catalyst compounds, catalyst systems and thier use in a
polymerization process
Abstract
The present invention relates to mixed catalyst compositions of
a Group 15 containing hafnium catalyst compound and a bulky ligand
metallocene-type catalyst compound, a unsupported and supported
catalyst systems thereof and to a process for polymerizing
olefin(s) utilizing them.
Inventors: |
Loveday, Donald R.;
(Houston, TX) ; McConville, David H.; (Houston,
TX) |
Correspondence
Address: |
Univation Technologies, LLC
5555 San Felipe, Suite 1950
Houston
TX
77056
US
|
Family ID: |
23699503 |
Appl. No.: |
09/827587 |
Filed: |
April 6, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09827587 |
Apr 6, 2001 |
|
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09428576 |
Oct 28, 1999 |
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Current U.S.
Class: |
502/117 ;
502/102; 502/103 |
Current CPC
Class: |
C08F 10/02 20130101;
C08F 4/65916 20130101; C08F 110/02 20130101; C08F 10/02 20130101;
C08F 10/02 20130101; C08F 4/659 20130101; C08F 2410/02 20130101;
C08F 4/64148 20130101; C08F 4/025 20130101; C08F 2500/26 20130101;
C08F 4/65904 20130101; C08F 2500/12 20130101; C08F 2500/12
20130101; C08F 210/14 20130101; C08F 2500/04 20130101; C08F 2500/04
20130101; C08F 2500/07 20130101; C08F 4/65925 20130101; C08F
2500/26 20130101; C08F 210/16 20130101; C08F 10/02 20130101; C08F
210/16 20130101; C08F 4/65912 20130101; C08F 110/02 20130101; C08F
10/02 20130101 |
Class at
Publication: |
502/117 ;
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 hafnium catalyst
compound and a bulky ligand metallocene-type catalyst compound.
2. The process of claim 1 wherein the Group 15 containing hafnium
catalyst compound is a Group 15 containing bidentate or tridentate
ligated hafnium catalyst compound.
3. The process of claim 1 wherein the Group 15 containing hafnium
catalyst compound is a hafnium metal atom bound to at least one
leaving group 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 hafnium
compound is represented by the formulae: 5wherein M is hafnium;
each X is independently 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: 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, 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.
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.
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.
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
hafnium catalyst compound, a bulky ligand metallocene-type catalyst
compound, an activator and a carrier.
19. The supported catalyst system of claim 18 wherein the Group 15
containing hafnium catalyst compound is a Group 15 containing
bidentate or tridentate ligated hafnium catalyst compound.
20. The supported catalyst system of claim 18 wherein the Group 15
containing hafnium catalyst compound and the bulky ligand
metallocene-type catalyst compound are contacted with the activator
to form a reaction product that is then contacted with the carrier.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a catalyst composition of
Group 15 containing hafnium transition metal catalyst compound and
a bulky ligand metallocene-type catalyst compound a catalysts
system thereof and its use in the polymerization of olefin(s).
BACKGROUND OF THE INVENTION
[0002] 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.
[0003] 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.
[0004] 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.
[0005] Traditional bulky ligand metallocene-type catalyst systems
produce polymers that are in some situations more difficult to
process into film, for example using old extrusion equipment. One
technique to improve these polymers is to blend them with other
polymers with the intent to create a blend having the desired
properties that each component individually would have. While the
two polymer blends tend to be more processable, it is expensive and
adds a cumbersome blending step to the manufacturing/fabrication
process.
[0006] Higher molecular weight confers desirable polymer mechanical
properties and stable bubble formation in the production of films.
However, this property also inhibits extrusion processing by
increasing backpressure in extruders, promotes melt fracture
defects in the inflating bubble and potentially, promotes too high
a degree of orientation in the finished film. The anionic,
multidentate heteroatom containing catalyst systems tend to produce
a very high molecular weight polymer. To remedy this, one may form
a secondary, minor component of lower molecular weight polymer to
reduce extruder backpressure and inhibit melt fracture. Several
industrial processes operate on this principle using multiple
reactor technology to produce a processable bimodal molecular
weight distribution (MWD) high density polyethylene (HDPE) product.
HIZEX.TM., a Mitsui Chemicals HDPE product, is considered the
worldwide standard. HIZEX.TM. is produced in a costly two or more
reactor process. In a multiple reactor process, each reactor
produces a single component of the final product.
[0007] Others in the art have tried to produce two polymers
together at the same time in the same reactor using two different
catalysts. PCT patent application WO 99/03899 discloses using a
typical bulky ligand metallocene-type catalyst and a
conventional-type Ziegler-Natta catalyst in the same reactor to
produce a bimodal polyolefin. Using two different types of
catalysts, however, result in a polymer whose characteristics
cannot be predicted from those of the polymers that each catalyst
would produce if utilized separately. This unpredictability occurs,
for example, from competition or other influence between the
catalyst or catalyst systems used.
[0008] Polyethylenes with a higher density and a higher molecular
weight are valued in film applications requiring high stiffness,
good toughness and high throughput. Such polymers are also valued
in pipe applications requiring stiffness, toughness and long-term
durability, and particularly resistance to environmental stress
cracking.
[0009] Thus, there is a desire for a combination of catalysts
capable of producing processable polyethylene polymers in
preferably a single reactor having desirable combinations of
processing, mechanical and optical properties.
