Note: Descriptions are shown in the official language in which they were submitted.
CA 2964598 2017-04-19
MEANS FOR INCREASING THE MOLECULAR WEIGHT AND DECREASING THE
DENSITY OF ETHYLENE INTERPOLYMERS EMPLOYING MIXED
HOMOGENEOUS CATALYST FORMULATIONS
BACKGROUND OF THE INVENTION
Solution polymerization processes are typically carried out at temperatures
that are
above the melting point of the ethylene homopolymer or copolymer product. In a
typical solution polymerization process, catalyst components, solvent,
monomers and
hydrogen are fed under pressure to one or more reactors.
For ethylene polymerization, or ethylene copolymerization, reactor
temperatures can
range from about 80 C to about 300 C while pressures generally range from
about
3MPag to about 45MPag. The ethylene homopolymer or copolymer produced
remains dissolved in the solvent under reactor conditions. The residence time
of the
solvent in the reactor is relatively short, for example, from about 1 second
to about 20
minutes. The solution process can be operated under a wide range of process
conditions that allow the production of a wide variety of ethylene polymers.
Post
reactor, the polymerization reaction is quenched to prevent further
polymerization, by
adding a catalyst deactivator. Optionally, if a heterogeneous catalyst
formulation is
employed in the third reactor, the deactivated solution is passivated, by
adding an acid
scavenger. The deactivated solution, or optionally the passivated solution, is
then
forwarded to polymer recovery where the ethylene homopolymer or copolymer is
separated from process solvent, unreacted residual ethylene and unreacted
optional
cc-olefin(s).
There is a need to improve the continuous solution polymerization process, for
example, to increase the' molecular weight of the ethylene interpolymer
produced at a
given reactor temperature. Given a specific catalyst formulation, it is well
known to
those of ordinary experience that polymer molecular weight increases as
reactor
temperature decreases. However, decreasing reactor temperature can be
problematic when the viscosity of the solution becomes too high. As a result,
in the
solution polymerization process there is a need for catalyst formulations that
produce
high molecular weight ethylene interpolymers at high reactor temperatures. The
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catalyst formulations and solution polymerization processes disclosed herein
satisfy
this need.
In the solution polymerization process there is also a need for catalyst
formulations
that are very efficient at incorporating one or more a-olefins into a
propagating
macromolecular chain. In other words, at a given [a-olefin/ethylene] weight
ratio in a
solution polymerization reactor, there is a need for catalyst formulations
that produce
lower density ethylene/a-olefin copolymers. Expressed alternatively, there is
a need
for catalyst formulations that produce an ethylene/a-olefin copolymer, having
a
specific density, at a lower (a-olefin/ethylene) ratio in the reactor feed.
Such catalyst
formulations efficiently utilize the available a-olefin and reduce the amount
of a-olefin
in solution process recycle streams.
The catalyst formulations and solution process disclosed herein, produce
unique
ethylene interpolymer products that have desirable properties in a variety of
end use
applications, for example applications that employ ethylene interpolymer
films. Non-
limiting examples of desirable film properties include higher film stiffness,
higher film
tensile yield, higher film tear resistance, lower hexane extractables, lower
seal
initiation temperature and improved hot tack performance. Films prepared from
the
ethylene interpolymer products, disclosed herein, have these desirable
properties.
SUMMARY OF THE INVENTION
One embodiment of this disclosure is an ethylene interpolymer product
comprising: (i)
a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii)
optionally a
third ethylene interpolymer: where the ethylene interpolymer product has a
dimensionless Long Chain Branching Factor (LCBF) greater than or equal to
about
0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium, and; from about
0.006
ppm to about 5.7 ppm of titanium.
Additional embodiments of this disclosure include ethylene interpolymer
products
comprising: (i) a first ethylene interpolymer; (ii) a second ethylene
interpolymer, and;
(iii) optionally a third ethylene interpolymer: where the ethylene
interpolymer product
has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal
to
about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about
0.006
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ppm to about 5.7 ppm of titanium, and; less than or equal to about 0.01
terminal vinyl
unsaturations per 100 carbon atoms.
Additional embodiments of this disclosure include ethylene interpolymer
products
comprising: (i) a first ethylene interpolymer; (ii) a second ethylene
interpolymer, and;
(iii) optionally a third ethylene interpolymer: where the ethylene
interpolymer product
has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal
to
about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about
0.006
ppm to about 5.7 ppm of titanium and; from about 0.03 ppm to about 6.0 ppm of
total
catalytic metal.
