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PROCESS FOR THE POLYMERIZATION OF ETHYLENE AND A SMALL AMOUNT OF A DIENE
FIELD OF THE INVENTION
The present invention relates to a polymerization process. In particular, the
invention relates to a process for improving the processability of bulky
ligand metallocene
catalyzed polymers by utilizing low levels of dime, to improve polymer
processability and
to independently control the polymer's melt index ratio.
BACKGROUND OF THE INVENTION
Polymers produced by bulky ligand metallocene catalysts have excellent
properties
such as mechanical strength and transparency. However, these polymers are
typically more
difficult to process. Processability is the ability to economically process
and shape a
polymer uniformly. Factors of processability include melt strength or the
polymer's
strength at its extrusion temperature, shear thinning or the ease at which the
polymer flows,
and whether or not the extrudate is distortion free.
Ethylene based polymers produced by bulky ligand metallocene catalysis (mPe),
for
example, are generally more difficult to process when compared to low density
polyethylenes (LDPE) prepared in a high pressure polymerization process.
Typically,
mPe's require more motor power and produce higher extrusion pressures to match
the
extrusion rate of LDPE's. This is typically evident where a polymer exhibits a
low melt
index ratio (MIR which is the ratio of ratio of Izl/I2., where. I2 is the MI
measured according
to ASTM D-1238, Condition E, at 190°C and where Iz, is the flow index
measured
according to ASTM D-1238, Condition F, at 190°C). In addition, mPE's
generally possess
a lower melt strength, which adversely affects bubble stability during blown
film extrusion,
and are prone to melt fracture at commercial shear rates. The relatively low
melt strength
and relatively low melt viscosity of mPe make the blown bubble extrusion
fabrication of
film more difficult and lower the rate of production when compared to other
types of
polymers processed by the same technique.
One method to improve the processability (both shear thinning and melt
strength) of
mPE is to introduce long chain branching (LCB) into the polymer. In LCB, the
polymer
has branching of sufficient length for chain entanglement, that is the length
of a branch is
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long enough, or contains sufficient carbons, to entangle with other polymer
molecules.
Generally, long chain branching involves a chain length of at least 6 carbons,
and usually
contains 10 or more carbons. The long chain branch may be as long as the
length of the
polymer backbone. Polyethylene containing long chain branching possesses good
strength
and low viscosity under high shear conditions which permits high processing
rates. In
addition, polyethylene containing long chain branching often exhibits strain
hardening, so
that films made from such polyethylene tend not to fail during manufacture.
Currently there is no effective way to independently control LCB in
polymerization
processes, and in particular in gas phase polymerization processes. In
addition, present gas
phase reactors target only the control of the polymer product's melt index
(MI) and density.
As a result of this two-dimensional polymer product property control, the
product's MIR,
which measures the shear thinning capability, is difficult to control
independently of the MI
and density. This is because the MIR varies with different MI and density
targets. For
example, the MIR increases with decreasing MI and increasing density.
U.S. Patent No. 5,492,986 issued Feb. 20, 1996 to Bai discloses a process for
the
production of homogeneous polyethylene having superior strain hardening
properties by
contacting ethylene, one or more alpha olefins, and one or more unconjugated
dimes under
polymerization conditions utilizing a vanadium catalyst.
European Patent Application EP 0 543 119 A2 discloses a prepolymerization
catalyst comprising an a-olefin and a polyene.
European Patent Application EP 0 743 327 A2 discloses polyethylene having
enhanced processability prepared utilizing racemic and meso stereoisomers of a
bridged
metallocene catalyst having facial chirality.
European Patent Application EP 0 784 062 A2 (EP'062) discloses a process for
making a polyethylene, having long chain branching, in the presence of a
polyene, or
hydrocarbon interlinking compound, in an amount sufficient to provide chain
entanglement
or long chain branching. The EP '062 application describes sufficient amounts
of dime
levels as from about 8000 to 35,000 ppm. However, this dime concentration
produces
polymer products with gels. In addition, the EP '062 application does not
independently
control the dime feed, but rather dissolves the dime in the hexene comonomer
and feeds
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the combined mixture into the reactor. Therefore, the EP'062 application
process couples
LCB and the density of the polymer product.
Study on Co- and Terpolymerization of Ethylene and Diene Using Metallocene
Catalysts, Pietikainene, P. et al., Polymer Technology Publication SeYies No.
16, (1993)
Helsinki Univ. of Technology, Espoo, Finland, generally reviews use of
metallocene
catalysts in the co- and terpolymerization of ethylene.
Copolymerization of Propene and Nonconjugated Diene Involving Intramolecular
Cyclization with MetallocenelMethaluminoxane, Naofwni Naga, et al.
Macromolecules,
32 (1999), 1348-1355, discloses the cyclization reaction of incorporated dimes
produced by
the copolymerization of propene with nonconjugated dimes (1,5-hexadiene and
1,7-
octadiene) utilizing a stereospecific metallocene catalyst.
Copolymerization of Ethylene and non-conjugated dimes with Cp~ZrCh/MAO
Catalyst System, Pietilcainene, P. et al., Eu~opeah Polymer Jou~fzal 35
(1999), 1047-1055,
discloses the cyclization of hexadiene to from five-member rings in
polyethylene produced
by metallocene catalysts.
While these polymerization process have been described in the art, a need
exists for
a process to improve mPe processability, to improve the MIR of mPe, and to
provide for
independent control the MI, density, and the MIR of polymer products.
SUMMARY OF THE INVENTION
This invention relates to a process for improving the processability of bulky
ligand
metallocene catalyzed polymers.
In one aspect, the invention provides a process for improving the
processability of
bulky ligand metallocene catalyzed polyethylenes by utilizing low levels of
dime, to
enhance the polymer's melt index ratio.
In another aspect, the invention provides a process for controlling the melt
index
ratio of bulky ligand metallocene catalyzed polyethylenes independently of the
melt index
and density by the introduction of low levels of dime in gas phase
polymerization
processes.
DETAILED DESCRIPTION OF THE INVENTION
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Introduction
The invention relates to the use of a low level of dime to introduce long
chain
branching into polymers produced in gas phase polymerization processes
utilizing bulky
ligand,metallocene polymerization catalysts. The invention also relates to the
use of low
level dimes to control the polymer product's melt index ratio independently of
the melt
index and density. The polymers, specifically polyethylenes, which include
ethylene
homopolymer, copolymer, and terpolymer, produced by this process possess
enhanced melt
strength and shear-thinning behavior, which allows for easier processing. This
enhanced
processability encompasses ease in both extrusion and fabrication processes,
such as in
blown film, blow molding, extrusion coating and wire and cable extrusion
operations.
Bulky Li~and Metallocene Catalyst Compounds
The process of the invention provides polymers of enhanced processability by
the
addition of a low level of dime during polymerization. Specifically the
process of the
invention enhances the processability of polyethylene polymers, produced in
gas phase
polymerization processes catalyzed by bulky ligand metallocene catalyst
compounds.
Generally, these 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
compounds are described as containing one or more bullcy ligand(s) and one or
more
leaving groups) bonded to at least one metal atom. In one preferred
embodiment, at least
one bulky ligands is ~-bonded to the metal atom, most preferably r~s-bonded to
a transition
metal atom.
The bulky ligands are generally represented by one or more open, acyclic, or
fused
rings) or ring systems) or a combination thereof. The rings) or ring systems)
of these
bulky ligands 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 rings) or ring systems) 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
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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.
In one embodiment, low level diene is added to a polymerization process
utilizing
the bulky ligand metallocene catalyst compounds represented by the formula:
LALBMQn (
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
zirconium, hafiiium
or titanium. The bulky ligands, LA and LB, are open, acyclic or fused rings)
or ring
systems) 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,
LA and LB may be any other ligand structure capable of r~-bonding to M,
preferably r~3-
bonding to M and most preferably r~s-bonding . In yet another embodiment, the
atomic
molecular weight (MW) of L" or LB exceeds 60 a.m.u., preferably greater than
65 a.m.u.. In
another embodiment, L" and LB 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" and LB bullcy ligands
include but are not
limited to bulky amides, phosphides, alkoxides, aryloxides, imides,
carbolides, borollides,
porphyrins, phthalocyanines, cornns and other polyazomacrocycles.
