U.S. patent application number 10/790887 was filed with the patent office on 2004-09-02 for catalyst for the production of olefin polymers.
Invention is credited to Wang, Chunming.
Application Number | 20040171857 10/790887 |
Document ID | / |
Family ID | 24312146 |
Filed Date | 2004-09-02 |
United States Patent
Application |
20040171857 |
Kind Code |
A1 |
Wang, Chunming |
September 2, 2004 |
Catalyst for the production of olefin polymers
Abstract
A catalyst composition for the polymerization of olefins is
provided, comprising a cyclopentadienyl transition metal catalyst
and an activating co-catalyst.
Inventors: |
Wang, Chunming; (Belle Mead,
NJ) |
Correspondence
Address: |
Univation Technologies, LLC
Suite 1950
5555 San Felipe
Houston
TX
77056
US
|
Family ID: |
24312146 |
Appl. No.: |
10/790887 |
Filed: |
March 1, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10790887 |
Mar 1, 2004 |
|
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09578273 |
May 25, 2000 |
|
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6723675 |
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Current U.S.
Class: |
556/42 ; 556/46;
556/52 |
Current CPC
Class: |
C08F 36/04 20130101;
C08F 110/02 20130101; C08F 36/04 20130101; C08F 210/18 20130101;
C08F 4/63912 20130101; C08F 2500/03 20130101; C08F 4/62 20130101;
C08F 210/06 20130101; C08F 2500/04 20130101; C08F 2500/07 20130101;
C08F 4/6392 20130101; C08F 2500/25 20130101; C08F 2500/03 20130101;
C08F 2500/12 20130101; C08F 2500/07 20130101; C08F 2500/07
20130101; C08F 210/14 20130101; C08F 10/00 20130101; C08F 110/02
20130101; C08F 210/18 20130101; C08F 210/16 20130101; C08F 110/02
20130101; C08F 10/00 20130101; C08F 210/16 20130101; C07F 17/00
20130101; C08F 2420/01 20130101 |
Class at
Publication: |
556/042 ;
556/046; 556/052 |
International
Class: |
C07F 017/00 |
Claims
What is claimed is:
1. A compound having the formula: 5wherein: R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are each independently selected from among
hydrogen and C.sub.1-C.sub.8 hydrocarbyl groups, wherein none, one
or two pairs of substituents selected from the group consisting of
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are linked to form saturated
or unsaturated rings; M is an atom selected from among the elements
of Groups IV, V and VI; m is 1, 2, 3 or 4; the or each X is
selected from among halide elements, C.sub.1-C.sub.8 hydrocarbyl
groups, C.sub.1-C.sub.8 alkoxy groups, C.sub.1-C.sub.8 carboxylate
groups and C.sub.1-C.sub.8 carbamate groups; n is 1, 2 or 3; the or
each L is an organic compound containing at least one lone pair of
electrons; Q is a divalent radical of the formula YR.sub.5R.sub.6,
wherein Y is a Group 14 atom, wherein R.sub.5 and R.sub.6 are each
independently selected from among hydrogen and C.sub.1-C.sub.8
hydrocarbyl groups, and wherein R.sub.5 and R.sub.6 are not linked
or are linked to form a saturated or unsaturated ring; E is a Lewis
basic group having formula (i) or (ii)
below:--C(R.sub.7).dbd.Z.sub- .1R.sub.8, (i)wherein R.sub.7 and
R.sub.8 are each independently selected from among hydrogen and
C.sub.1-C.sub.8 hydrocarbyl groups, and wherein R.sub.7 and R.sub.8
are not linked or are linked to form a saturated or unsaturated
ring; and Z.sub.1 is a nitrogen atom or a phosphorus atom, which
bonds to M; 6wherein Z.sub.2 is an oxygen atom, a sulphur atom or a
selenium atom, which bonds to M; and R.sub.9, R.sub.10 and R.sub.11
are each independently selected from among hydrogen and
C.sub.1-C.sub.8 hydrocarbyl groups, wherein no pair or one pair of
substituents selected from R.sub.9, R.sub.10 and R.sub.11 are
linked to form a saturated or unsaturated ring.
2. The compound of claim 1, wherein said compound is selected from
the group consisting of (i) 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclop- entadienyl chromium (III)
dichloride, (ii) 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclopentadienyl vanadium (III)
dichloride and (iii) 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclopentadienyl titanium (III)
dichloride.
Description
STATEMENT OF RELATED APPLICATIONS
[0001] The present application is a Divisional Application of, and
claims priority to U.S. Ser. No. 09/578,273 filed May 25, 2000, now
issued as U.S. Pat. No. ______
FIELD OF THE INVENTION
[0002] The invention relates to a family of novel catalyst
compounds and compositions for the polymerization of olefins. The
catalyst compounds and compositions of the invention are especially
useful for the production of copolymers of ethylene and alpha
olefins, copolymers of ethylene and cyclic olefins, or copolymers
of ethylene and alpha olefin-dienes.
BACKGROUND OF THE INVENTION
[0003] A variety of metallocenes and single site-like catalysts
have been developed to prepare olefin polymers. Metallocenes are
organometallic coordination complexes containing one or more
B-bonded moieties (i.e., cyclopentadienyl groups) in association
with a transition metal atom. Catalyst compositions containing
metallocenes and single site-like catalysts are used in the
preparation of polyolefins, producing relatively homogeneous
copolymers at acceptable polymerization rates while allowing one to
tailor closely the final properties of the polymer as desired.
[0004] For instance, D hring et al., "Donor-Ligand-Substituted
Cyclopentadienyl-chromium(III) Complexes: A New Class of Alkene
Polymerization Catalyst. 1. Amino-substituted Systems"
Organometallics, 2000, 19, 388-402 discloses complexes which,
according to the reference, when treated with MAO, lead to
formation of active catalysts for the oligomerization,
polymerization and copolymerization of ethylene. One example of
such a complex is (cyclo-C.sub.4H.sub.8NC.sub.2H.sub.4C.sub.5--
-Me.sub.4)CrCl.sub.2 and another is
(cyclo-C.sub.4H.sub.8NC.sub.2H.sub.4C.-
sub.5Me.sub.4)CrMe.sub.2.
[0005] Despite these efforts, a need has remained for catalyst
compounds and compositions which enable olefin polymerization
reactions to be performed more efficiently, in particular, with
enhanced activity. In addition, there has remained a need for
catalyst compounds and compositions which enable olefin
polymerization reactions to be more closely tailored so as to
provide polymer product having desired molecular weight
distribution. The catalyst compounds of the present invention, as
well as catalyst compositions which contain the catalyst compounds
of the present invention, and olefin polymerization reactions which
employ the catalyst compounds of the present invention, as
described below, satisfy these needs.
SUMMARY OF THE INVENTION
[0006] The present invention provides catalyst precursors for use
in olefin polymerization reactions. The precursors of the present
invention provide high activity for these polymerization reactions,
and can be used to produce polyolefins having desired molecular
weight distribution, e.g., a narrow molecular weight distribution
or a desired range of molecular weight distribution. The present
invention also provides catalyst compositions and catalyst systems
which comprise the catalyst precursors of the present invention and
a co-catalyst, as well as polymerization reactions conducted in the
presence of such catalyst precursors, compositions and systems.