Further embodiments of this disclosure include ethylene interpolymer products
comprising: (i) a first ethylene interpolymer; (ii) a second ethylene
interpolymer, and;
(iii) optionally a third ethylene interpolymer: where the ethylene
interpolymer product
has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal
to
about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about
0.006
ppm to about 5.7 ppm of titanium; less than or equal to about 0.01 terminal
vinyl
unsaturations per 100 carbon atoms, and; from about 0.03 ppm to about 6.0 ppm
of
total catalytic metal.
Embodiment of this disclosure include ethylene interpolymer products
comprising: (i) a
first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii)
optionally a
third ethylene interpolymer: where the ethylene interpolymer product has a
dimensionless Long Chain Branching Factor (LCBF) greater than or equal to
about
0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.006 ppm
to
about 5.7 ppm of titanium; less than or equal to about 0.01 terminal vinyl
unsaturations per 100 carbon atoms, and; from about 0.03 ppm to about 6.0 ppm
of
total catalytic metal.
Embodiments of this disclosure include ethylene interpolymer products having a
melt
index from about 0.3 to about 500 dg/minute. Further embodiments include
ethylene
interpolymer products having a density from about 0.855 to about 0.975 g/cc.
Other
embodiments include ethylene interpolymer products having a Mw/Mn from about
1.7
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to about 25. Embodiments include ethylene interpolymer products having a
CDBI50
(Composition Distribution Breadth Index) from about 1% to about 98%.
Embodiments include ethylene interpolymer products containing 5 to 60 wt% of a
first
ethylene interpolymer, 20 to 95 wt% of a second ethylene interpolymer and 0 to
30
wt% of a third ethylene interpolymer; where wt% is the weight of the first,
the second
or the optional third ethylene interpolymer, individually, divided by the
total weight of
the ethylene interpolymer product. Additional embodiments include ethylene
interpolymer products where the first ethylene interpolymer has a melt index
from
about 0.01 to about 200 dg/minute, the second ethylene interpolymer has melt
index
from about 0.3 to about 1000 dg/minute, and the third ethylene interpolymer
has a
melt index from about 0.5 to about 2000 dg/minute. Other embodiments include
ethylene interpolymer products where the first ethylene interpolymer has a
density
from about 0.855 g/cm3 to about 0.975 g/cc, the second ethylene interpolymer
has a
density from about 0.855 g/cm3 to about 0.975 g/cc, and the third ethylene
interpolymer has density,from about 0.855 g/cm3 to about 0.975 g/cc.
Embodiments include ethylene interpolymer products containing from 0 to 10
mole
percent of one or more a-olefin, where the a-olefins are C3 to Cio a-olefins.
Non-
limiting examples include ethylene interpolymer products containing the
following a-
olefins: 1-octene, 1-hexene or a mixture of 1-octene and 1-hexene.
Embodiments of this disclosure include a first ethylene interpolymer
synthesized using
at least one homogeneous catalyst formulation. Additional embodiments include
the
synthesis of a first ethylene interpolymer using a first homogeneous catalyst
formulation. One non-limiting example of the first homogeneous catalyst
formulation
is a bridged metallocene catalyst formulation containing a component A defined
by
Formula (I)
=
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R1
67 X (R6)
R4
NA -X PO
R5 4114µ31
(I)
R2
Embodiments of this disclosure include a second ethylene interpolymer
synthesized
using a second homogeneous catalyst formulation. Non-limiting examples of the
second homogeneous catalyst formulation include an unbridged single site
catalyst
formulation.
Optional embodiments include the synthesis of a third ethylene interpolymer
using a
heterogeneous catalyst formulation. Further optional embodiments include the
synthesis of the third ethylene interpolymer using a fifth homogeneous
catalyst
formulation. The fifth horn. ogeneous catalyst formulation may be: a bridged
metallocene catalyst formulation, an unbridged single site catalyst
formulation or a
fourth homogeneous catalyst formulation. The fourth homogeneous catalyst
formulation contains a bulky ligand-metal complex that is not a member of the
chemical genera that defines: a) the bulky ligand-metal complex employed in
the
bridged metallocene catalyst formulation, and; b) the bulky ligand-metal
complex
employed in the unbridged single site catalyst formulation.
Embodiments of this disclosure include ethylene interpolymer products
containing a
catalytic metal A that may range from about 2.4 ppm to about 0.0015 ppm, where
catalytic metal A originates from the first homogeneous catalyst formulation.
Ethylene
interpolymer products may also contain a catalytic metal C that may range from
about
2.9 ppm to about 0.006 ppm, where catalytic metal C originates from the second
homogeneous catalyst formulation. Non-limiting examples of metals A and C
include
titanium, zirconium and hafnium. Optionally, ethylene interpolymer products
may
contain a metal D that may range from 0.9 ppm to 0 ppm; where catalytic metal
D
originates from the fourth homogeneous catalyst formulation. Non-limiting
examples
of metal D include titanium, zirconium and hafnium. Additional optional
embodiments
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include ethylene interpolymer products that contain a catalytic metal Z that
may range
from about 3.9 ppm to about 0 ppm; where catalytic metal Z originates from a
heterogeneous catalyst formulation. Non-limiting examples of catalytic metal Z
includes: titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,
molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or
osmium.