Independently, each
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LA and LB 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 LA or LB is present.
Independently, each L" and L$ 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, alkyltluo
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, sulfux, germanium and the like, including olefins such as but not
limited to
olefinically unsaturated substituents including vinyl-terminated Iigands, 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 I-butanyl may
form a
carbon sigma bond to the metal M.
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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 catalyst
compound to
form a bulky ligand metallocene 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 catalyst compound.
Non-limiting examples of Q ligands include weak bases such as amines,
phosphines,
ethers, carboxylates, dimes, 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.
In a preferred embodiment, low level dime is added to a polymerization process
utilizing the bulky ligand metallocene catalyst compounds of formula (II)
where LA and LB
are bridged to each other by at least one bridging group, A, as represented in
the following
formula:
L"ALBMQn (II)
These bridged compounds represented by formula (II) are known as bridged,
bulky
ligand metallocene catalyst compounds. L", LB, 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
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represented by R'ZC, R'ZSi, R'zSi R'ZSi, R'zGe, 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 catalyst compounds of
formula (II)
have two or more bridging groups A (EP 664 301 B1).
In another embodiment, the bulky ligand metallocene catalyst compounds are
those
where the R substituents on the bulky ligands LA and LB 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 LA and LBof formulas (I) and (II) are
different
from each other.
Other bulky ligand metallocene catalyst compounds and catalyst systems useful
in
the invention may include those described in U.S. Patent 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
and 5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95107140, 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-B1-0 748 821 and EP-B1-0 757
996, all
of which are herein fully incorporated by reference.
In another embodiment, bulky ligand metallocene catalysts compounds useful in
the
invention include bridged heteroatom, mono-bulky ligand metallocene 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, W096/00244, WO 97/15602 and
WO 99/20637 and U.S. Patent 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.
In this embodiment, low level dime is added to a polymerization process
utilizing
the bulky ligand metallocene catalyst compound represented by formula (III):
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L~AJMQn (III)
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; LC
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~, A and J form a fused
ring system. In an
embodiment, L~ of formula (III) is as defined above for LA, 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.
In another embodiment, low level dime is added to a polymerization process
where the bulky ligand type metallocene catalyst compound utilized 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. Patent Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, all
of
which are herein fully incorporated by reference.
In another embodiment, low level dime is added to a polymerization process
utilizing bulky ligand metallocene catalyst compounds represented formula IV:
LDMQZ(YZ)X" (IV)
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; LD is a bulky ligand that
is bonded
to M; each Q is independently bonded to M and Qz(YZ) forms a unicharged
polydentate ligand; A or Q is a univalent anionic ligand also bonded to M; X
is a
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univalent aniouc group when n is 2 or X is a divalent anionic group when n is
1; n is
1 or 2.
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-,
-CR2- and -S-; Y is either C or S; Z is selected from the group consisting of -
OR,
NR2, -CR3, -SR, -SiR3, -PR2, -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, -NR2, -SR, -SiR3, -PR2 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 l; preferably X
is a
carbamate, carboxylate, or other heteroallyl moiety described by the Q, Y and
Z
combination.
In another embodiment of the invention, the bulky ligand metallocene-
type catalyst compounds are heterocyclic Iigand complexes where the bulky
ligands, the
rings) 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 catalyst compounds are described in WO
96/33202, WO
96/34021, WO 97/17379 and WO 98/22486 and EP-Al-0 874 005 and U.S. Patent No.
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.
In another embodiment, the bulky ligand metallocene 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
Serial No. 09/103,620 filed June 23, 1998, which is herein incorporated by
reference.
In another embodiment, the bulky Iigand metallocene catalyst compounds are
those
described in PCT publications WO 99/01481 and WO 98/42664, which are fully
incorporated herein by reference.
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In another embodiment, low level dime is added to a polymerization process
utilizing the bulky ligand metallocene catalyst compounds represented by
formula V:
((Z)~t(~'J))qMQn CV)
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 l; 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.
It is also within the scope of this invention, in one embodiment, that the
bulky
ligand metallocene catalyst compounds include complexes of Niz+ and Pd2+
described in
the articles Johnson, et al., "New Pd(II)- and Ni(II)- Based Catalysts for
Polymerization
of Ethylene and a-Olefins", J. Am. Chem. Soc. 1995, 117, 6414-6415 and
Johnson, et
al., "Copolymerization of Ethylene and Propylene with Functionalized Vinyl
Monomers by Palladium(II) Catalysts", J. Am. Chem. Soc., 1996, 118, 267-268,
and
WO 96/23010 published August l, 1996, WO 99/02472, U.S. Patent Nos. 5,852,145,
5,866,663 and 5,880,241, which are all herein fully incorporated by reference.
These
complexes can be either dialkyl ether adducts, or alkylated reaction products
of the
described dihalide complexes that can be activated to a cationic state by the
activators
of this invention described below.
Also included as bulky ligand metallocene catalyst are those diimine based
Iigands of Group 8 to 10 metal compounds disclosed in PCT publications WO
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96/23010 and WO 97/48735 and Gibson, et. al., Chem. Comm., pp. 849-850 (1998),
all
of which are herein incorporated by reference.
Other bulky ligand metallocene catalysts are those Group 5 and 6 metal imido
complexes described in EP-A2-0 816 384 and U.S. Patent No. 5,851,945, which is
incorporated herein by reference. In addition, bulky ligand metallocene
catalysts
include bridged bis(arylamido) Group 4 compounds described by D.H. McConville,
et
al., in Organometallics 1195, 14, 5478-5480, which is herein incorporated by
reference.
In addition, bridged bis(amido) catalyst compounds are described in WO
96/27439,
which is herein incorporated by reference. Other bulky ligand metallocene
catalysts are
described as bis(hydroxy aromatic nitrogen ligands) in U.S. Patent No.
5,852,146,
which is incorporated herein by reference. Other metallocene catalysts
containing one
or more Group 15 atoms include those described in WO 98/46651, which is herein
incorporated herein by reference. Still another metallocene bulky ligand
metallocene
catalysts include those multinuclear bulky ligand metallocene catalysts as
described in
WO 99/20665, which is incorporated herein by reference.
It is also contemplated that in one embodiment, the bulky ligand metallocene
catalysts of the invention described above include their structural or optical
or
enantiomeric isomers (meso and racemic isomers, for example see U.S. Patent
No.
5,852,143, incorporated herein by reference) and mixtures thereof.
Activator Compositions
The above described bulky ligand metallocene polymerization catalyst compounds
are typically activated in various ways to yield compounds having a vacant
coordination
site that will coordinate, insert, and polymerize olefin(s). 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 bulky ligand metallocene
catalyst.
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
bulky ligand metallocene catalyst to a catalytically active bulky ligand
metallocene catalyst
cation.
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It is within the scope of this invention to use as alumoxane or modified
alumoxanes
as an activator. There are a variety of methods for preparing alumoxane and
modified
alumoxanes, non-limiting examples of which are described in U.S. Patent No.
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-B 1-0 586 665, and PCT publication WO 94/10180, all of which are herein
fully
incorporated by reference.
In one embodiment aluminoxanes or modified alumoxanes are combined with
catalyst compound(s). In another embodiment modified methyl alumoxane in
heptane
(MMA03A), commercially available from Akzo Chemicals, Inc., Holland, under the
trade
name Modified Methylalumoxane type 3A , (see for example those aluminoxanes
disclosed
in U.S. Patent No. 5,041,584, which is herein incorporated by reference) is
combined with
the catalyst compounds) to form a catalyst system.