[0007] The catalyst precursors according to the present invention
include those having the formula: 1
[0008] wherein:
[0009] R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently
selected from among hydrogen and C.sub.1-C.sub.8 hydrocarbyl
groups, wherein none, one or two pairs of substituents selected
from the group consisting of R.sub.1, R.sub.2, R.sub.3 and R.sub.4
are linked to form saturated or unsaturated rings;
[0010] M is an atom selected from among the elements of Groups IV,
V and VI;
[0011] m is, 1, 2, 3 or 4;
[0012] the or each X is selected from among halide elements,
C.sub.1-C.sub.8 hydrocarbyl groups, C.sub.1-C.sub.8 alkoxy groups,
C.sub.1-C.sub.8 carboxylate groups and C.sub.1-C.sub.8 carbamate
groups;
[0013] n is 1, 2 or 3;
[0014] the or each L is an organic compound containing at least one
lone pair of electrons;
[0015] Q is a divalent radical of the formula YR.sub.5R.sub.6,
wherein Y is a Group 14 atom, wherein R.sub.5 and R.sub.6 are each
independently selected from among hydrogen and C.sub.1-C.sub.8
hydrocarbyl groups, and wherein R.sub.5 and R.sub.6 are not linked
or are linked to form a saturated or unsaturated ring;
[0016] E is a Lewis basic group having formula (i) or (ii)
below:
--C(R.sub.7).dbd.Z.sub.1R.sub.8, (i)
[0017] wherein R.sub.7 and R.sub.8 are each independently selected
from among hydrogen and C.sub.1-C.sub.8 hydrocarbyl groups, and
wherein R.sub.7 and R.sub.8 are not linked or are linked to form a
saturated or unsaturated ring; and
[0018] Z.sub.1is a nitrogen atom or a phosphorus atom, which bonds
to M; 2
[0019] wherein:
[0020] Z.sub.2is an oxygen atom, a sulphur atom or a selenium atom,
which bonds to M; and
[0021] R.sub.9, R.sub.10 and R.sub.11, are each independently
selected from among hydrogen and C.sub.1-C.sub.8 hydrocarbyl
groups, wherein no pair or one pair of substituents selected from
R.sub.9, R.sub.10 and R.sub.11 are linked to form a saturated or
unsaturated ring.
[0022] The invention also provides a catalyst composition
comprising a catalyst precursor according to the present invention
and an activating co-catalyst, as disclosed below.
[0023] The invention also provides a catalyst system comprising a
catalyst precursor according to the present invention and an
activating co-catalyst as described above, in which the catalyst
precursor and the activating co-catalyst are introduced to a
reaction system at different locations.
[0024] The invention further provides a process for producing an
olefin polymer, which comprises contacting at least one olefin
monomer under polymerization conditions with a catalyst precursor,
and/or a catalyst composition as described above.
[0025] The invention further provides olefin polymers, such as
ethylene polymers, produced by a process as described in the
preceding paragraph, and products, e.g., blow-molded articles, high
density films, etc., made from such olefin polymers.
DETAILED DESCRIPTION OF THE INVENTION
[0026] In this specification, the term "olefinically unsaturated
hydrocarbons" is often represented for convenience by
"olefins".
[0027] The expression "copolymer" (and other terms incorporating
this root), as used herein, refers to polymers containing two or
more comonomers, i.e, it encompasses copolymers, terpolymers,
etc.
[0028] The Group element notation in this specification is as
defined in the Periodic Table of Elements according to the IUPAC
1988 notation (IUPAC Nomenclature of Inorganic Chemistry 1960,
Blackwell Publ., London). Therein, Group IV, V, XIII, XIV and XV
correspond respectively to Groups IVB, VB, IIIA, IVA and VA of the
Deming notation (Chemical Rubber Company's Handbook of Chemistry
& Physics, 48th edition) and to Groups IVA, VA, IIIB, IVB and
VB of the IUPAC 1970 notation (Kirk-Othmer Encyclopedia of Chemical
Technology, 2nd edition, Vol. 8,p. 94).
[0029] As mentioned above, the catalyst precursor of the present
invention has the following formula: 3
[0030] wherein:
[0031] R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently
selected from among hydrogen and C.sub.1-C.sub.8 hydrocarbyl groups
(e.g., preferably methyl), wherein none, one or two pairs of
substituents selected from the group consisting of R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 are linked to form saturated or
unsaturated rings (e.g., R.sub.2 and R.sub.3 are preferably linked
to provide an indenyl group);
[0032] M is an atom selected from among the elements of Groups IV,
V and VI, preferably a transition metal in an oxidation state of
+3;
[0033] m is 1, 2, 3 or 4;
[0034] the or each X is selected from among halide elements,
C.sub.1-C.sub.8 hydrocarbyl groups, C.sub.1-C.sub.8 alkoxy groups,
C.sub.1-C.sub.8 carboxylate groups and C.sub.1-C.sub.8 carbamate
groups;
[0035] n is 1, 2 or 3;
[0036] the or each L is an organic compound containing at least one
lone pair of electrons;
[0037] Q is a divalent radical of the formula YR.sub.5R.sub.6,
wherein Y is a Group 14 atom, wherein R.sub.5 and R.sub.6 are each
independently selected from among hydrogen and C.sub.1-C.sub.8
hydrocarbyl groups, and wherein R.sub.5 and R.sub.6 are not linked
or are linked to form a saturated or unsaturated ring;
[0038] E is a Lewis basic group having formula (i) or (ii)
below:
--C(R.sub.7).dbd.Z.sub.1R.sub.8, (i)
[0039] wherein R.sub.7 and R.sub.8 are each independently selected
from among hydrogen and C.sub.1-C.sub.8 hydrocarbyl groups, and
wherein R.sub.7 and R.sub.8 are not linked or are linked to form a
saturated or unsaturated ring; and
[0040] Z.sub.1 is a nitrogen atom or a phosphorus atom, which bonds
to M; 4
[0041] wherein:
[0042] Z.sub.2 is an oxygen atom, a sulphur atom or a selenium
atom, which bonds to M; and
[0043] R.sub.9, R.sub.10 and R.sub.11 are each independently
selected from among hydrogen and C.sub.1-C.sub.8 hydrocarbyl
groups, wherein no pair or one pair of substituents selected from
R.sub.9, R.sub.10 and R.sub.11 are linked to form a saturated or
unsaturated ring.
[0044] The hydrocarbyl groups described above are preferably
selected from among branched or unbranched alkyl groups.
[0045] The catalyst precursor may be prepared by any suitable
synthesis method, a number of which will be readily apparent to
those of skill in the art.
[0046] One useful method of making the catalyst precursor is by
reacting a hydroxy aromatic nitrogen compound, which compounds are
commercially available, with a metallic deprotonating agent such as
an alkyllithium compound in an organic solvent to form the metal
salt of the hydroxy aromatic nitrogen compound. The resulting salt
may then be reacted with a salt of the desired transition metal,
preferably a transition metal halide (i.e., chromium tetrachloride
for a chromium-containing catalyst precursor) to form the
transition metal catalyst precursor. The catalyst precursor may be
isolated by methods well known in the art.
[0047] Two or more catalyst precursor compounds may be used in a
single catalyst composition to achieve a broadened molecular weight
distribution polymer product, if desired.
[0048] The activating co-catalyst is capable of activating the
catalyst precursor.
[0049] Preferred examples of suitable co-catalysts include linear
or cyclic (co)oligomeric compounds having a formula (a)
M.sub.co-catR.sub.12, M.sub.co-catR.sub.12R.sub.13,
M.sub.co-catR.sub.12R.sub.13R.sub.14, or
M.sub.co-catR.sub.12R.sub.13R.su- b.14R.sub.15, wherein
M.sub.co-cat is a metal selected from among alkali metals, alkali
earth metals, rare earth metals, aluminum and tin, aluminum being
preferred; R.sub.12, R.sub.13, R.sub.14 and R.sub.15, where
present, are each independently selected from among hydrogen,
C.sub.1-C.sub.8 hydrocarbyl groups and C.sub.1-Cs alkoxy groups, or
(b) (M.sub.co-catR.sub.16O).sub.p(M.sub.co-catR.sub.17O).sub.q,
wherein M.sub.co-cat is a metal selected from among alkali metals,
alkali earth metals, rare earth metals, aluminum and tin, aluminum
being preferred; R.sub.16 and R.sub.17 are each independently
selected from among hydrogen and C.sub.1-C.sub.8 hydrocarbyl
groups, and p and q are each independently an integer from 1 to
100. Specific preferred examples of such co-catalysts include the
aluminoxanes, in particular MAO, MMAO and IBAO, as well as
compounds such as MgR.sub.12R.sub.13, ZnR.sub.12R.sub.13,
SnR.sub.12R.sub.13R.sub.14R.sub.15, LiR.sub.12, alkali metal
alkyls, alkali earth metal alkyls, and aluminum alkyls.