Embodiments of the disclosed ethylene interpolymer products contain a first
ethylene
interpolymer having a first Mw/Mn from about 1.7 to about 2.8, a second
ethylene
interpolymer having a second Mw/Mn from about 1.7 to about 2.8 and an optional
third
ethylene interpolymer having a third Mw/Mn from about 1.7 to about 5Ø
Further embodiments of the ethylene interpolymer products contain a first
ethylene
interpolymer having a first CDBI50 from about 70 to about 98%, a second
ethylene
interpolymer having a second CDB150 from about 70 to about 98% and an optional
third ethylene interpolymer having a third CDB150from about 35 to about 98%.
This disclosure includes embodiment of a continuous solution polymerization
process
where a first and a second reactor are operated in series mode (i.e. the
effluent from
the first reactor flows into the second reactor), a first homogeneous catalyst
formulation is employed in the first reactor and a second homogeneous catalyst
formulations is employed in the second reactor; optionally a heterogeneous
catalyst
formulation or a fifth homogeneous catalyst formulation is employed in an
optional
third reactor. This embodiment of a continuous solution polymerization process
comprises: i) injecting ethylene, a process solvent, a first homogeneous
catalyst
formulation, optionally one or more a-olef ins and optionally hydrogen into a
first
reactor to produce a first exit stream containing a first ethylene
interpolymer in
process solvent; ii) passing the first exit stream into a second reactor and
injecting
into the second reactor, ethylene, process solvent, a second homogeneous
catalyst
formulation, optionally one or more a-olefins and optionally hydrogen to
produce a
second exit stream containing a second ethylene interpolymer and the first
ethylene
interpolymer in process solvent; iii) passing the second exit stream into a
third reactor
and optionally injecting into the third reactor, ethylene, process solvent,
one or more
a-olefins, hydrogen and a fifth homogeneous catalyst formulation and/or a
heterogeneous catalyst formulation to produce a third exit stream containing
an
optional third ethylene interpolymer, the second ethylene interpolymer and the
first
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ethylene interpolymer in process solvent; iv) phase separating the third exit
stream to
recover an ethylene interpolymer product comprising the first ethylene
interpolymer,
the second ethylene interpolymer and the optional third ethylene interpolymer.
The
solution process, series mode embodiments, were improved by having a lower [(I-
S olefin/ethylene] weight ratio in the first reactor and/or the first
reactor produces a
higher molecular first ethylene interpolymer. In some embodiments, the
disclosed
solution process had at least an 70% improved (reduced) [a-olefin/ethylene]
weight
ratio as defined by the following formula
(a ¨ olefin\ A (a ¨ olefin \c
[
a ¨ ole fin ethylene) ethylene)
% Reduced _________________ = 100 x <-70%
ethylene I (a ¨
olefin C
k. ethylene
where (a-olefin/ethylene)A was calculated by dividing the weight of a-olefin
added to
the first reactor by the weight of ethylene added to the first reactor where a
first
ethylene interpolymer having a target density was produced by the first
homogeneous
catalyst formulation, and; (a-olefin/ethylene)c was calculated by dividing the
weight of
a-olefin added to the first reactor by the weight of ethylene added to the
first reactor
where a control ethylene. interpolymer having the target density was produced
by
replacing the first homogeneous catalyst formulation with a third homogeneous
catalyst formulation. In other embodiments of the solution polymerization
process had
at least a 5% improved weight average molecular weight as defined by the
following
formula
% Improved Mw = 100% x (M,,,/-Mwc)/Mwc 5%
where Mw A was the weight average molecular weight of the first ethylene
interpolymer
and Mwc was the weight average molecular weight of a comparative ethylene
interpolymer; where the comparative ethylene interpolymer was produced in the
first
reactor by replacing the first homogeneous catalyst formulation with the third
homogeneous catalyst formulation.
In another embodiment of the continuous solution polymerization process the
first and
second reactors are operated in parallel mode, i.e. the first exit stream
(exiting the first
reactor) by-passes the second reactor and the first exit stream is combined
with the
second exit stream (exiting the second reactor) downstream of the second
reactor.