SUMMARY OF THE INVENTION
[0010] This invention provides for an improved catalyst compound, a
catalyst system and for its use in a polymerizing process.
[0011] In one embodiment, the invention is directed to a catalyst
composition including a Group 15 containing hafnium catalyst
compound and a bulky ligand metallocene-type catalyst compound, a
catalyst system of the catalyst composition and to its use in the
polymerization of olefin(s).
[0012] In another embodiment, the invention is directed to a
catalyst composition of a Group 15 containing bidentate or
tridentate ligated hafnium transition metal catalyst compound and a
bulky ligand metallocene-type catalyst compound, a catalyst system
thereof and to its use in the polymerization of olefin(s).
[0013] In another embodiment, the invention is directed to a
catalyst composition of a catalyst compound having a hafnium
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 bulky ligand
metallocene-type catalyst composition; a catalyst system of the
catalyst composition; and to its use in the polymerization of
olefin(s).
[0014] In still another embodiment, the invention is directed to a
method for supporting the multidentate hafnium based catalyst
compounds and the bulky ligand metallocene-type catalyst compounds
on the same or different supports; to the supported catalyst system
itself; and to their use in the polymerization of olefin(s).
[0015] 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, more preferably in a
continuous gas phase single reactor process producing a multimodal
polymer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a gel permeation chromatogram representative of
the polymers of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Introduction
[0018] It has unexpectedly been found that the hafnium based Group
15 containing catalyst compounds exhibit a much higher catalyst
productivity as compared to their zirconium or titanium analogs.
Furthermore, it has also been discovered that these Group 15
containing hafnium catalyst compounds provide for an improved
supported catalysts system, particularly for use in slurry phase or
gas phase polymerizations. The polymer produced using these Group
15 containing compounds typically have a very high molecular
weight. Bulky ligand metallocene-type catalysts typically have a
high catalyst productivity and generally produce polymers having a
lower molecular weight. As a result of this discovery it is now
possible to provide for a mixed catalyst system using components
each of which having a commercially acceptable level of
productivity, especially when used in a supported form in a slurry
or gas phase polymerization process, particularly in a continuous
gas phase process. Also, the mixed catalysts of the invention are
particularly useful in producing a multimodal, especially a
bimodal, polymer having a high molecular weight and a low molecular
weight component.
[0019] Group 15 containing Hafnium Catalyst Compound and Catalyst
Systems
[0020] In one embodiment, the hafnium based catalyst compounds of
the invention are Group 15 bidentate or tridentate ligated hafnium
transition metal compound, the preferred Group 15 elements are
nitrogen and/or phosphorous, most preferably nitrogen.
[0021] The Group 15 containing hafnium catalyst compounds of the
invention generally include a hafnium metal atom 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.
[0022] 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.
[0023] In an embodiment of the invention, the Group 15 containing
hafnium compound of the invention is represented by the formulae:
1
[0024] wherein M is hafnium; 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;
[0025] y is 0 or 1 (when y is 0 group L' is absent);
[0026] n is the oxidation state of M, preferably +2, +3 or +4, and
more preferably +4;
[0027] m is the formal charge of the YZL or the YZL' ligand,
preferably 0, -1, -2 or -3, and more preferably -2;
[0028] L is a Group 15 or 16 element, preferably nitrogen;
[0029] L' is a Group 15 or 16 element or Group 14 containing group,
preferably carbon, silicon or germanium;
[0030] Y is a Group 15 element, preferably nitrogen or phosphorus,
and more preferably nitrogen;
[0031] Z is a Group 15 element, preferably nitrogen or phosphorus,
and more preferably nitrogen;
[0032] 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;
[0033] 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;
[0034] 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;
[0035] 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;
[0036] 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
[0037] R* is absent, or is hydrogen, a Group 14 atom containing
group, a halogen, a heteroatom containing group.
[0038] 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.
[0039] 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.
[0040] 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.
[0041] In a preferred embodiment R.sup.4 and R.sup.5 are
independently a group represented by the following formula: 2
[0042] 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.
[0043] In a particularly preferred embodiment R.sup.4 and R.sup.5
are both a group represented by the following formula: 3
[0044] In this embodiment, M is hafnium; 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.
[0045] In a particularly preferred embodiment the Group 15
containing metal compound is represented by the formula: 4
[0046] Ph equals phenyl. For convenience the above formula will be
referred to as Compound (1) (Hf-HN3).
[0047] The Group 15 containing hafnium 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 HfX.sub.n, n is the
oxidation state of Hf, 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.
[0048] In one embodiment the Group 15 containing hafnium 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 HfX.sub.n (where n is the
oxidation state of Hf, 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.
[0049] Bulky Ligand Metallocene-Type Catalyst Compounds
[0050] Generally, bulky ligand metallocene-type catalyst compounds
include half and full sandwich compounds having one or more bulky
ligands bonded to at least one metal atom. Typical bulky ligand
metallocene-type compounds are generally described as containing
one or more bulky ligand(s) and one or more leaving group(s) bonded
to at least one metal atom. In one preferred embodiment, at least
one bulky ligands is .eta.-bonded to the metal atom, most
preferably .eta..sup.5-bonded to the metal atom.