[0050] Further examples of preferred co-catalysts which can be used
according to the present invention include non-coordinating anion
activators. Examples of suitable non-coordinating anion activators
include compounds where boron is the anion, e.g., compounds of the
formula B(Ar.sub.1Ar.sub.2A.sub.3), wherein B is boron in a valence
state of 3; Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently
selected from among optionally substituted C.sub.6-C.sub.20
aromatic hydrocarbon radicals. Suitable aromatic hydrocarbon
radicals include, but are not limited to, phenyl, naphthyl and
anthracenyl radicals. These radicals may be unsubstituted or
substituted one or more times with one or more substituents.
Suitable substituents include, but are not limited to, hydrocarbyl
radicals, organometalloid radicals, alkoxy and aryloxy radicals,
alkylamido radicals, fluorine, fluorocarbyl radicals and
fluorohydrocarbyl radicals. Such substituent(s) may be at any
possible position(s) on the aromatic hydrocarbon radical(s), e.g.,
ortho, meta or para relative to the carbon atom bonded to the
anion. One example of such a compound is B(C.sub.6F.sub.5).sub.3.
U.S. Pat. No. 5,599,761 discloses some examples of non-coordinating
anion compounds which are suitable for use as co-catalysts
according to the present invention.
[0051] Additional examples of non-coordinating anion activators
which are preferred co-catalysts for use according to the present
invention include compounds having the formula
[L-H].sup.+[BAr.sub.1Ar.sub.2Ar.sub.3Ar.sub.- 4].sup.-,
wherein:
[0052] [L-H].sup.+ is a Bronsted acid, H being a hydrogen atom;
[0053] B is boron in a valence state of 3; and
[0054] Ar.sub.1, Ar.sub.2, Ar.sub.3 and Ar.sub.4, are independently
selected from among optionally substituted C.sub.6-C.sub.20
aromatic hydrocarbon radicals. Suitable aromatic hydrocarbon
radicals include, but are not limited to, phenyl, naphthyl and
anthracenyl radicals. These radicals may be unsubstituted or
substituted one or more times with one or more substituents.
Suitable substituents include, but are not limited to, hydrocarbyl
radicals, organometalloid radicals, alkoxy and aryloxy radicals,
alkylamido radicals, fluorine, fluorocarbyl radicals and
fluorohydrocarbyl radicals. Such substituent(s) may be at any
possible position(s) on the aromatic hydrocarbon radical(s), e.g.,
ortho, meta or para relative to the carbon atom bonded to the
anion.
[0055] Co-catalysts as described above are known in the art, and
can be prepared by those of ordinary skill in the art using any of
a variety of known techniques. For instance, aluminoxanes may be
prepared in a variety of ways. According to one method of preparing
aluminoxanes, a mixture of linear and cyclic aluminoxanes is
obtained in the preparation of aluminoxanes from, for example,
trimethylaluminum and water. For example, an aluminum alkyl may be
treated with water in the form of a moist solvent. Alternatively,
an aluminum alkyl, such as trimethylaluminum, may be contacted with
a hydrated salt, such as hydrated ferrous sulfate. The latter
method comprises treating a dilute solution of trimethylaluminum
in, for example, toluene with a suspension of ferrous sulfate
heptahydrate. It is also possible to form methylaluminoxanes by the
reaction of a tetraalkyldialuminoxane containing C.sub.2 or higher
alkyl groups with an amount of trimethylaluminum that is less than
a stoichiometric excess. The synthesis of methylaluminoxanes may
also be achieved by the reaction of a trialkyl aluminum compound or
a tetraalkyldialuminoxane containing C.sub.2 or higher alkyl groups
with water to form a polyalkyl aluminoxane, which is then reacted
with trimethylaluminum. Further modified methylaluminoxanes, which
contain both methyl groups and higher alkyl groups, i.e., isobutyl
groups, may be synthesized by the reaction of a polyalkyl
aluminoxane containing C.sub.2 or higher alkyl groups with
trimethylaluminum and then with water as disclosed in, for example,
U.S. Pat. No. 5,041,584.
[0056] When the activating co-catalyst is of the formula
AlR.sub.12R.sub.13R.sub.14, the mole ratio of aluminum atoms
contained in the AIR.sub.12R.sub.13R.sub.14, compound to total
metal atoms contained in the catalyst precursor is generally in the
range of from about 2:1 to about 100,000:1, preferably in the range
of from about 10:1 to about 10,000:1, and most preferably in the
range of from about 50:1 to about 2,000:1. When the activating
co-catalyst is of the formula
(AlR.sub.15O).sub.p(Al.sub.R16O).sub.q, the mole ratio of aluminum
atoms contained in the (AlR.sub.15O).sub.p(Al.sub.R16O).sub.q
compound to total metal atoms contained in the catalyst precursor
is generally in the range of from about 1:1 to about 100,000:1,
preferably in the range of from about 5:1 to about 2000:1, and most
preferably in the range of from about 50:1 to about 250:1.
[0057] The catalyst precursor and the activating co-catalyst may be
independently or simultaneously (a) impregnated onto a solid
support, (b) in liquid form such as a solution or dispersion, (c)
spray dried with a support material, (d) in the form of a
prepolymer, or (e) formed in the reactor in-situ during
polymerization. Where the catalyst precursor and the activating
co-catalyst are to be provided simultaneously, they are preferably
first combined and mixed with each other for at least 5 minutes,
preferably at least 30 minutes, to provide a composition.
[0058] In the case of a supported catalyst composition, the
catalyst composition may be impregnated in or deposited on the
surface of an inert substrate such as silica, carbon black,
polyethylene, polycarbonate porous crosslinked polystyrene, porous
crosslinked polypropylene, alumina, thoria, zirconia, or magnesium
halide (e.g., magnesium dichloride), and mixtures thereof, such
that the catalyst composition is between 0.1 and 90 percent by
weight of the total weight of the catalyst composition and the
support. These supports preferably have been calcined at a
temperature sufficient to remove substantially all physically bound
water. Conventional techniques, such as those disclosed in U.S.
Pat. No. 4,521,723, can be employed for impregnating the catalyst
composition onto a catalyst support.
[0059] A preferred support material is a silica material. For
example, some such materials are described in U.S. Pat. No.
5,264,506. Desirably, the silica support has an average particle
size of from about 60 to 200 (preferably about 70 to 140) microns;
no more than about 30 percent by weight silica should have a
particle size below about 44 microns. Further, the silica support
has an average pore diameter of greater than about 100 Angstrom
units, preferably greater than about 150 Angstrom units. It is also
desirable for the silica support to have a surface area greater
than about 200 square meters per gram. The support should be dry,
that is, free of adsorbed water. Drying of the silica is carried
out by heating it at a temperature of from about 100 to 800 degrees
C., e.g., about 600 degrees C.
[0060] Spray-drying may be effected by any spray-drying method
known in the art. Spray-drying can be useful to provide catalysts
having a narrow droplet size distribution (and resulting narrow
particle size distribution) for efficient use of the catalyst and
to give more uniform pellets and better performance, in addition to
having beneficial morphology.
[0061] For example, one example of a suitable spray-drying method
comprises atomizing a solution, suspension or dispersion of the
catalyst and/or the activating co-catalyst, optionally together
with a filler, and optionally with heating of the solution,
suspension or dispersion. Atomization is accomplished by means of
any suitable atomizing device to form discrete spherically shaped
particles. Atomization is preferably effected by passing the slurry
through the atomizer together with an inert drying gas, i.e., a gas
which is nonreactive under the conditions employed during
atomization. An atomizing nozzle or a centrifugal high speed disc
can be employed to effect atomization, whereby there is created a
spray or dispersion of droplets of the mixture. The volumetric flow
of drying gas, if used, preferably considerably exceeds the
volumetric flow of the slurry to effect atomization of the slurry
and/or evaporation of the liquid medium. Ordinarily the drying gas
is heated to a temperature as high as about 160 degrees C. to
facilitate atomization of the slurry; however, if the volumetric
flow of drying gas is maintained at a very high level, it is
possible to employ lower temperatures. Atomization pressures of
from about 1 psig to 200 psig are suitable. Some examples of
suitable spray-drying methods include those disclosed in U.S. Pat.