Organoaluminum compounds useful as activators include trimethylaluminum,
triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-
octylaluminum and the
like.
It is within the scope of this invention to use an ionizing or stoichiometric
activator,
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 bulky ligand metallocene catalyst compound. It
is also within
the scope of this invention to use neutral or ionic activators alone or in
combination with
alumoxane or modified alumoxane activators.
Examples of neutral stoichiometric activators include tri-substituted boron,
tellurium, aluminum, gallium and indium or mixtures thereof. The three
substituent groups
are each independently selected from alkyls, alkenyls, halogen, substituted
alkyls, aryls,
arylhalides, alkoxy and halides. Preferably, the three groups are
independently selected
from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls,
and alkenyl
compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20
carbon
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atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20
carbon
atoms and aryl groups having 3 to 20 carbon atoms (including substituted
aryls). More
preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl,
napthyl or
mixtures thereof. Most preferably, the neutral stoichiometric activator is
trisperfluorophenyl boron or trisperfluoronapthyl boron.
Ionic stoichiometric activator compounds may contain an active proton, or some
other ration 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. Patent Nos. 5,153,157,
5,198,401,
5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent
Application
Serial No. 08/285,380, filed August 3, 1994, all of which are herein fully
incorporated by
reference.
In a preferred embodiment, the stoichiometric activators include a ration and
an
anion component, and may be represented by the following formula:
(L-H)a (Ad ) (VI)
wherein L is an neutral Lewis base;
H is hydrogen;
(L-H)+is a Bronsted acid
Ad- is a non-coordinating anion having the charge d-
d is an integer from 1 to 3.
The ration component, (L-H)d+ may include Bronsted acids such as protons or
protonated Lewis bases or reducible Lewis acids capable of protonating or
abstracting a
moiety, such as an akyl or aryl, from the bulky ligand metallocene or Group 15
containing
transition metal catalyst precursor, resulting in a cationic transition metal
species.
The activating ration (L-H)a may be a Bronsted acid, capable of donating a
proton
to the transition metal catalytic precursor resulting in a transition metal
ration, including
ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, preferably
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ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-
methylaniline,
diphenylamine, trimethylamine, triethylamine, N,N- dimethylasuline,
methyldiphenylamine,
pyridine, p-bromo N,N-dimethylaniline, p-vitro-N,N-dimethylaniline,
phosphoniums from
triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from
ethers such
as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from
thioethers,
such as diethyl thioethers and tetrahydrothiophene and mixtures thereof. The
activating
cation (L-H)d+ may also be an abstracting moiety such as silver, carboniums,
tropylium,
carbeniums, ferroceniums and mixtures, preferably carboniums and ferroceniums.
Most
preferably (L-H)d+ is triphenyl carbonium.
The anion component Ad- include those having the formula ~M''~Q"]d- wherein k
is an
integer from 1 to 3; n is an integer from 2-6; n - k = d; M is an element
selected from Group
13 of the Periodic Table of the Elements and Q is independently a hydride,
bridged or
unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted
hydrocarbyl,
halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals,
said Q having
up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q
a halide.
Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 caxbon
atoms, more
preferably each Q is a fluorinated aryl group, and most preferably each Q is a
pentafluoryl
aryl group.
Most preferably, the ionic stoichiometric activator (L-H)a (Ad-) is N,N-
dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium
tetra(perfluorophenyl)borate.
Examples of suitable Ad- also include diboron compounds as disclosed in U.S.
Pat.
No. 5,447,895, which is fully incorporated herein by reference.
In one embodiment, an activation method using ionizing ionic compounds not
containing an active proton but capable of producing a bulky ligand
metallocene catalyst
cation and their non-coordinating anion are also contemplated, and are
described in EP-A- 0
426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein
incorporated
by reference.
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
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example, alumoxanes and ionizing activators in combinations, see for example,
EP-B 1 0
573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S. Patent Nos.
5,153,157 and 5,453,410 all of which are herein fully incorporated by
reference.
Other suitable activators are disclosed in WO 98/09996, incorporated herein by
reference, wluch describes activating bulky ligand metallocene 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)~4THF as an activator for a bulky ligand metallocene
catalyst compound.
WO 99/18135, incorporated herein by reference, describes the use of organo-
boron-
aluminum acitivators. 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 bulky ligand metallocene catalyst compound or precursor to a bulky
ligand
metallocene cation capable of polymerizing olefins. Other activators or
methods for
activating a bulky ligand metallocene catalyst compound are described in for
example, U.S.
Patent Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO 99/42467
(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)
benzimidazolide), which
are herein incorporated by reference.
Supports, Carriers and General Supporting Tecliniques
nThe above described catalyst and/or activators 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 to form a supported catalyst system. For example, catalysts)
and/or
activators) may be deposited on, contacted with, vaporized with, bonded to, or
incorporated within, adsorbed or absorbed in, or on, a support or carrier.
The terms "support" or "carrier", for purposes of this patent specification,
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
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supports, such as polystyrene divinyl benzene polyolefins or polymeric
compounds,
zeolites, talc, clays, or any other organic or inorganic support material and
the like, or
mixtures thereof.
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, magnesium
chloride, and mixtures thereof. Other useful supports include magnesia,
titania, zirconia,
montmorillonite (EP-B 1 0 511 665), phyllosilicate, 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.
It is preferred that the carrier, most preferably an inorganic oxide, has a
surface area
in the range of from about 10 to about 700 m2/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 ~,m.
More preferably, the surface area of the carrier is in the range of from about
50 to about 500
m2/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 ~,m. Most preferably the surface area of the Garner is
in the range is
from about 100 to about 400 m2/g, pore volume from about 0.8 to about 3.0 cc/g
and
average particle size is from about 5 to about 100 ~,m. The average pore size
of the carrier
of the invention typically has pore size in the range of from 10 to 1000,
preferably 50 to
about SOON, and most preferably 75 to about 3501.
Examples of supporting bulky ligand metallocene catalyst systems are described
in
U.S. Patent 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 Serial Nos. 271,598 filed July 7, 1994 and
788,736
filed January 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO
96/06187
and WO 97/02297, and EP-B 1-0 685 494 all of which are herein fully
incorporated by
reference.
There are various other methods in the art for supporting the polymerization
catalysts. For example, the bulky ligand metallocene catalyst compound may
contain a
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polymer bound ligand as described in U.S. Patent Nos. 5,473,202 and 5,770,755,
which is
herein fully incorporated by reference, or may be spray dried as described in
U.S. Patent
No. 5,648,310, which is herein fully incorporated by reference. The support
used with the
bulky ligand metallocene catalyst system of the invention may be
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 may be selected as
described in U.S.
Patent No. 5,688,880, which is herein fully incorporated by reference.
In another embodiment, an antistatic agent or surface modifier, that is used
in the
preparation of the supported catalyst system as described in PCT publication
WO 96/11960,
which is herein fully incorporated by reference, may be used. The catalyst
system may be
prepared in the presence of an olefin, for example hexene-1.
In another embodiment, catalyst may 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, oleatP.s and cyclohexylbutyrates, as described
in U.S.
Application Serial No. 09/113,216, filed July 10, 1998.
A preferred method for producing a supported bulky ligand metallocene catalyst
system is described below, and is described in U.S. Application Serial Nos.
265,533, filed
June 24, 1994 and 265,532, filed June 24, 1994 and PCT publications WO
96/00245 and
WO 96/00243 both published January 4, 1996, all of which are herein fully
incorporated by
reference. In this preferred method, the catalyst compound is slurried in a
liquid to form a
catalyst solution or emulsion. 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 compounds and/or activator. In the most
preferred
embodiment the liquid is a cyclic aliphatic or aromatic hydrocarbon, most
preferably
toluene. The catalyst compound and activator solutions are mixed together
heated and
added to a heated porous support or a heated porous support is added to the
solutions such
that the total volume of the bulky ligand metallocene catalyst compound
solution and the
activator solution or the bulky ligand metallocene catalyst compound 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.