[0051] The bulky ligands are generally represented by one or more
open, acyclic, or fused ring(s) or ring system(s) or a combination
thereof. These bulky ligands, preferably the ring(s) or ring
system(s) are typically composed of atoms selected from Groups 13
to 16 atoms of the Periodic Table of Elements, preferably the atoms
are selected from the group consisting of carbon, nitrogen, oxygen,
silicon, sulfur, phosphorous, germanium, boron and aluminum or a
combination thereof. Most preferably the ring(s) or ring system(s)
are composed of carbon atoms such as but not limited to those
cyclopentadienyl ligands or cyclopentadienyl-type ligand structures
or other similar functioning ligand structure such as a pentadiene,
a cyclooctatetraendiyl or an imide ligand. The metal atom is
preferably selected from Groups 3 through 15 and the lanthanide or
actinide series of the Periodic Table of Elements. Preferably the
metal is a transition metal from Groups 4 through 12, more
preferably Groups 4, 5 and 6, and most preferably the transition
metal is from Group 4.
[0052] In one embodiment, the bulky ligand metallocene-type
catalyst compounds of the invention are represented by the
formula:
L.sup.AL.sup.BMQ.sub.n (I)
[0053] where M is a metal atom from the Periodic Table of the
Elements and may be a Group 3 to 12 metal or from the lanthanide or
actinide series of the Periodic Table of Elements, preferably M is
a Group 4, 5 or 6 transition metal, more preferably M is a Group 4
transition metal, even more preferably M is zirconium, hafnium or
titanium. The bulky ligands, L.sup.A and L.sup.B, are open, acyclic
or fused ring(s) or ring system(s) and are any ancillary ligand
system, including unsubstituted or substituted, cyclopentadienyl
ligands or cyclopentadienyl-type ligands, heteroatom substituted
and/or heteroatom containing cyclopentadienyl-type ligands.
Non-limiting examples of bulky ligands include cyclopentadienyl
ligands, cyclopentaphenanthreneyl ligands, indenyl ligands,
benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands,
cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands,
azenyl ligands, azulene ligands, pentalene ligands, phosphoyl
ligands, phosphinimine (WO 99/40125), pyrrolyl ligands, pyrozolyl
ligands, carbazolyl ligands, borabenzene ligands and the like,
including hydrogenated versions thereof, for example
tetrahydroindenyl ligands. In one embodiment, L.sup.A and L.sup.B
may be any other ligand structure capable of .eta.-bonding to M,
preferably .eta..sup.3-bonding to M and most preferably
.eta..sup.5-bonding. In yet another embodiment, the atomic
molecular weight (MW) of L.sup.A or L.sup.B exceeds 60 a.m.u.,
preferably greater than 65 a.m.u.. In another embodiment, L.sup.A
and L.sup.B may comprise one or more heteroatoms, for example,
nitrogen, silicon, boron, germanium, sulfur and phosphorous, in
combination with carbon atoms to form an open, acyclic, or
preferably a fused, ring or ring system, for example, a
hetero-cyclopentadienyl ancillary ligand. Other L.sup.A and L.sup.B
bulky ligands include but are not limited to bulky amides,
phosphides, alkoxides, aryloxides, imides, carbolides, borollides,
porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
Independently, each L.sup.A and L.sup.B may be the same or
different type of bulky ligand that is bonded to M. In one
embodiment of formula (I) only one of either L.sup.A or L.sup.B is
present.
[0054] Independently, each L.sup.A and L.sup.B may be unsubstituted
or substituted with a combination of substituent groups R.
Non-limiting examples of substituent groups R include one or more
from the group selected from hydrogen, or 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. In a
preferred embodiment, substituent groups R have up to 50
non-hydrogen atoms, preferably from 1 to 30 carbon, that can also
be substituted with halogens or heteroatoms or the like.
Non-limiting examples of alkyl substituents R include methyl,
ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl,
benzyl or phenyl groups and the like, including all their isomers,
for example tertiary butyl, isopropyl, and the like. Other
hydrocarbyl radicals include fluoromethyl, fluroethyl,
difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl
substituted organometalloid radicals including trimethylsilyl,
trimethylgermyl, methyldiethylsilyl and the like; and
halocarbyl-substituted organometalloid radicals including
tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,
bromomethyldimethylgermyl and the like; and disubstitiuted boron
radicals including dimethylboron for example; and disubstituted
pnictogen radicals including dimethylamine, dimethylphosphine,
diphenylamine, methylphenylphosphine, chalcogen radicals including
methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.
Non-hydrogen substituents R include the atoms carbon, silicon,
boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur,
germanium and the like, including olefins such as but not limited
to olefinically unsaturated substituents including vinyl-terminated
ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the
like. Also, at least two R groups, preferably two adjacent R
groups, are joined to form a ring structure having from 3 to 30
atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon,
germanium, aluminum, boron or a combination thereof. Also, a
substituent group R group such as 1-butanyl may form a carbon sigma
bond to the metal M.
[0055] Other ligands may be bonded to the metal M, such as at least
one leaving group Q. For the purposes of this patent specification
and appended claims the term "leaving group" is any ligand that can
be abstracted from a bulky ligand metallocene-type catalyst
compound to form a bulky ligand metallocene-type catalyst cation
capable of polymerizing one or more olefin(s). In one embodiment, Q
is a monoanionic labile ligand having a sigma-bond to M. Depending
on the oxidation state of the metal, the value for n is 0, 1 or 2
such that formula (I) above represents a neutral bulky ligand
metallocene-type catalyst compound.