Nos. 5,290,745, 5,652,314, 4,376,062, 4,728,705, 5,604,172,
5,306,350 and 4,638,029.
[0062] Another type of suitable spray-drying method comprises
forming a liquid mixture comprising a nonvolatile materials
fraction, a solvent fraction and at least one compressed fluid; and
spraying the liquid mixture at a temperature and pressure that
gives a substantially decompressive spray by passing the mixture
through an orifice into an environment suitable for forming solid
particulates by solvent evaporation. For example, such a method is
disclosed in U.S. Pat. No. 5,716,558.
[0063] In general, spray-drying produces discrete, substantially
round, abrasive resistant particles with relatively narrow particle
size distribution. By adjusting the size of the orifices of the
atomizer employed during spray drying, it is possible to obtain
particles having desired average particle size, e.g., from about 5
micrometers to about 200 micrometers. The particles recovered from
the spray drying step can optionally be decarboxylated by heating
the particles, e.g., as disclosed in U.S. Pat. No. 5,652,314.
[0064] As mentioned above, catalyst precursor and/or activating
co-catalyst may be in the form of a prepolymer. Such prepolymers
can be formed in any suitable manner, e.g., by forming one or more
polymer or copolymer (which may be the same or different from the
polymer(s) and/or copolymer(s) to be collected in the reactor) in
the presence of the catalyst precursor and/or activating
co-catalyst. For example, processes which provide catalyst
precursor and/or activating co-catalyst attached to and at least
partially covered by polymeric and/or copolymeric material may be
suitable.
[0065] The catalyst composition may be used for the polymerization
of olefins by any suspension, solution, slurry, or gas phase
process, using known equipment and reaction conditions, and is not
limited to any specific type of reaction system. Such
polymerization can be conducted in a batchwise mode, a continuous
mode, or any combination thereof. Generally, suitable olefin
polymerization temperatures are in the range of from about 0
degrees C. to about 200 degrees C. at atmospheric, subatmospheric,
or superatmospheric pressures.
[0066] Preferably, gas phase polymerization is employed, at
superatmospheric pressure in the range of from about 1 to about
1000 psi, preferably 50 to 400 psi, most preferably 100 to 300 psi,
and at temperatures in the range of from about 30 degrees C. to
about 130 degrees C., preferably about 65 degrees C. to about 110
degrees C. Stirred or fluidized bed gas phase reaction systems are
particularly useful. Generally, a conventional gas phase, fluidized
bed process is conducted by passing a stream containing one or more
olefin monomers continuously through a fluidized bed reactor under
reaction conditions and in the presence of catalyst composition at
a velocity sufficient to maintain a bed of solid particles in a
suspended condition. A stream containing unreacted monomer is
withdrawn from the reactor continuously, compressed, cooled,
optionally fully or partially condensed as disclosed in U.S. Pat.
Nos. 4,543,399, 4,588,790, 5,352,749 and 5,462,999, and recycled to
the reactor. Product is withdrawn from the reactor and make-up
monomer is added to the recycle stream. As desired for temperature
control of the system, any gas inert to the catalyst composition
and reactants may also be present in the gas stream. In addition, a
fluidization aid such as carbon black, silica, clay, or talc may be
used, as disclosed in U.S. Pat. No. 4,994,534.
[0067] Slurry or solution polymerization processes may utilize
subatmospheric or superatmospheric pressures and temperatures in
the range of from about 40 degrees C. to about 110 degrees C.
Useful liquid phase polymerization reaction systems are known in
the art, e.g., as described in U.S. Pat. No. 3,324,095, U.S. Pat.
No. 5,453,471, U.S. Pat. No. 5,834,571, WO 96/04322
(PCT/US95/09826) and WO 96/04323 (PCT/US95/09827). Liquid phase
reaction systems generally comprise a reactor vessel to which
olefin monomer and catalyst composition are added, and which
contains a liquid reaction medium for dissolving or suspending the
polyolefin. The liquid reaction medium may consist of the bulk
liquid monomer or an inert liquid hydrocarbon that is nonreactive
under the polymerization conditions employed. Although such an
inert liquid hydrocarbon need not finction as a solvent for the
catalyst composition or the polymer obtained by the process, it
usually serves as solvent for the monomers employed in the
polymerization. Among the inert liquid hydrocarbons suitable for
this purpose are isopentane, hexane, cyclohexane, heptane, benzene,
toluene, and the like. Reactive contact between the olefin monomer
and the catalyst composition should be maintained by constant
stirring or agitation. Preferably, reaction medium containing the
olefin polymer product and unreacted olefin monomer is withdrawn
continuously from the reactor. Olefin polymer product is separated,
and unreacted olefin monomer is recycled into the reactor.
[0068] Polymerization may be carried out in a single reactor or in
two or more reactors in series. In a preferred aspect of the
invention, e.g., where a broader molecular weight distribution is
desired, tandem reactors are employed (i.e., two or more reactors
in series), and two or more of the reactors each have a unique set
of reaction conditions, i.e., one or more reaction condition (e.g.,
which affects polymer molecular weight) is different in one reactor
relative to one or more other reactor.
[0069] Polymerization is preferably conducted substantially in the
absence of catalyst poisons. Organometallic compounds may be
employed as scavenging agents for removal of poisons, when
necessary, to increase catalyst activity. Examples of scavenging
agents include metal alkyls, preferably aluminum alkyls, most
preferably triisobutylaluminum.
[0070] Conventional adjuvants may be included in the process,
provided they do not interfere with the operation of the catalyst
composition in forming the desired polyolefin. Hydrogen or a metal
or non-metal hydride, e.g., a silyl hydride, may be used as a chain
transfer agent in the process. Hydrogen may be used in amounts up
to about 10 moles of hydrogen per mole of total monomer feed.
[0071] Other conventional additives may be included in the process,
provided they do not interfere with the operation of the catalyst
composition in forming the desired polyolefin. For example, other
additives which may be introduced into one or more streams entering
polymer formulation include antioxidants, coupling agents,
ultraviolet absorbers or stabilizers, antistatic agents, pigments,
dyes, nucleating agents, reinforcing fillers or polymer additives,
slip agents, plasticizers, processing aids, lubricants, viscosity
control agents, tackifiers, anti-blocking agents, surfactants,
extenders oils, metal deactivators, voltage stabilizers, flame
retardant fillers and additives, crosslinking agents, boosters, and
catalysts, and smoke suppressants. Fillers and additives can be
added in amounts ranging from less than about 0.1 to more than
about 200 parts by weight for each 100 parts by weight of the base
resin, for example, polyethylene.
[0072] Examples of antioxidants are: hindered phenols such as
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane,
bis[(beta-(3,5-di-tert-butyl-4-hydroxybenzyl)-methyl-carboxyethyl)]sulphi-
de, 4,4'-thiobis-(2-methyl-6-tert-butylphenol),
4,4'-thio-bis(2-tert-butyl- -5-methyl-phenol),
2,2'-thiobis-(4-methyl-6-tert-butylphenol), and thiodiethylene
bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate; phosphites and
phosphonites such as tris(2,4-di-tert-butylphenyl) phosphite and
di-tert-butylphenyl-phosphonite; thio compounds such as
dilaurylthiodipropionate, dimyristylthiodipropionate, and
distearylthiodipropionate; various siloxanes; and various amines
such as polymerized 2,2,4-trimethyl-1,2-dihydroquinoline.