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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 limes, Total Porosity and
Particle
Density of Fluid Catalysts By Liquid TitYation, Vol. 28, No. 3, Analytical
Chemistry 332-
334 (March, 1956).
Diene
The addition of a low concentration of diene, is utilized in the
polymerization
processes, preferably in the gas phase polymerization processes, of the
invention to improve
product processability. Dimes, as is known in the art, belong to the class of
unsaturated
hydrocarbons that contain two carbon-carbon double bonds, and are classified
as cumulated,
conjugated, or isolated according to whether the double bonds constitute a CCC
unit, a CC-
CC unit, or a CC-(CXY)n-CC unit, respectively. In the present invention, a low
level of
dime is introduced into the reactor to control and improve the polymer
product's melt index
ratio independently of the products melt index and density, and is believed to
independently
control long chain branching without gel formation.
Any diene, or mixtures of dimes, containing enough carbon atoms to incorporate
long chain branching may be utilized in the process of the invention.
Preferably, the dime
does not act as a poison to the catalyst, or undergo cyclization which would
prevent further
chain growth. The diene(s) utilized may be aliphatic, alicyclic or aromatic
and is preferably
aliphatic. More preferably, the dime is an aliphatic linear dime contaiung non-
conjugated
double bonds and most preferably containing isolated double bonds. To
facilitate long
chain branching, it is most preferable that both of the double bonds of the
diene(s) be able
to react and insert into growing polymer chains.
For use in gas phase polymerization processes, the dime's vapor pressure and
boiling point must be such as to allow sufficient dispersion within the
reactor. Failure of
the dime to disperse well will result in gel formation and will also present
problems in
down stream product purging. Tn addition, diene(s) most suitable for use in
the gas phase
processes of the invention should not possess a strong odor. Therefore, it is
preferable that
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the diene(s) is an aliphatic linear or branched dime having 5 to 12 carbon
atoms and
preferably 6 to I O carbon atoms. Examples of suitable dimes useful in the
process of the
invention include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene,
1,7-
octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene and mixtures
thereof. In an
especially preferred embodiment the dime is a a,c~-diene or one that contains
double bonds
at both ends. More preferably the diene comprises 1,7-octadiene, I,8-nonadiene
or I,9-
decadiene and most preferably comprises 1,7-octadiene.
Any amount of diene or mixture of dimes effective to produce LCB and/or to
enhance the shear thinning property of bulky ligand metallocene catalyzed
polymer
products may be utilized. Preferably, in gas phase polymerization processes,
the amount of
dime utilized is from about 1 to about 1000ppm of dime based upon the total
weight of
monomer feed to the process, or about 0.255 to about 255 ppm of dime based on
total
moles of monomer feed. Total weight or moles of monomer feed means the weight
or
moles of the monomer utilized, for example ethylene, and does not include the
weight or
moles of comonomer. More preferably the amount of dime utilized is from about
10 to
about 900ppm weight or about 2.55 to about 229.5 ppm molar, more preferably
from about
15 to about 850ppm weight or about 3.82 to about 216.4 ppm molar , more
preferably from
about 20 to about 800ppm weight or about 5.1 to about 203.6 ppm molar, more
preferably
from about 50 to about 750ppm weight or about 12.7 to about 191 ppm molar,
more
preferably from about 100 to about 700ppm weight or about 25.5 to about 178.2
ppm molar
and most preferably from about 150 to about 650ppm weight or about 38.2 to
about 165.5
ppm molar dime.
Polymerization Process
The addition of dime to control polymer product processability may be utilized
in
any prepolymerization and/or polymerization process. The polymerization may be
conducted in solution, gas phase, slurry phase or in a high pressure process
or a
combination thereof. Preferred is a gas phase or slurry phase polymerization
of one or more
olefins at least one of which is ethylene or propylene. Most preferably,
polymerization is
conducted in a gas phase polymerization process.
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In the process of the invention, the diene(s) must be properly dispersed
within the
reactor. Proper dispersion of dime reduces the possibility of gel formation
and allows for
uniform incorporation of LCB and control of the polymer product's MIR
independent of its
MI and density. For example, at the same MI and density, it has been found
that MIR
increases with increasing diene level and the product possesses melt strength
similar to the
product prepared without dime addition. Therefore, without wishing to be
limited by
theory, it is believed that the addition of dime generates LCB, which appears
to be a star
type of branch, since there is significant enhancement in shear thinning and
little increases
in melt strength of the polymer products.
Preferably, the dime is dissolved in a suitable solvent, for example hexane or
iso-
pentane, to form a dime solution which is then introduced into the reactor.
More
preferably, the introduction of dime and/or dime solution into the reactor is
independently
controlled and may be introduced into the reactor by any suitable means as is
known in the
art. By controlling the reactor dime level, the LCB present in bulky ligand
metallocene
catalyzed polymer products may be controlled. Most preferably, and to achieve
maximum
dime dispersion, a controlled amount of the dime or dime solution is first
introduced to the
comonomer, the inducing condensing agent (ICA) feed, and/or other feeds which
are known
in the axfi, before entering the reactor.
In one embodiment, the process of this invention is directed toward utilizing
a low
level of diene(s) in polymerization or copolymerization reactions involving
the
polymerization of one or more olefin monomers having from 2 to 30 carbon
atoms,
preferably 2 tol2 carbon atoms, and more preferably 2 to 8 caxbon atoms. The
invention is
particularly well suited to the polymerization of two or more olefin monomers
of ethylene,
propylene, butene-l, pentene-1, 4-methyl-pentene-1, hexene-1, octene-l and
decene-1, 3-
methyl pentene-1, 3,5,5-trimethyl-hexene-1 and cyclic olefins or combinations
thereof.
Other monomers useful in the polymerization process of the invention include
ethylenically
unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or
nonconjugated
dimes, polyenes, vinyl monomers and cyclic olefins. Other monomers useful in
the
invention may include norbornene, norbornadiene, isobutylene, isoprene,
vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene
norbornene,
dicyclopentadiene and cyclopentene.
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In a preferred embodiment the process of this invention is directed toward
utilizing a
low level of diene(s) to produce a copolymer of ethylene, 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 polymerization process.
In another embodiment of the process of the invention, a low level of diene(s)
is
utilized when ethylene or propylene is polymerized with at least two different
comonomers,
to form a terpolymer.
In one embodiment, the invention is directed to utilizing a low level of
diene(s) in a
polymerization 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.
Polypropylene polymers may be produced using the particularly bridged bulky
ligand
metallocene catalysts as described in U.S. Patent Nos. 5,296,434 and
5,278,264, both of
which are herein incorporated by reference.
1 S In a preferred embodiment ethylene and optionally a comonomer, and the
dime
compound are contacted with an effective amount of bulky ligand metallocene
catalyst, as
described above, at a temperature and pressure sufficient to initiate
polymerization. In a
typically 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. Patent 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.)
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The reactor temperature in a gas phase process may vary from about 30°C
to about
120°C, preferably from about 60°C to about 115°C, more
preferably in the range of from
about 70°C to 110°C, and most preferably in the range of from
about 70°C to about 95°C.
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).
The productivity of the catalyst or catalyst system is influenced by the main
monomer partial pressure. The preferred mole percent of the main monomer,
ethylene or
propylene, preferably ethylene, is from about 25 to 90 mole percent and the
monomer
partial pressure is in the range of from about 75 Asia (517 kPa) to about 300
psia (2069
kPa), which are typical conditions in a gas phase polymerization process.
In a preferred embodiment, the reactor utilized in the process of the present
invention is capable of 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 lbslhr (29,000 Kg/hr) to
greater than
100,000 lbs/hr (45,500 Kg/hr).