[0056] Non-limiting examples of Q ligands include weak bases such
as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl
radicals having from 1 to 20 carbon atoms, hydrides or halogens and
the like or a combination thereof. In another embodiment, two or
more Q's form a part of a fused ring or ring system. Other examples
of Q ligands include those substituents for R as described above
and including cyclobutyl, cyclohexyl, heptyl, tolyl,
trifluromethyl, tetramethylene, pentamethylene, methylidene,
methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),
dimethylamide, dimethylphosphide radicals and the like.
[0057] In one embodiment, the bulky ligand metallocene-type
catalyst compounds of the invention include those of formula (I)
where L.sup.A and L.sup.B are bridged to each other by at least one
bridging group, A, such that the formula is represented by
L.sup.AAL.sup.BMQ.sub.n (II)
[0058] These bridged compounds represented by formula (II) are
known as bridged, bulky ligand metallocene-type catalyst compounds.
L.sup.A , L.sup.B, M, Q and n are as defined above. Non-limiting
examples of bridging group A include bridging groups containing at
least one Group 13 to 16 atom, often referred to as a divalent
moiety such as but not limited to at least one of a carbon, oxygen,
nitrogen, silicon, aluminum, boron, germanium and tin atom or a
combination thereof. Preferably bridging group A contains a carbon,
silicon or germanium atom, most preferably A contains at least one
silicon atom or at least one carbon atom. The bridging group A may
also contain substituent groups R as defined above including
halogens and iron. Non-limiting examples of bridging group A may be
represented by R'.sub.2C, R'.sub.2Si, R'.sub.2Si R'.sub.2Si,
R'.sub.2Ge, R'P, where R' is independently, a radical group which
is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl,
substituted halocarbyl, hydrocarbyl-substituted organometalloid,
halocarbyl-substituted organometalloid, disubstituted boron,
disubstituted pnictogen, substituted chalcogen, or halogen or two
or more R' may be joined to form a ring or ring system. In one
embodiment, the bridged, bulky ligand metallocene-type catalyst
compounds of formula (II) have two or more bridging groups A (EP
664 301 B1).
[0059] In one embodiment, the bulky ligand metallocene-type
catalyst compounds are those where the R substituents on the bulky
ligands L.sup.A and L.sup.B of formulas (I) and (II) are
substituted with the same or different number of substituents on
each of the bulky ligands. In another embodiment, the bulky ligands
L.sup.A and L.sup.B of formulas (I) and (II) are different from
each other.
[0060] Other bulky ligand metallocene-type catalyst compounds and
catalyst systems useful in the invention may include those
described in U.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819,
5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106, 5,329,031,
5,304,614, 5,677,401, 5,723,398, 5,753,578, 5,854,363, 5,856,547
5,858,903, 5,859,158, 5,900,517, 5,939,503 and 5,962,718 and PCT
publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO
98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 and
European publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513
380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0 739
361, EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein
fully incorporated by reference.
[0061] In one embodiment, bulky ligand metallocene-type catalysts
compounds useful in the invention include bridged heteroatom,
mono-bulky ligand metallocene-type compounds. These types of
catalysts and catalyst systems are described in, for example, PCT
publication WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506,
WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Pat. Nos.
5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405
and European publication EP-A-0 420 436, all of which are herein
fully incorporated by reference.
[0062] In this embodiment, the bulky ligand metallocene-type
catalyst compound is represented by the formula:
L.sup.CAJMQ.sub.n (III)
[0063] where M is a Group 3 to 16 metal atom or a metal selected
from the Group of actinides and lanthanides of the Periodic Table
of Elements, preferably M is a Group 4 to 12 transition metal, and
more preferably M is a Group 4, 5 or 6 transition metal, and most
preferably M is a Group 4 transition metal in any oxidation state,
especially titanium; L.sup.C is a substituted or unsubstituted
bulky ligand bonded to M; J is bonded to M; A is bonded to M and J;
J is a heteroatom ancillary ligand; and A is a bridging group; Q is
a univalent anionic ligand; and n is the integer 0,1 or 2. In
formula (III) above, L.sup.C, A and J form a fused ring system. In
an embodiment, L.sup.C of formula (III) is as defined above for
L.sup.A , A, M and Q of formula (III) are as defined above in
formula (I). In formula (III) J is a heteroatom containing ligand
in which J is an element with a coordination number of three from
Group 15 or an element with a coordination number of two from Group
16 of the Periodic Table of Elements. Preferably J contains a
nitrogen, phosphorus, oxygen or sulfur atom with nitrogen being
most preferred.
[0064] In another embodiment, the bulky ligand type
metallocene-type catalyst compound is a complex of a metal,
preferably a transition metal, a bulky ligand, preferably a
substituted or unsubstituted pi-bonded ligand, and one or more
heteroallyl moieties, such as those described in U.S. Pat. Nos.
5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which are
herein fully incorporated by reference.