Antioxidants can be used in amounts of about 0.1 to about 5 parts
by weight per 100 parts by weight of polyethylene.
[0073] Olefin polymers and copolymers that may be produced
according to the invention include, but are not limited to,
ethylene homopolymers, homopolymers of linear or branched higher
alpha-olefins containing 3 to about 20 carbon atoms, and copolymers
of olefin (preferably ethylene) and (a) higher alpha-olefins, (b)
cyclic olefins or (c) alpha olefin-dienes. Suitable higher
alpha-olefins include, for example, propylene, 1-butene, 1-pentene,
1-hexene, 4-methyl-1-pentene, 1-octene, and
3,5,5-trimethyl-1-hexene. Suitable cyclic olefins include, for
example, norbomene. Suitable alpha olefin-dienes include linear,
branched, or cyclic hydrocarbon dienes having from about 4 to about
20, preferably 4 to 12, carbon atoms. Preferred dienes include
1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbomene, 1,7-octadiene,
vinyl cyclohexene, dicyclopentadiene, butadiene, isobutylene,
isoprene, ethylidene norbomene and the like.
[0074] Aromatic compounds having vinyl unsaturation such as styrene
and substituted styrenes, and polar vinyl monomers such as
acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters,
methacrylate esters, vinyl trialkyl silanes and the like may be
polymerized according to the invention as well.
[0075] Specific olefin polymers that may be made according to the
invention include, for example, polyethylene, higher olefins, e.g.,
polypropylene, ethylene/higher olefin, e.g., propylene rubbers
(e.g., EPR's), ethylene/higher olefin, e.g. propylene/diene
terpolymers (e.g., EPDM's), ethylene/higher olefin, e.g.,
propylene/cyclic olefin terpolymers, polybutadiene, polyisoprene
and the like.
[0076] Polymers produced by methods according to the present
invention can be crosslinked by adding a crosslinking agent to the
composition or by making the resin hydrolyzable, by adding
hydrolyzable group. Suitable cross-linking agents are organic
peroxides such as dicumyl peroxide;
2,5-dimethyl-2,5-di(t-butylperoxy)hexane; t-butyl cumyl peroxide;
and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3. Dicurnyl peroxide
is preferred. Hydrolyzable groups can be added to polymers produced
by methods according to the present invention, for example, by
copolymerizing ethylene with an ethylenically unsaturated compound
having one or more --Si(OR).sub.3 groups such as
vinyltrimethoxy-silane, vinyltriethoxysilane, and
gamma-methacryloxypropyltrimethoxysilane or grafting these silane
compounds to the resin in the presence of the aforementioned
organic peroxides. The hydrolyzable resins are then crosslinked by
moisture in the presence of a silanol condensation catalyst such as
dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate,
stannous acetate, lead naphthenate, and zinc caprylate. Dibutyltin
dilaurate is preferred.
[0077] Examples of hydrolyzable copolymers and hydrolyzable grafted
copolymers are ethylene/vinyltrimethoxy silane copolymer,
ethylene/gamma -methacryloxypropyltrimethoxy silane copolymer,
vinyltrimethoxy silane grafted ethylene/ethyl acrylate copolymer,
vinyltrimethoxy silane grafted linear low density ethylene/1-butene
copolymer, and vinyltrimethoxy silane grafted low density
polyethylene.
[0078] The present invention enables production of polymer product,
and articles formed of such product, having desirable
polydispersity index (defined as the ratio of the weight average
molecular weight of the polymer to the number average molecular
weight of the polymer (M.sub.w/M.sub.n)), melt index (determined,
e.g., according to ASTM D-1238--Condition E), flow index
(determined, e.g., according to ASTM D-1238--Condition F), melt
flow ratio (i.e., the ratio of flow index to melt index), density
(determined, e.g., according to ASTM D-1505), bulk density
(determined, e.g., according to ASTM D-1895--Method B),
unsaturation (determined, e.g., using an infrared
spectrophotometer, such as a Perkin Elmer Model 21), haze
(determined, e.g., according to ASTM D1003-61--Procedure B), gloss
(determined, e.g., according to ASTM D2457-70), rheological
properties (e.g., via dynamic oscillatory shear experiments
conducted with a Weissenberg Rheogoniometer commercially available
from TA Instruments.), melt strength behavior, shear thinning
behavior, relaxation spectrum index, crystallizable chain length
distribution index (determined, e.g., using Temperature Rising
Elution Fractionation (TREF), as described in Wild et al., J.
Polymer Sci. Poly. Phys. Ed., Vol. 20, p. 441 (1982), compositional
homogeneity, ratio of long chain branches to main chain carbon
atom, production rate, morphology, avoidance of chips and chunks,
avoidance of process upsets, avoidance of particle agglomeration,
viscosity, heat of fusion, branching (determined, e.g., by Carbon
13 NMR), and/or short chain branch frequency, (determined, e.g., by
infrared spectroscopy as described by Blitz and McFaddin in J.
Appl. Pol. Sci., 1994,51, 13).
[0079] Polymers produced according to the present invention can be
used in a variety of applications, representative examples
including, e.g., blow-molded articles, high-density films, etc.
[0080] The following examples further illustrate the invention.
EXAMPLES
[0081] Materials
[0082] Methylalumoxane (MAO) was purchased from the Albemarle
Corporation and had a nominal concentration of 3.2 mol(Al)/L.
Modified methylalumoxane (MMAO) was purchased from the Akzo
Corporation and had a nominal concentration of 1.8 mol(Al)/L.
Isobutylalumoxane (IBAO) was purchased from Akzo and had a nominal
concentration of 0.98 mol (Al)/L.
Example 1
Synthesis of Catalyst Precursor, 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetrameth- ylcyclopentadienyl chromium (III)
dichloride (compound I)
[0083] a) Preparation of 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclop- entadiene
[0084] Lithium tetramethylcyclopentadienyl (10.1 g, 78.8 mmol) was
suspended in THF (100 mL) in a 200 cc Schlenk flask and cooled in a
dry ice acetone bath. Into this flask was added dropwise a hexane
(20 mL) solution of 2-picolyl chloride (10.0 g, 78.4 mmol). The
resulting suspension was warmed to room temperature gradually and
stirred overnight. Solvent was removed under vacuum and the
resulting residue was extracted with hexane (2.times.30 mL) and
filtered, removal of hexane via vacuum resulting in a yellow oil
(yield, 17.6 g).
[0085] b) Preparation of lithium, 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramet- hyl-cyclopentadienyl
[0086] The above oil was redissolved into hexane (100 cc) in a 200
cc Schlenk flask and cooled in a dry ice acetone bath. BuLi (13.2
mL, 2.5 M in hexane, 33 mmol) was added dropwise, the resulting
suspension was warmed to room temperature gradually and stirred
overnight. The resulting yellow suspension was filtered and washed
with hexane (2.times.10 mL) and dried under vacuum to yield a
yellow-brown solid (yield, 7.8 g ).
[0087] c) Preparation of 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclop- entadienyl chromium (III)
dichloride (compound I)
[0088] CrCl.sub.3(THF).sub.3(from Aldrich, 3.0 g, 7.8 mmol) was
suspended in THF (40 mL) in a 200 cc Schlenk flask and cooled in a
dry ice acetone bath. Into this flask was added dropwise via a
cannula a THF (20 mL) solution of lithium, 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclopent- adienyl (1.7 g, 7.8 mmol).
The resulting brownish suspension was warmed to room temperature
gradually (a dark-blue solid appeared upon warm-up) and stirred
overnight. It was filtered and washed with 10 cc hexane and dried
under vacuum to result in a bright-blue solid (1.5 g). THF was
removed and the resulting residue was extracted with
CH.sub.2Cl.sub.2 and filtered again, removal of
CH.sub.2Cl.sub.2further resulted in 1.0 g of product. Total yield
2.5 g. +APCl/MS spectrum from THF volatilized: [Cr*Cl]+, calculated
m/e 299.05, [Cr*Cl-THF]+, calculated m/e 371.11; [Cr*Cl]+, found
m/e 298.9, [Cr*Cl-THF]+, found m/e 370.9.