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. Patent Nos. 5,627,242, 5,665,818
and
5,677,375, and European publications EP-A- 0 794 200 EP-B 1-0 649 992, EP-A- 0
802 202
and EP-B- 634 421 all of which are herein fully incorporated by reference.
A preferred process of the invention is where the process is operated in the
presence
of a bullcy ligand metallocene catalyst system 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. Patent
No.
5,712,352 and 5,763,543, which are herein fully incorporated by reference.
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In one embodiment of the invention, olefin(s), preferably C2 to C30 olefins)
or
c
alpha-olefm(s), preferably ethylene or propylene or combinations thereof are
prepolymerized 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. Patent 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.
Optionally, unreacted dime may be removed from the polymer product by methods
known in the art such as, for example, purging with an inert gas, such as
nitrogen, purging
with and inert gas and water vapor or oxygen, by heating under vacuum or
combinations
thereof.
Polymer Products
The polymers produced by the process of the invention can be used in a wide
variety
of products and end-use applications and may include linear low density
polyethylene,
elastomers, plastomers, high density polyethylenes, medium density
polyethylenes, low
density polyethylenes, polypropylene and polypropylene copolymers.
The polymers of the present invention, preferably ethylene based polymers,
have a
melt index (MI) or (I2) as measured by ASTM-D-1238-E in the range of from Iess
than 0.01
dg/min to 1000 dg/rnin, more preferably from about less than 0.01 dg/min to
about 100
dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and
most
preferably from about 0.1 dg/min to about 10 dg/min.
The polymers of the invention in a preferred embodiment have a melt index
ratio
(I21/IZ) ( IZ, is measured by ASTM-D-1238-F) of from preferably greater than
10, more
preferably greater than 30, even more preferably greater that 40, still even
more preferably
greater than 50 and most preferably greater than 65. In one embodiment, the
polymer of the
invention may have a narrow molecular weight distribution and a broad
composition
distribution or vice-versa, and may be those polymers described in U.S. Patent
No.
5,798,427 incorporated herein by reference.
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The polymers of the invention, typically ethylene based polymers, have a
density in
the range of from 0.86g/cc to 0.97 g/cc, preferably in the range of from 0.88
g/cc to 0.965
g/cc, more preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more
preferably in
the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the
range from 0.910
g/cc to 0.940 g/cc, and most preferably greater than 0.915 g/cc, preferably
greater than
0.920 g/cc, and most preferably greater than 0.925 g/cc. Density is measured
in accordance
with ASTM-1505.
In another embodiment the polymer produced herein has a melt strength of 7 cN
or
more, preferably 9 cN or more, more preferably 10 cN or more, and even more
preferably
12 cN or more, as measured with an Instron capillary rheometer in conjunction
with the
Goettfert Rheotens melt strength apparatus. A polymer melt strand extruded
from the
capillary die is gripped between two counter-rotating wheels on the apparatus.
the take up
speed is increased at a constant acceleration of 24 mmlsec2, which is
controlled by the
Acceleration Programmer (Model 45917, at a setting of 12). The maximum pulling
force
(in cN) achieved before the strand breaks or starts to show draw resonance is
determined as
the melt strength. The temperature of the rheometer is set at 190°C.
The capillary die has a
length of one inch (2.54 cm) and a diameter of 0.06 inch( 0.15 cm). The
polymer melt is
extruded from the die at a piston speed of 3 inch/min (7.62 cm/min). The
distance between
the die exit and the wheel contact point should be 3.94 inches (100 mm).
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 (MW/Mn) of greater than 1 to about 40, preferably greater than 1.5 to
about 15, more
preferably greater than 2 to about 10, most preferably greater than about 2.0
to about 8.
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 February 18, 1993,
which is
fully incorporated herein by reference.
The polymers of the invention in one embodiment have CDBI's generally in the
range of greater than 50% to 100%, preferably 99%, preferably in the range of
55% to 85%,
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and more preferably 60% to 80%, even more preferably greater than 60%, still
even more
preferably greater than 65%.
In another embodiment, polymers produced by the process of the invention have
a
CDBI less than 50%, more preferably less than 40%, and most preferably less
than 30%.
In yet another embodiment, propylene based polymers are produced in the
process
of the invention. These polymers include atactic polypropylene, isotactic
polypropylene,
hemi-isotactic and syndiotactic polypropylene. Other propylene polymers
include
propylene block or impact copolymers. Propylene polymers of these types are
well known
in the art see for example U.S. Patent Nos. 4,794,096, 3,248,455, 4,376,851,
5,036,034 and
5,459,117, all of which are herein incorporated by reference.
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 produced via conventional Ziegler-Natta and/or bulky ligand
metallocene
catalysis, elastomers, plastomers, high pressure low density polyethylene,
high density
polyethylenes, polypropylenes and the like.
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, inj ection 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. Particularly preferred methods to form the polymers
into films
include extrusion or coextrusion on a blown or cast film line. 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, 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.
In another embodiment, the films produced in the process of the invention may
further contain additives such as slip, antiblock, antioxidants, pigments,
fillers, antifog, W
stabilizers, antistats, polymer processing aids, neutralizers, lubricants,
surfactants, pigments,
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dyes and nucleating agents. Preferred additives include silicon dioxide,
synthetic silica,
titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearates,
calcium
stearate, zinc stearate, talc, BaS04, diatomaceous earth, wax, carbon black,
flame retarding
additives, low molecular weight resins, hydrocarbon resins, glass beads and
the like. The
additives may be present in the typically effective amounts well known in the
art, such as
0.001 weight % to 10 weight %.
EXAMPLES
In order to provide a better understanding of the present invention including
representative advantages thereof, the following examples of polymerization
processes and
their polymerization results, are offered.
The examples were run in a continuous gas phase fluidized bed reactor. Ten
polyethylene polymer products were produced at 6 different dime levels. The
process run
conditions averaged over a period of time at steady state appear in Table I,
and the
characteristics of each run's polymer product appear in Table 2. Data obtained
from
comparative example 1b and from four polymer products, which were further
processed
into film, appears in Tables 3-6. The amount of dime is reported in ppm based
upon the
total weight of monomer feed as described above.
Comparative Example 1 (2MI/0.920D)
Before dime was introduced into the reactor, a control run, for 2MI/0.920D
condition, was performed to establish a baseline. After stable operation for
7.2 Bed Turn
Over's (BTO) and collecting one box of product, the tetraethylaluminium (TEAL)
pump
was flushed with hexane into the reactor. As used herein, BTO (production/bed
weight)
means the replacement, over time as polymer is being continuously produced and
withdrawn from the reactor, the amount of product the reactor may contain at
any one time
(about 3001bs (136 kg) in the present examples). In addition, as used herein,
one box of
product means about 600 to 800 pounds (about 272 to 363 kg) of polymer. Due to
residual
TEAL being flushed into the reactor and to some bed weight control problems,
the reactor
was killed at 12.3 BTO's due to a product discharge line plug. Catalyst,
dimethylsilyl-
bis(tetranydroindenyl) zirconium dichloride, was cut briefly to stabilize the
reactor. Catalyst
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productivity averaged 3,650 g/g (where g/g is g polymer/g catalyst) on
2.23MI/0.918D
condition.
Comparative Example 1b (Second Startup)
The reactor was restarted on 2MI/0.920D condition after the shut down. There
were
no reactor continuity problems and reactor stayed on this condition for
5.8BTOs. Catalyst
productivity averaged 3,366 g/g.
Example 2 (2MI/0.920D, 50ppm Diene)
After stabilized on the 2MI/0.920D control condition, the reactor was
transitioned to
a SOppm dime condition by starting a 1% 1,7-octadiene solution in hexane using
the TEAL
pump. Diene was on flow ratio control to ethylene feed to maintain SOppm dime
to
ethylene weight ratio. Hydrogen concentration and hexene flow ratio was held
constant at
the 2MI control condition. The reactor was lined out at 1.SMI with SOppm diene
and one
box of product was collected. The dime SOppm condition was run for 5.6 BTO
with
4,130g/g average productivity.