[0065] In an embodiment, the bulky ligand metallocene-type catalyst
compound is represented by the formula:
L.sup.DMQ.sub.2(YZ)X.sub.n (IV)
[0066] where M is a Group 3 to 16 metal, preferably a Group 4 to 12
transition metal, and most preferably a Group 4, 5 or 6 transition
metal; L.sup.D is a bulky ligand that is bonded to M; each Q is
independently bonded to M and Q.sub.2(YZ) forms a unicharged
polydentate ligand; A or Q is a univalent anionic ligand also
bonded to M; X is a univalent anionic group when n is 2 or X is a
divalent anionic group when n is 1; n is 1 or 2.
[0067] In formula (IV), L and M are as defined above for formula
(I). Q is as defined above for formula (I), preferably Q is
selected from the group consisting of --O--, --NR--, --CR.sub.2-
and --S--; Y is either C or S; Z is selected from the group
consisting of --OR, --NR.sub.2, --CR.sub.3, --SR, --SiR.sub.3,
--PR.sub.2, --H, and substituted or unsubstituted aryl groups, with
the proviso that when Q is --NR-- then Z is selected from one of
the group consisting of --OR, --NR.sub.2, --SR, --SiR.sub.3,
--PR.sub.2 and --H; R is selected from a group containing carbon,
silicon, nitrogen, oxygen, and/or phosphorus, preferably where R is
a hydrocarbon group containing from 1 to 20 carbon atoms, most
preferably an alkyl, cycloalkyl, or an aryl group; n is an integer
from 1 to 4, preferably 1 or 2; X is a univalent anionic group when
n is 2 or X is a divalent anionic group when n is 1; preferably X
is a carbamate, carboxylate, or other heteroallyl moiety described
by the Q, Y and Z combination.
[0068] In another embodiment of the invention, the bulky ligand
metallocene-type catalyst compounds are heterocyclic ligand
complexes where the bulky ligands, the ring(s) or ring system(s),
include one or more heteroatoms or a combination thereof.
Non-limiting examples of heteroatoms include a Group 13 to 16
element, preferably nitrogen, boron, sulfur, oxygen, aluminum,
silicon, phosphorous and tin. Examples of these bulky ligand
metallocene-type catalyst compounds are described in WO 96/33202,
WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095 (dicarbamoyl
metal complexes) and EP-A1-0 874 005 and U.S. Pat. Nos. 5,637,660,
5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and
5,856,258 all of which are herein incorporated by reference.
[0069] In another embodiment, the bulky ligand metallocene-type
catalyst compounds are those complexes known as transition metal
catalysts based on bidentate ligands containing pyridine or
quinoline moieties, such as those described in U.S. application
Ser. No. 09/103,620 filed Jun. 23, 1998, which is herein
incorporated by reference.
[0070] In another embodiment, the bulky ligand metallocene-type
catalyst compounds are those described in PCT publications WO
99/01481 and WO 98/42664, which are fully incorporated herein by
reference.
[0071] In one embodiment, the bulky ligand metallocene-type
catalyst compound is represented by the formula:
((Z)XA.sub.t(YJ)).sub.qMQ.sub.n (V)
[0072] where M is a metal selected from Group 3 to 13 or lanthanide
and actinide series of the Periodic Table of Elements; Q is bonded
to M and each Q is a monovalent, bivalent, or trivalent anion; X
and Y are bonded to M; one or more of X and Y are heteroatoms,
preferably both X and Y are heteroatoms; Y is contained in a
heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen
atoms, preferably 2 to 30 carbon atoms; Z is bonded to X, where Z
comprises 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon
atoms, preferably Z is a cyclic group containing 3 to 50 atoms,
preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a
bridging group joined to at least one of X,Y or J, preferably X and
J; q is 1 or 2; n is an integer from 1 to 4 depending on the
oxidation state of M. In one embodiment, where X is oxygen or
sulfur then Z is optional. In another embodiment, where X is
nitrogen or phosphorous then Z is present. In an embodiment, Z is
preferably an aryl group, more preferably a substituted aryl
group.
[0073] It is also contemplated that in one embodiment, the bulky
ligand metallocene-type catalysts of the invention described above
include their structural or optical or enantiomeric isomers (meso
and racemic isomers, for example see U.S. Pat. No. 5,852,143,
incorporated herein by reference) and mixtures thereof.
[0074] Activator and Activation Methods
[0075] The above described Group 15 containing hafnium catalyst
compounds and bulky ligand metallocene-type 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).
[0076] 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 hafnium catalyst
compounds and the bulky ligand metallocene-type 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
hafnium catalyst compound to a catalytically active Group 15
containing hafnium cation and/or a neutral bulky ligand
metallocene-type catalyst compound to a catalytically active bulky
ligand metallocene-type 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
hafnium catalyst compounds of this invention.
[0077] 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.
[0078] 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.
[0079] Organoaluminum compounds as activators include
trimethylaluminum, triethylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, tri-n-octylaluminum and the like.
[0080] 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. Pat. application Ser. No. 08/285,380, filed Aug. 3, 1994,
all of which are herein fully incorporated by reference.
[0081] 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).multidot.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), electro-chemical 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
(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazol-
ide), which are herein incorporated by reference.
[0082] In another embodiment, the invention provides for one or
more Group 15 containing hafnium catalyst compounds and one or more
bulky ligand metallocene-type catalyst compounds used in
combination with one or more activators discussed above.