Example 2
Synthesis of Catalyst Precursor, 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetrameth- ylcyclopentadienyl Vanadium (III)
dichloride (compound II)
[0089] VCl.sub.3(THF).sub.x (from Strem, 3.4 g, 10.1 mmol) was
suspended in CH.sub.2Cl.sub.2 (40 mL) in a 200 cc Schlenk flask and
cooled in a dry ice acetone bath. Into this flask was added
dropwise via a cannula a CH.sub.2Cl.sub.2(20 mL) solution of
lithium, 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclopentadienyl (2.2 g, 10.0 mmol).
The resulting brownish-suspension was warmed to room temperature
gradually (which changed into a dark-purple color upon warm-up) and
stirred overnight. After filtration, the solvent was removed under
vacuum and the resulting solid was washed with hexane (2.times.10
cc) and dried under vacuum. Yield 4.24 g, brown solid. +APCl/MS
spectrum from THF volatilized: [V*Cl]+, calculated m/e 298.06,
[Cr*Cl-THF]+, calculated m/e 370.11, [V*Cl]+, found m/e 297.9,
[V*Cl-THF]+, found m/e 370.0.
Example 3
Synthesis of Catalyst Precursor, 5[(2-pyridyl)
methyl]-1,2,3,4-tetramethyl- cyclopentadienyl titanium (III)
dichloride (compound III)
[0090] TiCl.sub.3(THF).sub.3 (from Aldrich, 3.48 g, 9.1 mmol) was
suspended in THF (40 mL) in a 200 cc Schlenk flask and cooled in a
dry ice acetone bath. Into this flask was added dropwise via a
cannula a THF (20 mL) solution of lithium, 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylc- yclopentadienyl (2.0 g, 9.2 mmol).
The resulting suspension was warmed to room temperature gradually
and stirred overnight. It was filtered and washed with 10 cc hexane
and dried under vacuum to result in a brownish-red solid (1.7 g).
+APCl/MS spectrum from THF volatilized: [Ti*Cl-THF]+, calculated
m/e 367.11; [Ti*Cl-THF]+, found m/e 367.0.
Example 4
Synthesis of Catalyst Precursor, (2-pyridylmethyl)-cyclopentadienyl
chromium(III) dichloride (compound IV)
[0091] a) Preparation of (2-pyridylmethyl)-cyclopentadiene
[0092] Lithium cyclopentadienyl (7.3 g, 102 mmol) was suspended in
THF (150 mL) in a 300 cc Schlenk flask and cooled in a dry ice
acetone bath. Into this flask was added slowly a THF (60 mL)
solution of 2-picolyl chloride (13 g, 102 mmol). The resulting
suspension was warmed to room temperature gradually and stirred
overnight. Solvent was removed under vacuum and the resulting
residue was extracted with hexane (2.times.30 mL) and filtered,
removal of hexane via vacuum resulting in a redish-brown oil
(yield, 6.8 g).
[0093] b) Preparation of lithium
(2-pyridylmethyl)-cyclopentadienyl
[0094] The above oil (6.8 g, 43 mmol) was redissolved into hexane
(40 cc) in a 200 cc Schlenk flask and cooled in a dry ice acetone
bath. BuLi (17.2 mL, 2.5 M in hexane, 43 mmol) was added dropwise,
the resulting suspension was warmed to room temperature gradually
and stirred overnight. The resulting suspension was filtered and
washed with diethyl ether (2.times.10 mL) and dried under vacuum to
yield a dark-brown solid (yield, 7.1 g ).
[0095] c) Preparation of (2-pyridylmethyl)-cyclopentadienyl
chromium (III) dichloride
[0096] CrCl.sub.3(THF).sub.3 (from Aldrich, 3.0 g, 7.8 mmol) was
suspended in THF (25 mL) in a 200 cc Schlenk flask and cooled to
-46.degree. C. Into this flask was added dropwise via a cannula a
THF (20 mL) solution (cooled at -46 degrees C.) of lithium
(2-pyridylmethyl)-cyclopentadienyl (1.4 g, 8.4 mmol). The resulting
brownish suspension was warmed to room temperature gradually (a
dark-blue solid appeared upon warm-up) and stirred overnight. It
was filtered and washed with 10 cc hexane and dried under vacuum to
result in a blue solid (0.7 g). THF was removed and the resulting
residue was extracted with CH.sub.2Cl.sub.2 and filtered again,
removal of CH.sub.2Cl.sub.2further resulted in 1.6 g of product.
Total yield 2.3 g.
Example 5
Synthesis of Catalyst Precursor, 1-(2-pyridlylmethyl)-indenyl
chromium (III) dichloride (compound V)
[0097] a) Preparation of (2-pyridylmethyl)-indene
[0098] Lithium indenyl (3.0 g, 24.6 mmol) was suspended in THF (20
mL) in a 300 cc Schlenk flask and cooled in a dry ice acetone bath.
Into this flask was added slowly a THF (15 mL) solution of
2-picolyl chloride (3.13 g, 24.6 mmol). The resulting suspension
was warmed to room temperature gradually and stirred overnight.
Solvent was removed under vacuum and the resulting residue was
extracted with ether (2.times.30 mL) and filtered, removal of ether
via vacuum resulting in a dark-brown oil (yield, 4.0 g).
[0099] b) Preparation of lithium (2-pyridylmethyl)-indenyl
[0100] The above oil (4.0 g, 19 mmol) was redissolved into
THF/hexane (15 cc/15 cc) in a 200 cc Schlenk flask and cooled in a
dry ice acetone bath. BuLi (8.0 mL, 2.5 M in hexane, 20 mmol) was
added dropwise, the resulting suspension was warmed to room
temperature gradually and stirred overnight. The resulting
suspension was filtered and washed with hexane (2.times.15 mL) and
dried under vacuum to yield a purple solid (yield, 4.2 g )
[0101] c) Preparation of (2-pyridylmethyl)-indenyl chromium (III)
dichloride
[0102] CrCl.sub.3(THF).sub.3 (from Aldrich, 3.0 g, 7.8 mmol) was
suspended in THF (25 mL) in a 200 cc Schlenk flask and cooled to
-46.degree. C. Into this flask was added dropwise via a cannula a
THF (20 mL) solution (cooled at -46 degrees C.) of lithium
(2-pyridylmethyl)-indenyl (1.7 g, 8 mmol). The resulting suspension
was warmed to room temperature gradually (a dark-green solid
appeared upon warm-up) and stirred overnight. It was filtered and
washed with 10 cc hexane and dried under vacuum to result in a dark
green-yellow solid (1.15 g). THF was removed and the resulting
residue was extracted with CH.sub.2Cl.sub.2 and filtered again,
removal of CH.sub.2Cl.sub.2 further resulted in 1.65 g of product.
Total yield 2.8 g.
Example 6
Synthesis of Catalyst Precursor,
5-[(2-quinolinyl)methyl]-1,2,3,4-tetramet- hylcyclopentadienyl
chromium (III) dichloride (compound VI)
[0103] a) Preparation of
5-[(2-quinolinyl)methyl]-1,2,3,4-tetramethylcyclo- pentadiene
[0104] Lithium tetramethylcyclopentadienyl (7.8 g, 60.8 mmol) was
suspended in THF (100 mL) in a 300 cc Schlenk flask and cooled in a
dry ice acetone bath. Into this flask was added dropwise a hexane
(20 mL) solution of 2-chloromethyl quinoline (10.0 g, 59 mmol). The
resulting suspension was warmed to room temperature gradually and
stirred overnight. Solvent was removed under vacuum and the
resulting residue was extracted with hexane (2.times.30 mL) and
filtered, removal of hexane via vacuum resulting in a brown oil
(yield, 14 g).