Example 3 (2MI/0.920D,100ppm Diene)
After finishing the SOppm condition (Example 2), the reactor was transitioned
to a
100ppm condition by increasing the dime flow rate while keeping hydrogen and
hexene
concentration constant. Bed weight still fluctuated and the reactor was killed
at 2.SBT0
due to product discharge plug. Catalyst productivity was about 3,850g/g before
shutdown.
Comparative Example Ic (Third Startup)
The reactor was restarted with the control condition (2MI/0.920D) and ran for
4.~BT0's without any skin temperature activity or chip formation. Catalyst
productivity
was between 3,300 to 3,600g/g. Product MIR was 34 at 1.93MI/0.9178D.
Example 4 (1MI/0.920D 150ppm diene)
After stabilizing the reactor on 2MI/0.920D condition, the reactor was
transitioned
to a 150ppm condition by starting dime flow and increasing hydrogen
concentration from
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950 to 1000ppm. Catalyst productivity was about 3,750 g/g. One box of product
was
collected with 50.9 MIR at 0.95MI/0.9181D.
Example 5 (0.75MI/0.920D 150ppm diene)
Reactor hydrogen was lowered to 950ppm to get 0.75MI product at 150ppm dime
level. There were no continuity problems. ' Average catalyst productivity was
3,650g/g.
One box of product was collected with 54.73 MIR at 0.82MI/0.9179D.
Example 6 (1MI/0.920D 250ppm diene)
The reactor was transitioned to a 250ppm dime condition by increasing dime
feed.
The dime solution concentration was increased to 8% to maintain pump speed
between 200
to 400 cc/hr. Hydrogen level was increased to 1075ppm from 950ppm to
compensate for
increasing dime level. The reactor was on this condition for 4.47BT0 and one
box of
product collected with 55.53 MIR at l.OlMI/0.9200D.
Example 7 (0.75MI10.920D 250ppm dime)
Hydrogen concentration was reduced from 1,075 PPM to 1,OOOppm to get 0.75MI
product at 250ppm diene. Catalyst productivity averaged 3,400 g/g. One box of
product
was collected with 60.03MTR at 0.86MI/0.9205D.
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Example 8 (0.75MI/0.920D 400 ppm diene)
The reactor was transitioned to a 400ppm condition by increasing dime flow at
1,OOOppm hydrogen. After MI drifted down to 0.56, hydrogen was raised to 1,100
ppm and
MI started to come back to 0.71. However, the dime solution ran out for 2
hours. MI
responded quickly to dime lose, jumping from 0.71 to 1.41 and finally to 1.67.
MI
eventually settled down to 0.75g/lOmin at 1075ppm hydrogen when the dime
solution was
put back on line. This incidence demonstrated the ability of dime to couple
chains and
lower MI. Average catalyst productivity was 3,850 g/g, and one box of product
was
collected with 74.71 MIR at 0.75MI/0.9206D.
Example 9 (0.75MI/0.920D 600ppm dime)
The reactor was transitioned from the 400 ppm to a 600 ppm diene condition by
increasing dime flow and raising hydrogen level to 1,200 ppm. Hydrogen level
was further
raised to 1,300 ppm to get to 0.75MI target. Average catalyst productivity was
3,400 g/g.
One box of product was collected with 82.09 MIR at 0.80MI/0.920D.
Example 10 (1MI/0.920D 600ppm dime)
Hydrogen level was further raised to 1,400ppm to target 1MI product. Due to
slow
MI response to hydrogen, hydrogen level was raised up to 1,500 ppm. This
apparently
overshot the hydrogen and MI climbed to 1.49 at one point and finally settled
around 1MI
at 1,350 ppm hydrogen. Average catalyst productivity was 3,800g/g. One box of
product
was collected with 75.12 MIR at 1.12MI/0.9218D.
Reactor Continuity
Reactor continuity was fairly good throughout the example runs. There were no
skin temperature excursion and no major sheeting incidence. Some small chips
came out
occasionally, but the amount was small (0.1-0.2% of product) and did not cause
major
continuity disruptions. There were two shutdowns in the beginning part of the
run, but
none of them were directly related to dime injection. The first shutdown
occurred before
dime condition and was caused by residual tetraethylaluminum (TEAL) being
flushed out
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and by bed weight control problems. The second shutdown happened at the 100ppm
dime
condition and was probably caused by the bed weight control problem. Most of
the
conditions (7) were finished after the third startup and the run was completed
with a
scheduled shutdown. Upon completion of the run, the reactor and cooler were
opened for
inspections and were found clean. Some coating formed on the expanded section
wall and
was easily blown off.
Catalyst Productivity
Catalyst productivities were between 3,SOOg/g to 4,OOOg/g and there was no
major
activity loss with diene. Actually, all the dime run activities were higher
than the control
run at beginning of the dime run, which may have been caused by a difference
in catalyst
batches.
Gels
Gel formation is a major concern especially if the polymer is to be utilized
in the
production of film. In the preceding examples, the diene solution was
dispersed into hexene
feed before it entered the reactor to achieve good dispersion. Extra care was
taken during
the run to avoid getting into the gel region too quickly since it may take a
long time for gels
to clear up. Gel tape was run at each condition to help deciding next dime
level. As shown
in Table 2, gel level was at baseline up to 400ppm dime. At 600 ppm, some
partially
melted gel particles showed up on gel tape. However, after the granules were
compounded
and pelletized with a twin-screw extruder, the tape was virtually gel free.
Since there was
only about 0.1 dime per chain even at 600ppm level, the partially melted gels
were likely
caused by non-uniform dispersion of dime in gas phase, which could be
minimized with
better dime dispersion.
Purging and Odor Issues
Diene level during the run was monitored for any exposure and/or odor issues.
Compared to
aromatic dimes (ethylidene norbornene (ENB), etc.), the aliphatic dime used
did not have a
noticeable odor during processing. In addition, using normal gas phase reactor
purging
practices, the polymer product had no noticeably odor, and no dime was
detected by
headspace gas chromatograph analysis of the 600ppm dime run granular product.
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Product Processibility
Eight products were pelleted by a twin screw extruder with a standard additive
package as is known in the art. The MI of the pellets, however, was higher
than that of
granules with the difference increasing with increasing diene level. This
difference was
likely caused by a lack of homogeneousness in the melt indexer when measuring
the
granule MI. The pellet MI was used in characterizing film product. Table 3
lists the
characterization results of the pelleted dime products. As diene level
increased from 0 to
600 ppm, there was significant increase in weight (MW) and the Z-averaged
molecular
weight (MZ) measured by light-scattering and viscometer detectors, as is known
in the art,
even though number average molecular weight (M~ was roughly the same or even
smaller.
While not wishing to be limited by theory, it is thought that since light
scattering and
viscometer detectors are more sensitive to the high MW fraction, dime re-
incorporation
mostly likely occurred in the high MW portion.
Pellet products from representative examples (1b, 5, 7, 8, 9) were further
blown into
1 mil film using a blown film Line. A control standard with same MI/density
produced in a
commercial reactor with the same catalyst was run under the same conditions.
Table 4
compares dime product processability at standard output rate (188 lb/hr or
85.3 kg/hr) on a
pilot scale blow film line. At the same MI and density (1MI/0.920D), product
processability improves with increasing dime level. Comparing the 400ppm dime
product
with the control, motor load decreases from 51.6% to 41.7%, die press
decreases from 3460
to 2710 psi (23856 to 18685 kPa), melt temperature decreases from 378°F
(192.2°C) to 369
°F (187.2°C). Specific output increases from 11.79 to 13.96
lb/hr (5.35 to 6.33 kg/hr).