[0083] It is further contemplated by the invention that a
conventional-type catalyst compound can be combined with the Group
15 containing hafnium catalyst compounds and bulky ligand
metallocene-type catalyst compounds of this invention.
[0084] Supports, Carriers and General Supporting Techniques
[0085] The above described Group 15 containing hafnium catalysts
and bulky ligand metallocene-type catalysts 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, the mixed catalyst system of the
invention 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. Also, it is
also contemplated that the bulky ligand metallocene-type catalyst
system is supported on a separate carrier than the Group 15
containing hafnium catalyst system, particulary for use in a
multiple reactor system where one supported catalyst system is used
in one reactor to produce the high molecular weight component and
the other supported catalyst system is used in another reactor to
produce the low molecular component.
[0086] 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.
[0087] 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.
[0088] 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..
[0089] Examples of supporting the catalysts 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.
[0090] 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 hafnium catalyst
compounds and bulky ligand metallocene-type 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 hafnium catalyst
compounds and the bulky ligand metallocene-type 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 hafnium catalyst
compounds and the bulky ligand metallocene-type 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.
[0091] In a preferred embodiment, the invention provides for a
Group 15 containing hafnium catalyst system and the bulky ligand
metallocene-type catalyst compounds that 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.
[0092] In a preferred embodiment, the Group 15 containing hafnium
catalyst system and the bulky ligand metallocene-type catalyst
compounds 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.
[0093] A preferred method for producing a supported Group 15
containing hafnium catalyst system and the bulky ligand
metallocene-type 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. This procedure is used
either with the Group 15 containing hafnium catalyst compounds
together with or separately from the bulky ligand metallocene-type
catalyst compounds. In this preferred method, the catalyst compound
or compounds are 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 catalyst compound or
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 catalyst compound or
compounds and activator solutions are mixed together and added to a
porous support such that the total volume of the catalyst compound
or compounds solution and the activator solution or the catalyst
compound or compounds 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.
[0094] 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). The most preferred methods for
supporting the Group 15 metal hafnium 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.
[0095] The Group 15 hafnium compound and the bulky ligand
metallocene-type catalyst compound of the invention are combined at
molar ratios of 1:1000 to 1000:1, preferably 1:99 to 99:1,
preferably 10:90 to 90:10, more preferably 20:80 to 80:20, more
preferably 30:70 to 70:30, more preferably 40:60 to 60:40.
[0096] In one embodiment, particulary in a slurry polymerization
process, the loading of the total of Group 15 containing hafnium
compound and the bulky ligand metallocene-type catalyst compound in
.mu.mmol per gram (g) of finished supported catalyst (includes the
support material, the mixed catalysts and the activator) is about
40 .mu.mmol per gram, preferably about 38 .mu.mmol/g.
[0097] In one embodiment, particulary in a gas phase polymerization
process, the loading of the total of Group 15 containing hafnium
compound and the bulky ligand metallocene-type catalyst compound in
.mu.mmol per gram of finished supported catalyst (includes the
support material, the mixed catalysts and the activator) is less
than 30 .mu.mmol per gram, preferably less than 25 .mu.mmol/g, more
preferably less than 20 .mu.mmol/gram.
[0098] 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 hafnium catalyst
and/or the bulky ligand metallocene-type catalyst 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.
[0099] Polymerization Process
[0100] 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.
[0101] 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.
[0102] 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.
[0103] 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.
[0104] 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.
[0105] 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.
[0106] 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.
[0107] 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.)
[0108] 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).
[0109] 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.
[0110] 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.
[0111] 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).
[0112] 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.
[0113] 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.
[0114] 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).
[0115] 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.
[0116] A preferred process of the invention is where the process,
preferably a slurry or gas phase process is operated in the
presence of mixed 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.
[0117] In an embodiment, the method of the invention provides for
injecting an unsupported mixed catalyst system into a reactor,
particularly a gas phase reactor. In one embodiment the
polymerization catalysts of the invention are 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 or catalyst(s) 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.
[0118] The hydrogen concentration in the reactor is about 100 to
5000 ppm, preferably 200 to 2000 ppm, more preferably 250 to 1900
ppm, more preferably 300 to 1800 ppm, and more preferably 350 to
1700 ppm, more preferably 400 to 1600 ppm, more preferably 500 to
1500 ppm, more preferably 500 to 1400 ppm, more preferably 500 to
1200 ppm, more preferably 600 to 1200 ppm, preferably 700 to 1100
ppm, and more preferably 800 to 1000 ppm. The hydrogen
concentration in the reactor being inversely proportional to the
polymer's weight average molecular weight (M.sub.w).
[0119] Polymer Products
[0120] 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.
Preferably the new polymers include polyethylene, and even more
preferably include bimodal polyethylene produced in a single
reactor. In addition to bimodal polymers, it is not beyond the
scope of the present application to produce a unimodal or
multi-modal polymer.
[0121] The polyolefins, particularly polyethylenes, produced by the
present invention, have a density of 0.89 to 0.97g/cm.sup.3.