[0105] b) Preparation of lithium
5-[(2-quinolinyl)methyl]-1,2,3,4-tetramet- hylcyclopenta
-dienyl
[0106] The above oil was redissolved into hexane (200 cc) in a 500
cc Schlenk flask and cooled in a dry ice acetone bath. BuLi (12 mL,
2.5 M in hexane, 30 mrnol) was added dropwise, the resulting
suspension was warmed to room temperature gradually and stirred
overnight. The resulting yellow suspension was filtered and washed
with hexane (3.times.10 mL) and dried under vacuum to yield a dark
solid (yield, 10.7 g )
[0107] c) Preparation of
5-[(2-quinolinyl)methyl]-1,2,3,4-tetramethylcyclo- pentadienyl
Chromium (III) dichloride (compound VI)
[0108] CrCl.sub.3(THF).sub.3 (from Aldrich, 3.0 g, 7.8 mmol) was
suspended in THF (25 mL) in a 200 cc Schlenk flask and cooled at
-46.degree. C. Into this flask was added dropwise via a cannula a
THF (15 mL) solution (cooled at -46 degrees C.) of lithium
5-[(2-quinolinyl)methyl]-1,2,3,4-te- tramethylcyclopentadienyl (2.1
g, 7.8 mmol). The resulting dark suspension was warmed to room
temperature gradually (a dark-blue solid appeared upon warm-up) and
stirred overnight. It was filtered and washed with 10 cc hexane and
dried under vacuum to result in a blue-green solid (1.5 g). THF was
removed and the resulting residue was extracted with
CH.sub.2C.sub.2 and filtered again, removal of CH.sub.2Cl.sub.2
further resulted in 0.7 g of product. Total yield 2.2 g. +APCl/MS
spectrum from THF volatilized: [Cr*Cl]+, calculated m/e 349.07,
[Ti*Cl-THF]+, calculated m/e 421.13; [Cri*Cl]+, found m/e 348.9,
[Cr*Cl-THF]+, found m/e 421.0.
Example 7
Synthesis of Catalyst Precursor,
5-[(2-quinolinyl)methyl]-1,2,3,4-tetramet- hylcyclopentadienyl
vanadium(III) dichloride (compound VII)
[0109] VCl.sub.3(THF).sub.x (from Strem, 3.0 g, 8.9 mmol) was
suspended in THF (30 mL) in a 200 cc Schlenk flask and cooled at
-46.degree. C. Into this flask was added dropwise via a cannula a
THF (20 mL) solution (cooled at -46 degrees C.) of lithium
(2-quinolinylmethyl)-tetramethylcyc- lopentadienyl (2.8 g, 10.4
mmol). The resulting dark suspension was warmed to room temperature
gradually (a dark-blue solid appeared upon warm-up) and stirred
overnight. It was filtered and then THF was removed, the resulting
residue was extracted with CH.sub.2Cl.sub.2 and filtered again,
removal of CH.sub.2Cl.sub.2 resulted in 1.8 g of dark solid. Total
yield 2.2 g.
Example 8
Ethylene Polymerization
[0110] 500 cc hexane and a scavenger were added into a 1 L
stainless-steel reactor (Fluitron.RTM.) which had been dried by
flowing nitrogen through it while it was held at 100 degrees C. for
at least 1 hour (h.), it was passivated at least for 0.5 h. Next,
ethylene was introduced into the reaction at 110 psi total pressure
and the temperature was allowed to equilibrate at 65 degrees C. The
desired amount of MAO (in toluene, or MMAO in heptane) preactivated
catalyst was injected using a pressure-proof syringe. The pressure
in the reaction was kept constant by supplying ethylene and the
temperature was maintained at 85 degrees C. through jack-cooling.
After 0.5 hour, the polymerization was stopped and the polymer was
taken out from the reactor and dried first overnight at ambient
temperature and further dried at 50 degrees C. under vacuum. The
results are shown in Tables 1 and 2.
1TABLE 1 Ethylene polymerization results at 85 degree C. Activity
[M] C2 Time Yield (kg/mmol/h/100 psi Run Catalyst .quadrature.mol
Co-cat Al/M Partial(psi) (h) (g) C2) 1 I 1 MAO 200 100 0.5 52 110 2
I 0.5 MMAO- 300 100 0.5 60 215 3A 3 II 1.2 MAO 200 100 0.5 91 135 4
III 1.7 MAO 300 100 0.5 42 43 5 IV 5.7 MAO 210 100 0.5 45 15 6 V 1
MAO 300 100 0.5 27 45 7 VI 1 MAO 100 100 1.5 62 38 8 VII 1 MAO 100
100 0.5 20 37 [M] = catalyst loading, micromol Al/M = molar ratio
Al/M
[0111]
2TABLE 2 Analytical Data For Runs 1-8 Run Tm (.degree. C.).sup.a
Density (g/cc) Mw (.times.10.sup.-3).sup.b MWD 1 130 0.954 230 5.8
3 132 0.970 30 3.0 4 133 >0.970 16 2.3 5 132 0.966 too high -- 6
133 0.955 135 10.6 7 134 0.946 238 2.3 8 125 0.943 94 2.6
.sup.aDetermined by DSC, 2.sup.nd heat .sup.bDetermined by GPC
[0112] It is significant to note that in the above examples,
promoters for eventing extensive reduction of the metal in the
catalyst are not required, although such promoters can be used if
desired. In the past, vanadium catalysts have typically required a
promoter to prevent extensive reduction of the vanadium, e.g., from
an oxidation state of +4 to +2, such promoters including, e.g.,
CBr.sub.4 or CCl.sub.4.
Example 9
Ethylene/1-hexene copolymerization using compound I
[0113] The polymerization run procedures were identical to those of
Example 8 except that the desired amounts of 1-hexene were added.
The polymerization results and analytical data are shown in Tables
3 and 4.
3TABLE 3 1-Hexene/Ethylene Copolymerization Results using compound
I Activity [M] 1-Hexene Time Yield (kg/mmol/h/ Run .quadrature.mol
Co-cat Al/M (cc) (h) (g) 100 psi C2) 9 1 MMAO 90 0 0.5 65 120 10 1
MMAO 90 20 0.5 31 62 11 1 MMAO 90 60 0.5 17 35
[0114]
4TABLE 4 Analytical Data for run 9-11 Run Tm (.degree. C.).sup.a
Density (g/cc) Mw (.times.10.sup.-3).sup.b MWD 9 132 0.952 209 7.7
10 127 0.944 84 2.3 11 122 0.937 91 2.5 .sup.aDetermined by DSC,
2.sup.nd heat .sup.bDetermined by GPC
Example 10
Ethylene/1-hexene copolymerization using compound II
[0115] The polymerization run procedures were identical to Example
8 except that the desired amounts of 1-hexene were added. The
polymerization results and analytical data are shown in Tables 5
and 6.
5TABLE 5 1-Hexene/Ethylene Copolymerization Results using compound
II Activity [M] 1-Hexene Time Yield (kg/mmol/h/ Run .mu.mol Co-cat
Al/M (cc) (h) (g) 100 psi C2) 12 1 MMAO 300 0 0.5 91 135 13 1 MMAO
300 20 0.5 48 79 14 1 MMAO 300 60 1 57 52
[0116]
6TABLE 6 Analytical Data for run 12-14 Run Tm (.degree. C.).sup.a
Density (g/cc) Mw (.times.10.sup.-3).sup.b MWD 12 132 0.970 30 3.0
13 127 0.962 22 2.9 14 124 0.954 22 2.0 .sup.aDetermined by DSC,
2.sup.nd heat .sup.bDetermined by GPC
Example 11
Ethylene/Propylene/ENB terpolymerization
[0117] A small glass vial was charged with a magnetic stirbar and a
toluene solution of MAO (3 g, 3.15 M) and compound I (14 mg, 0.041
mmol) and stirred for 0.5 hour. 500 mL hexane was charged into a
1.0 L stainless-steel reactor (Fluitron.RTM.) which had been dried
by flowing nitrogen through it while it was held at 100 degrees C.