Table 5 compares maximum output rates of the different diene products. Since
the
extruder was not powder limited, the maximum rate was primarily determined by
bubble
stability. At the maximum output rate, melt temperature and pressure decreased
from
385°F (196 °C) and 4440 psig (30613 kPa) for the control
standard to 374°F (190 °C) and
2340 psig (15918 kPa) for the 400ppm dime sample, indicating significant
shearing with
increasing diene level. The maximum output rate is obtained at 400ppm diene
level, 323
Ib/hr (147 kg/hr) compared with 294 lb/hr (I33 kg/hr) for the control.
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Film Properties
Table 6 compares product characteristics of films produced at 188 lb/hr (85.3
kg/hr)
output rate. The best balance of processibility and film properties seem to be
achieved from
about 250ppm to about 400ppm dime. At 250ppm dime, the processibility
increases by 20
to 25% as measured by maximum rate, specific output (lb/hp-hr), motor load,
head pressure
and melt temperature. Overall film properties of the 250ppm dime product are
similar to
the control without diene. Film hardness is basically the same as control
(MD/TD modulus,
MD/TD yield). Fihn toughness (MD/TD tensile, puncture force/energy) and film
IO appearance(haze and gloss) are also similar to control standard. Dart
impact of 250ppm
dime product is slightly better than control (10%). MD and TD tear of the
250ppm diene
product is somehow defensive to the control. By changing dime level, product
processibility can be significantly enhanced without comprising most of the
film properties.
I S Conclusion
By using small amount dime, shear thinning property of bulky ligand
metallocene
catalyzed polymer products were enhanced by 50-100% without major impact on
process
continuity or catalyst productivity. The process provides a new means of
controlling
product LCB by controlling reactor diene level, and may be utilized to broaden
the product
20 window of existing bulky ligand metallocene catalyst. The process of the
invention
enlarges product property control from the traditional two dimensions (MI and
density) to
three dimensions (MI, density and LCB). For example at the same MI and
density, it has
been found that MIR increases with increasing dime level. At 250-600 ppm dime,
MIR
increases by 50-100% when compared to the product made without dime. For
instance,
25 MIR of 1MI/0.920D product increases from 38.2 without dime to 63.2 with
400ppm (wt)
dime. Product processibility improves with increasing dime level as measured
by specific
out put, pressure drop and melt temperature. Product melt strength is similar
to the product
prepared without dime addition. Most film properties (hardness, toughness and
dart impact)
are similar to control and MD/TD tear is defensive to control.
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Table 1. Diane Run Process Conditions
Example # Comparative Comparative 2
1a 1b
Description No diene No diene 50ppm diene
BTO's 12.28 5.80 5.63
Catalyst Data
Catalyst Dimethylsilyl-same same
bis(tetrahydroindenyl)
zirconium dichloride
Cat Bulk Den (g/cc) 0.330 0.330 0.330
Feeder Efficiency 1.000 1.000 1.000
Cat Feed (sacs) 20 17 20
Cat Prod AI (ppm) 4609 2836 3909
Cat Prod Zr (ppm) 4760 3008 3871
Cat Prod (matt Bal) 3,650 3,366 4,130
QC Lab Data
MI (1Z g/l0min) 2.23 1.58 1.49
MIR (IZi/IZ) 36.55 37.39 40.22
Density (g/cc) 0.9184 0.9189 0.9193
Bulk Density (g/cc) 0.4481 0.4381 0.4618
APS (microns) 794.1 701.2 843.2
COV (%) 44.7 42.8 40.5
PSD <250N (%) 3.70 5.25 3.60
PSD <125N (%) 0.90 1.25 1.20
Pan (%) 0.10 0.15 0.40
Flow Time (sec) 7.43 7.45 7.54
MCL Data
Ash (ppm) 220 353 232
Zr by ICPES (ppm) 0.6933 1.0970 0.8526
AI by ICPES (ppm) 25.21 40.97 29.73
Process Data
Prod Rate Ibs/hr 81.0 (36.7) 66.6 (30.2) 87.3 (39.6)
(Kg/hr)
Hydrogen (ppm) 927.2 927.6 52.8
Ethylene (mole%) 70.0 70.0 70.1
Hexane (mole%) 0.74 0.70 0.63
Ethylene Partial 220.4 (1520) 219.6 (1514) 220.5 (1520)
Pressure psia (kPa)
H2/C2 Conc Ratio 13,24 13.28 13.57
(mole %)
C6/C2 Conc Ratio ' 0.0110 0.0100 0.0089
(mole %)
C6/C2 Flow Ratio 0.0765 0.0700 0.0701
(Ib/Ib)
Temperature F (C) 185.0 (85.0) 185.1 (85.1) 184.9 (84.9)
Bed Weight Ibs (Kg) 298.0 (135.2) 297.9 (135.1) 362.5 (164.4)
Residence Time (hrs)3.71 4.52 4.77
Gas Velocity ft/sec 2.25 (0.686) 2.25 (0.686) 2.25 (0.686)
(m/sec)
Corr. Plate dP inch 16.2 (41.1) 16.4 (41.6) 15.8 (40.1)
H20 (cm Hz0)
Corr. Cooler dP psig17.95 (124) 17.35 (120) 17.82 (123)
(kPa)
RX Pressure psig 300.0 (2068) 300.0 (2068) 300.0 (2068)
(kPa)
C2 Feed Ib/hr (Kg/hr)122.9 (55.4) 106.7 (48.4) 130.5 (59.2)
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Table 1. Diene Run Process Conditions Continued
Example # 3 Comparative 4
1c
Description 100ppm diene No diene 150ppm diene,
1M1
BTO's 2.50 4.81 2.96
Catalyst Data
Catalyst Type Dimethylsilyl-same Same
bis(tetrahydroindenyl)
zirconium dichloride
Cat Bulk Den (g/cc) 0.330 0.330 0.330
Feeder Efficiency 1.000 1.000 1.000
Cat Feed (sets) 18.3 17.3 19.0
Cat Prod AI (ppm) 3785 2912 3637
CatProd Zr(ppm) 3991 3008 3880
Cat Prod (matt Bal) 4,178 3,793 3,733
QC Lab Data
MI (1Z g/10min) 1.36 1.93 0.95
MIR (121/12) 41.97 34.09 50.90
Density (g/cc) 0.9196 0.9178 0.9181
Bulk Density (g/cc) 0.4595 0.4265 0.4578
APS (microns) 805.3 738.6 794.4
COV (%) 41.500 43.000 42.2
PSD <250u (%) 3.20 5.10 2.60
PSD <125u (%) 0.80 1.50 1.10
Pan (%) 0.20 0.40 0.10
Flow Time (sec) 7.54 7.38 7.29
MCL Data
Ash (ppm) 271 377 288
Zr by ICPES (ppm) 0.8268 1.0970 0.8505
AI by ICPES (ppm) 30.70 39.90 31.95
Process Data
Prod Rate Ibs/hr 76.5 (34.7) 73.1 (33.2) 72.1 (32.7)
(Kg/hr)
Hydrogen (ppm) 947.3 948.5 950.8
Ethylene (mole%) 69.75 69.73 70.0
Hexene (mole%) 0.64 0.74 0.74
Ethylene Partial 218.54 (1507) 219.37 (1513) 220.8 (1522)
Pressure psia (kPa)
H2/C2 Conc Ratio 13.5800 13.6000 13.58
(mole %)
C6/C2 Conc Ratio 0.0092 0.0106 0.0105
(mole %)
C6/C2 Flow Ratio 0.0699 0.0694 0.0700