Preferably, polyethylenes having a density of 0.910 to 0.965
g/cm.sup.3, more preferably 0.915 to 0.960 g/cm.sup.3, and even
more preferably 0.920 to 0.955 g/cm.sup.3 can be produced. In some
embodiments, a density of 0.915 to 0.940 g/cm.sup.3 would be
preferred, in other embodiments densities of 0.930 to 0.970
g/cm.sup.3 are preferred. Density is measured in accordance with
ASTM-D-1238.
[0122] 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 5, particularly greater than
10.
[0123] 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.
[0124] 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%.
[0125] In a preferred embodiment, the polyolefin recovered
typically has a melt index 12 (as measured by ASTM D-1238,
Condition E at 190.degree. C.) of about 0.01 to 1000 dg/min or
less. In a preferred embodiment, the polyolefin is ethylene
homopolymer or copolymer. In a preferred embodiment for certain
applications, such as films, pipes, molded articles and the like, a
melt index of 10 dg/min or less is preferred. For some films and
molded articles, a melt index of 1 dg/min or less is preferred.
Polyethylene having a 12 between 0.01 and 10 dg/min is
preferred.
[0126] In a preferred embodiment the polymer produced herein has an
I.sub.21 (as measured by ASTM-D-1238-F, at 190 .degree. C.) of 0.1
to 100 dg/min, preferably 0.5 dg/min to 50 dg/min, more preferably
2 dg/min to 20 dg/min (especially for pipe applications), and most
preferably for film applications from 5 dg/min to 10 dg/min.
[0127] 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 80, more preferably
greater than 90, even more preferably greater that 100, still even
more preferably greater than 110 and most preferably greater than
120.
[0128] The Group 15 containing hafnium 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).
[0129] The bulky ligand metallocene-type catalyst compound, when
use alone produces a low weight average molecular weight polymer
such as for example below 100,000, preferably below 80,000, more
preferably below 60,000, still more preferably below 50,000, still
even more preferably below 40,000, and most preferably less than
30,000 and greater than 5,000.
[0130] In another embodiment the polymer has one or more of the
following properties in addition to a combination of those
above:
[0131] (a) M.sub.w/M.sub.n of between 15 and 80, preferably between
20 and 60, preferably between 20 and 40. Molecular weight (M.sub.w
and M.sub.n) are measured as described below in the examples
section;
[0132] (b) a density (as measured by ASTM 2839) of 0.94 to 0.970
g/cm.sup.3; preferably 0.945 to 0.965 g/cm.sup.3; preferably 0.945
g/cm.sup.3 to 0.960 g/cm.sup.3;
[0133] (c) a residual metal content of 5.0 ppm transition metal or
less, preferably 2.0 ppm transition metal or less, preferably 1.8
ppm transition metal or less, preferably 1.6 ppm transition metal
or less, preferably 1.5 ppm transition metal or less, preferably
2.0 ppm or less of Group 4 metal, preferably 1.8 ppm or less of
Group 4 metal, preferably 1.6 ppm or less of Group 4 metal,
preferably 1.5 ppm or less of Group 4 metal (as measured by
Inductively Coupled Plasma Emission Spectroscopy (ICPES) run
against commercially available standards, where the sample is
heated so as to fully decompose all organics and the solvent
comprises nitric acid and, if any support is present, another acid
to dissolve any support (such as hydrofluoric acid to dissolve
silica supports) is present; and/or
[0134] (d) 35 weight percent or more high weight average molecular
weight component, as measured by size-exclusion chromatography,
preferably 40% or more. In a particularly preferred embodiment the
higher molecular weight fraction is present at between 35 and 70
weight %, more preferably between 40 and 60 weight %.
[0135] In one preferred embodiment the catalyst composition
described above is used to make a polyethylene having a density of
between 0.94 and 0.970 g/cm.sup.3 (as measured by ASTM D 2839) and
an I.sub.2 of 0.5 or less g/10 min or less. In another embodiment
the catalyst composition described above is used to make a
polyethylene having an I.sub.21 of less than 10 and a density of
between about 0.940 and 0.950 g/cm.sup.3 or an I.sub.21 of less
than 20 and a density of about 0.945 g/cm.sup.3 or less.
[0136] In another embodiment, the polymers of the invention,
including those described above, have an ash content less than 100
ppm, more preferably less than 75 ppm, and even more preferably
less than 50 ppm is produced. In another embodiment, the ash
contains negligibly small levels, trace amounts, of titanium as
measured by Inductively Coupled Plasma/Atomic Emission Spectroscopy
(ICPAES) as is well known in the art.
[0137] 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.
[0138] 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
[0139] In order to provide a better understanding of the present
invention including representative advantages thereof, the
following examples are offered. The following examples below use
the bulky ligand metallocene-type catalyst compound
(n-propyl-cyclopentadienyl).sub.2ZrCl.- sub.2 which was obtained
from Boulder Scientific, Meade, Colo.
Example 1
Preparation of
[(2,4,6-Me.sub.3C.sub.6H.sub.2)NHCH.sub.2CH.sub.2].sub.2NH
[0140] A 2 L one-armed Schlenk flask was charged with a magnetic
stir bar, diethylenetriamine (23.450 g, 0.227 mol), mesityl bromide
(90.51 g, 0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041
g, 1.14 mmol), racemic-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl
(2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol),
and toluene (800 mL). The reaction mixture was heated to 95.degree.