for at least 1 hour (h.), followed by 1 mL of TIBA and 3 mL of ENB
(ethylidene norbomene). The reactor was sealed and heated to 60
degrees C., where it was held throughout the remainder of the run
by a combination of cold water and steam flowed through the reactor
jacket. When the reactor had reached approximately 40 degrees C.,
the reactor was vented of most of the nitrogen, resealed, and
pressurized with a mixture of propylene and ethylene, with the
propylene flow made to equal that of ethylene, both measured in
L/min. When the reactor had reached ca. 87 psig pressure, the ratio
of propylene to ethylene flows was adjusted to 1:3. The reactor
temp was then reduced to 50 degrees C. and above catalyst solution
(0.5 ml) was injected. When exotherm was over, the temperature was
increased to 60 degrees C. and continued for 1 hour (additional 0.5
mL ENB were added at 10 and 20 min into the run) at which point the
reactor was vented and the temperature rapidly cooled to room
temperature. The polymer was recovered by transfer of the polymer
solution to a large glass beaker, to which were added ca. 500 mL of
methanol. The recovered polymer was further dried in vacuum oven
and weighed 52 g. The polymer contained 9.7 weight % propylene and
6.8 weight % norbomene by NMR. DSC on the polymer revealed a
crystallinity of 39.9 % on first heat.
Example 12
Ethylene polymerization using a supported catalyst
[0118] Preparation of Supported Catalyst. In the glovebox under
nitrogen, a 500 mL 2-neck round-bottom flask was charged with a
stirbar, 50 g porous silica (Davison.RTM.955, previously calcined
at 250 degrees C.), and 200 hexane. The flask was sealed attached
to the vacuum line under nitrogen. In a 250 mL two-necked
round-bottom flask were placed a stirbar, 150 g MMAO-3A (Akzo, 1.87
M in heptane), and 0.62 g of 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclopenta-dienyl chromium (III)
dichloride (I). This mixture was stirred at RT for about 40 minutes
and then cannular transferred into the silica-containing flask in
0.5 h. It was further stirred for 1 additional hour, and the
solvent was subsequently removed first by N.sub.2 purge and
followed by vacuum. Final yield was 82 g of a light purple
free-flowing powder. The Kaydol oil catalyst slurry was prepared by
adding 0.4 g catalyst in 10 cc oil and sufficiently mixing.
[0119] Polymerization Run 500 cc hexane and 1.0 cc Tiba were added
into a 1 L stainless-steel reactor (Fluitron.RTM.) which had been
dried by flowing nitrogen through it while it was held at 100
degrees C. for at least 1 hour (h.), and it was passivated at least
for 0.5 h at 50 degrees C. Next, the temperature was raised to 65
degrees C. and overhead pressure was vented off. 2.0 cc of the
pre-prepared catalyst oil-slurry was injected and ethylene was
quickly introduced into the reaction at 110 psi total pressure, and
the temperature was raised to 95 degrees C. The pressure in the
reaction was kept constant by supplying ethylene and the
temperature was maintained at 95 degrees C. through jack-cooling.
After 0.5 hour, the polymerization was stopped and the polymer was
taken out from the reactor and dried overnight at ambient
temperature to yield 68 g of polymer, activity 73 kg PE/mmol cat.
h. 100 psi.
Example 13
Ethylene/Norbornene copolymerization using compound I
[0120] Norbomene hexane solution: Norbomene (Aldrich, 11.2 g. 0.12
mol) was dissolved in 100 cc hexane, 14.5 wt %.
[0121] The polymerization run procedures were identical to those of
Example 8 except that the desired amounts of norbomene hexane
solution were added. The polymerization results and analytical data
are shown in Table 7.
7TABLE 7 Norbornene/Ethylene Copolymerization Results using
compound I Activity [M] Norbornene Yield (kg/mmol/h/100 psi Density
Run .mu.mol Co-cat Al/M (g) (g) C2) Ml2 (g/cc) 15 1 MMAO 300 0.4 48
89 1.4 -- 16 1 MMAO 300 1.9 59 103 102 0.954
Example 14
Ethylene polymerization using IBAO as co-catalyst
[0122] Synthesis of 5-[(2-pyridyl) methyl)]-1,
2,3,4-tetramethylcyclopenta- dienyl Chromium (III) dibenzyl (VIII):
5-[(2-pyridyl) methyl)]-1,2,3,4-tetramethylcyclopentadienyl
chromium (III) dichloride (1.0 g 2.98 mmol) was suspended in 20 cc
toluene and cooled to -78 degrees C., and to this suspension was
added benzyl magnesium chloride (Aldrich, 2.0 M, 3.0 cc, 3.0 mmol)
drop-wise. The resulting solution was warmed to RT (room
temperature) slowly and turned into a brownish-green solution. It
was stirred for 12 h. It was then filtered and the solvent was
removed by vacuum to result in an oily brown-green solid. It was
further washed with hexane (2.times.10 cc) and dried again under
vacuum to yield 1.1 g (85%) of a brown-green solid.
[0123] Synthesis of 5-[(2-pyridyl)
methyl)]-1,2,3.4-tetramethylcyclopentad- ienyl chromium (III)
dimethyl (compound IX): To a 100 cc Schlenk flask were added
CrCl.sub.3 (1.58 g, 10 mmol) and ligand 5-[(2-pyridyl)
methyl)]-1,2,3,4-tetramethylcyclopentadienyl lithium salt (2.19 g,
10 mmol), and subsequently was added 25 cc THF at RT . A green-blue
suspension was observed immediately, and stirring was continued for
5 hours at RT. Then it was cooled to -78 degrees C. MeLi (1.4 M in
ether, 14.3 cc, 20 mmol) was added drop-wise and a dark-red
solution was observed. It was slowly warmed to RT and stirred for
12 hours. The solvent was removed by vacuum and the resulting solid
was extracted with toluene (2.times.10 cc). Removal of toluene and
further wash with hexane (10 cc) resulted in a dark-red solid (2.6
g, 88% based on CrCl.sub.3). +APCl/MS spectrum from THF
volatilized: [Cr*Me]+, calculated m/e 279.11, [Cr*Me-THF]+,
calculated m/e 351.17; [Cr*Me]+, found m/e 278.9, [Cr*Me -THF]+,
found m/e 351.0.
[0124] A hexane stock solution (5.7 mM) was prepared by dissolving
17 mg VIV in 10 cc hexane.
[0125] Polymerization Run 500 cc hexane and 1.5 cc IBAO-80 were
added into a 1 L stainless-steel reactor (Fluitron.RTM.) which had
been dried by flowing nitrogen through it while it was held at 100
degrees C. for at least 1 hour (h.), and it was passivated at least
for 0.5 h at 50 degrees C. Next, ethylene was introduced into the
reaction at 110 psi total pressure and the temperature was allowed
to equilibrate at 65 degrees C. The catalyst stock solution (0.15
cc) was injected using a pressure-proof syringe and the temperature
was quickly brought to 85 degrees C. The pressure in the reaction
was kept constant by supplying ethylene and the temperature was
maintained at 85 degrees C. through jack-cooling. After 0.5 hour,
the polymerization was stopped and the polymer was taken out from
the reactor and dried overnight at ambient temperature to yield 39
g of polymer, activity 92 kg PE/mmol cat. h. 100 psi.
[0126] It is significant to note that in the past, where IBAO has
been employed as the activating co-catalyst, activity has usually
been unsatisfactory. However, in Example 14 herein, surprisingly,
activity was good. This is particularly important in view of the
fact that IBAO is currently significantly less expensive to obtain
or produce than other co-catalyst materials, e.g., MAO and
MMAO.
[0127] Although the compounds, compositions and processes in
accordance with the present invention have been described in
connection with preferred embodiments, it will be appreciated by
those skilled in the art that modifications not specifically
described may be made without departing from the spirit and scope
of the invention defined in the following claims.
[0128] Each of the U.S. Patents and PCT Publications identified
above are hereby expressly incorporated by reference in their
entireties.
* * * * *