(Ib/Ib)
Temperature F (C) 184.8 (84.9) 185.1 (85.1) 185.0 (85.0)
Bed Weight Ibs (Kg) 314.16 (142.7)297.81 (135.1 300.5 (136.3)
)
Residence Time (hrs)4.47 4.12 4.36
Gas Velocity ft/sec 2.3 (0.701 2.3 (0.701 ) 2.25 (0.686)
(m/sec) )
Corr. Plate dP inch 15.93 (40.5) 15.53 (39.4) 15.5 (39.4)
Ha0 (cm H20)
Corr. Cooler dP psig17.8 (123) 17.4 (120) 17.79 (123)
(kPa)
RX Pressure psig 300.0 (2068) 300.0 (2068) 300.0 (2068)
(kPa)
C2 Feed Ib/hr (Kg/hr)118.23 (53.6) 128.84 (58.4) 122.7 (55.7)
I I
CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
-3 6-
Table 1. Diene Run Process Conditions Continued
Example # 5 6 7
Description 150ppm diene, 250ppm diene, 250ppm diene,
0.75M1 1M1 0.75M1
BTO's 2.83 4.47 5.82
Catalyst Data
Catalyst Type Dimethylsilyl-same same
bis(tetrahydroindenyl)
zirconium dichloride
Cat Bulk Den (glcc) 0.330 0.330 0.330
Feeder Efficiency 1.000 1.000 1.000
Cat Feed (sets) 18 18 18
Cat Prod AI (ppm) 3545 3447 3276
Cat Prod Zr (ppm) 3720 3412 3435
Cat Prod (matt Bal) 3,268 3,964 3,774
Cat Prod (ash) 3,288 3,056
QC Lab Data
MI (g/l0min)
0.82 1.01 0.86
MIR (HLMI/MI) 54.73 55.53 60.03
Density (g/cc) 0.9179 0.9200 0.9205
Bulk Density (g/cc) 0.4610 0.4743 0.4720
APS (microns) 737.5 742.8 742.9
COV (%) 43.700 43.4 44.200
PSD ~250N (%) 4.10 4.90 4.00
PSD <125N (%) 1.00 0.70 0.70
Pan (%) 0.10 0.10 0.10
Flow Time (sec) 7.61 7.16 7.15
MCL Data
Ash (ppm) 291 362 298
Zr by ICPES (ppm) 0.8871 0.9672 0.9607
AI by ICPES (ppm) 32.78 33.71 35.47
Process Data
Prod Rate Ibs/hr 67.3 (30.5) 81.7 (37.1) 77.8 (35.3)
(Kg/hr)
Hydrogen (ppm) 958.3 960.2 960.2
Ethylene (mole%) 69.110 69.140 69.140
Hexene (mole%) 0.698 0.697 0.697
Ethylene Partial 217.48 (1499) 217.6 (1500) 217.57 (1500)
Pressure psia (kPa)
H2/C2 Conc Ratio 13.87 13.89 13.8900
(mole %)
C6/C2 Conc Ratio 0.0101 0.0101 0.0101
(mole %)
C6/C2 Flow Ratio 0.0705 0.0669 0.0669
(Ib/Ib)
Temperature F (C) 184.9 (84.9) 185.0 (85.0) 185.0 (85.0)
Bed Weight Ibs (Kg) 297.74 (135.1)300.6 (136.4) 297.95 (135.1)
Residence Time (hrs)4.57 3.70 3.88
Gas Velocity ft/sec 2.3 (0.701 2.25 (0.686) 2.3 (0.701 )
(m/sec) )
Corr. Plate dP inch 14.91 (37.9) 14.9 (37.8) 14.92 (37.9)
H20 (cm HZO)
Corr. Cooler dP psig17.87 (123) 17.87 (123) 17.87 (123)
(kPa)
RX Pressure psig 300.0 (2068) 300.0 (2068) 300.0 (2068)
(kPa)
~2 Feed Ib/hr (Kg/hr)123.1 (55.8) 122.7 (55.7) 114.32 (51.9)
I
CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
-3 7-
Table 1. Diene Run Process Conditions Continued
Example # 8 9 10
Description 400ppm diene, 600ppm diene, 600ppm diene,
0.75M1 0.75M1 1M1
BTO's 11.27 8.16 7.18
Catalyst Data
Catalyst Type Dimethylsilyl-same Same
bis(tetrahydroindenyl)
zirconium dichloride
Cat Bulk Den (g/cc)0.330 0.330 0.330
Feeder Efficiency 1.000 1.000 1.000
Cat Feed (sets) 18 20 20
Cat Prod AI (ppm) 3835 3473 3776
Cat Prod Zr (ppm) 3984 3346 3867
Cat Prod (matt Bal)3,344 3,366 3,337
Cat Prod (ash) 3,925 3,741
QC Lab Data
MI (g/10min) 0.75 0.80 1.12
MIR (HLMI/MI) 74.71 82.09 75.12
Density (g/cc) 0.9206 0.9200 0.9218
Bulk Density (g/cc)0.4774 0.4946 0.4945
APS (microns) 746.3 680.2 643.2
COV (%) 43.000 46.033 47.100
PSD <250N (%) 3.50 4.13 4.80
PSD <125N (%) 0.60 0.46 0.70
Pan (%) 0.10 0.10 0.10
Flow Time (sec) 6.96 6.74 6.62
MCL Data
Ash (ppm) 232 243 334
Zr by ICPES (ppm) 0.8284 0.9862 0.8533
AI by ICPES (ppm) 30.30 33.46 30.77
Process Data
Prod Rate Ibs/hr 68.9 (31.3) 31.3 (14.2) 61.9 (28.1 )
(Kg/hr)
Hydrogen (ppm) 960.2 1361.00 1384.0
Ethylene (mole%) 69.14 70.0 69.69
Hexene (mole%) 0.70 0.70 0.70
Ethylene Partial 217.57 (1500) 219.9600 (1517)218.98 (1510)
Pressure psia (kPa)
H2/C2 Conc Ratio 13.89 19.44 19.86
(mole %)
C6IC2 Conc Ratio 0.010 0.010 0.010
(mole %)
C6/C2 Flow Ratio 0.067 0.067 0.068
(Ib/Ib)
Temperature F (C) 185.0 (85) 185.00 (85) 184.8 (84.9)
Bed Weight Ibs (Kg)287.67 (130.5)295.25 (133.9)298.89 (135.6)
Residence Time (hrs)4.22 4.81 4.87
Gas Velocity ft/sec2.25 (0.686) 2.25 (0.686) 2.3 (0.701 )
(m/sec)
Corr. Plate Dp inch14.92 (37.9) 15.2 (38.6) 14.48 (36.8)
HZO (cm Hz0)
Corr. Cooler dP 17.78 (123) 17.14 (118) 14.04 (96.8)
psig (kPa)
RX Pressure psig 300.0 (2068) 300.0 (2068) 300.0 (2068)
(kPa) ~
C2 Feed Ib/hr (Kg/hr)104.00 (47.2) 100.34 (45.4) 100.55 (45.6)
CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
-38-
Table 2. Diene Run Products (Granular)
Ex. Diene MI MIR Density Gel Tape Gel Tape
(PPm) ~z) (Iznlz) (g/cc) (granule) (pellet)
1 0 2.0 36.55 0.9184 Baseline Baseline
2 50 1.49 40.22 0.9189 Baseline Baseline
3 100 1.36 41.97 0.9196 Baseline Baseline
4 150 0.95 50.90 0.9181 Baseline Baseline
150 0.825 54.73 0.9179 Baseline Baseline
6 250 1.01 55.53 0.9200 Baseline Baseline
7 250 0.86 60.03 0.9205 Baseline Baseline
8 400 0.75 74.71 0.9206 Few partially Almost baseline
melted gels
9 600 0.80 82.09 0.9200 Sorne partiallyAlmost baseline
melted gels
600 1.12 75.12 0.9218 Some partially Almost baseline
melted gels
CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
-39-
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CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
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CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
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CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
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CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
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CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
-44-
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CA 02400665 2002-08-16
WO 01/62808 PCT/USO1/03273
-45-
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,
more than one
dime may be added and/or more than one bulky ligand metallocene type catalyst
compound
may be utilized. For this reason, then, reference should be made solely to the
appended
claims for purposes of determining the true scope of the present invention.