C. and stirred. After 4 days the reaction was complete, as judged
by proton NMR spectroscopy. All solvent was removed under vacuum
and the residues dissolved in diethyl ether (1 L). The ether was
washed three times with water (1 L) and saturated aqueous NaCl (500
mL) and dried over magnesium sulfate. 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 .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). .sup.13C NMR .delta.143.74, 131.35, 129.83, 129.55,
50.17, 48.56, 20.70, 18.51.
Example 2
[0141] 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)
[0142] 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.
Example 3
Preparation of Mixed Catalyst A
[0143] To 1.85 g of MAO (6.18 g of a 30 weight percent solution in
toluene, Albemarle Corporation, Baton Rouge, La.) and 6.63 g of
toluene in a 100 mL round bottom flask was added 0.139 g of Hf-HN3
and 0.025 g of (n-propyl-cyclopentadienyl).sub.2ZrCl.sub.2. The
solution was stirred for 10 minutes. 4.98 g of silica (Crossfield
ES-70, calcined at 600.degree. C., available from Crosfield
Limited, Warrington, England) was added followed by mixing. The
mixture was dried overnight under vacuum. Dry Witco Aluminum
Stearate #22 (AlSt #22) (CH.sub.3(CH.sub.2).sub.16COO).sub-
.2Al--OH available from Witco Corporation, Memphis, Tenn. (0.28 g,
6 weight percent) was added with mixing to yielding 7.15 g of
finished catalyst with a loading of 38 .mu.mol/g of total catalyst,
a total metal to aluminum ratio of 120:1, and a Hf-HN3 to
(n-propyl-cyclopentadienyl).s- ub.2ZrCl.sub.2 ratio of 3:1.
Example 4
Slurry-Phase Ethylene Polymerization
[0144] Polymerization is 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 is
dried and degassed at 160.degree. C. Isobutane (400 mL) is added as
a diluent and 0.7 mL of a 25 weight percent trioctyl aluminum
solution in hexane is added as a scavenger using a gas tight
syringe. The reactor was heated to 90.degree. C. 0.100 g of Mixed
Catalyst A was added with ethylene pressure and the reactor was
pressurized with 136 psi (938 kPa) of ethylene. The polymerization
was continued for 30 minutes while maintaining the reactor at
90.degree. C. and 136 psi (938 kPa) by constant ethylene flow. The
reaction was stopped by rapid cooling and venting. 83.0 g of
ethylene homopolymer were recovered (I.sub.21=3.5, activity is 4770
g PE/mmol cat..multidot.atm.multidot.h).
Example 5
Preparation of Mixed Catalyst B
[0145] To 7.95 g of MAO (26.50 g of a 30 weight percent solution in
toluene, Albemarle Corporation, Baton Rouge, La.) and 94.41 g of
toluene in a 1000 mL round bottom flask was added 0.596 g of Hf-HN3
and 0.108 g of (n-propyl-cyclopentadienyl).sub.2ZrCl.sub.2. The
solution was stirred for 10 minutes. 51.35 g of silica (Crossfield
ES-70, calcined at 600.degree. C., available from Crosfield
Limited, Warrington, England) was added followed by mixing. The
mixture was dried overnight under vacuum. Dry Witco Aluminum
Stearate #22 (AlSt #22) (CH.sub.3(CH.sub.2).sub.16COO).sub.2Al--OH
available from Witco Corporation, Memphis, Tenn. (2.40 g, 6 weight
percent) was added with mixing to yielding 62.33 g of finished
catalyst with a loading of 19 .mu.mol/g of total catalyst and a
total metal to Al ration of 120:1.
Example 6
Gas-Phase Ethylene-Hexene Polymerization
[0146] Mixed Catalyst B described above was used for
ethylene-hexene copolymerization studies described below. A
continuous fluid bed gas-phase reactor operated at 300 psi (2069
kPa) total pressure and 1.60 ft/s cycle gas velocity (49 cm/s)was
used for determining catalyst efficiency, ability to incorporate
comonomer (1-hexene) and molecular weight capability. The polymer
properties are as follows: I.sub.21=10.1, I.sub.10=0.95,
I.sub.2=0.008, M.sub.w=185,143, M.sub.n=12,861,
M.sub.w/M.sub.n=14.4, density 0.9487 g/cm.sup.3. A summary of the
process data is included in Table 1.
1 TABLE 1 Process Conditions Results H.sub.2 conc. (ppm) 802
C.sub.2 conc. (mol %) 34.9 Hexene conc. (mol %) 0.08
H.sub.2/C.sub.2 Ratio 23.0 C.sub.6/C.sub.2 Ratio 0.002 Reactor Temp
(.degree. F./.degree. C.) 185/85.0 Avg. Bed weight (g) 1911
Production (g/h) 282 Residence Time (h) 6.8 Productivity (g/g) -
MB.sup.1 696 Total Bed Turnovers 5.9 .sup.1MB = Material
Balance
[0147] 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 with
an unsupported bulky ligand metallocene-type catalyst compound.
Also it is contemplated that a Group 15 containing hafnium catalyst
compound can be used with a Group 15 containing titanium or
zirconium catalyst compound and a bulky ligand metallocene-type
catalyst compound. For this reason, then, reference should be made
solely to the appended claims for purposes of determining the true
scope of the present invention.
* * * * *