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Parallel mode embodiments comprises: i) injecting ethylene, a process solvent,
a first
homogeneous catalyst formulation, optionally one or more a-olefins and
optionally
hydrogen into a first reactor to produce a first exit stream containing a
first ethylene
interpolymer in process solvent; ii) injecting ethylene, process solvent, a
second
homogeneous catalyst formulation, optionally one or more a-olefins and
optionally
hydrogen into a second reactor to produce a second exit stream containing a
second
ethylene interpolymer in process solvent; iii) combining the first and second
exit
streams to form a third exit stream; iv) passing the third exit stream into a
third reactor
and optionally injecting into the third reactor, ethylene, process solvent,
one or more
a-olefins, hydrogen and a fifth homogeneous catalyst formulation and/or a
heterogeneous catalyst formulation to produce a fourth exit stream containing
an
optional third ethylene interpolymer, the second ethylene interpolymer and the
first
ethylene interpolymer in said process solvent; v) phase separating the fourth
exit
stream to recover an ethylene interpolymer product comprising the first
ethylene
interpolymer, the second ethylene interpolymer and the optional third ethylene
interpolymer. Parallel mode embodiment were improved by having a lower [cc-
olefin/ethylene] weight ratio in the first reactor and/or a higher molecular
first ethylene
interpolymer, as characterized by the series mode embodiments described
immediately above.
=
Additional embodiments of the series and parallel solution polymerization
processes
include the post reactor addition of a catalyst deactivator to neutralize or
deactivate
the catalysts, forming a deactivated solution. If a heterogeneous catalyst
formulation
was employed in the third reactor, the continuous solution polymerization
process
included an additional step where a passivator was added to the deactivated
solution,
forming a passivated solution. Additional embodiments included steps where the
catalyst inlet temperature was adjusted to optimize the activity of the
bridged
metallocene catalyst formulation.
The disclosed solution polymerization processes include embodiments where the
heterogeneous catalyst formulation was a Ziegler-Natta catalyst formulation
prepared
using an in-line process, hereinafter 'the in-line Ziegler-Natta catalyst
formulation'. In
alternative embodiments the heterogeneous catalyst formulation was a Ziegler-
Natta
catalyst formulation prepared using a batch process, hereinafter 'the batch
Ziegler-
Natta catalyst formulation'.
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Further embodiments include the solution process synthesis of an ethylene
interpolymer product that includes a means for reducing, by at least -70%, the
[a-
olefin/ethylene] weight ratio required to produce the first ethylene
interpolymer (in the
ethylene interpolymer product), where the first ethylene interpolymer has a
target
density; the means involves the appropriate selection of the catalyst
formulation
employed in the first reactor.
Further embodiments include the synthesis of a solution process ethylene
interpolymer product that includes a means for increasing, by at least 5%, the
weight
average molecular weight (Mw) of the first ethylene interpolymer (in the
ethylene
interpolymer product); the means involves the appropriate selection of the
catalyst
formulation employed in the first reactor.
Further embodiments of the present disclosure include manufactured articles;
non-
limiting examples of manufactured articles include flexible articles such as
films and
rigid articles such a containers.
Manufactured articles embodiments include a polyethylene film comprising at
least
one layer, where the layer comprises at least one of the ethylene interpolymer
products disclosed herein. Such films had a machine direction 1% secant
modulus
that was improved (by at, least 25%) and a transverse direction 1% secant
modulus
that was improved (by at least 50% higher); relative to a comparative
polyethylene film
of the same composition but the first ethylene interpolymer (in the ethylene
interpolymer product) was replaced with a comparative ethylene interpolymer,
where
the first ethylene interpolymer was produced with a bridged metallocene
catalyst
formulation and the comparative ethylene interpolymer was produced with an
unbridged single site catalyst formulation. Film examples also had improved
machine
direction 2% secant modulus (by at least 25%) and an improved transverse
direction
2% secant modulus (by at least 50%); relative to a film produced from the
comparative
ethylene interpolymer. Further film embodiments had an improved machine
direction
tensile yield (by at least 10%) and an improved transverse direction tensile
yield (by at
least 30%); relative to the film produced from the comparative ethylene
interpolymer.
Films disclosed herein had improved (lower) hexane extractables, i.e. the
amount of
hexane soluble material (weight %) extracted from films containing the
ethylene
interpolymer product was about 50% lower, relative to films prepared from the
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comparative ethylene interpolymer. Additional film embodiments had improved
(lower) seal initiation temperature (at least 5% lower), relative to films
prepared from
comparative ethylene interpolymers. The hot tack performance of films prepared
from
the disclosed ethylene interpolymer products were also improved; e.g., the
temperature at the onset of film Tack (at a force of 1.0N) was improved (lower
by
about 10%), relative to a comparative polyethylene film of the same
composition but
said first ethylene interpolymer (in the ethylene interpolymer product) was
replaced
with a comparative ethylene interpolymer; where the first ethylene
interpolymer was
produced with a bridged metallocene catalyst formulation and the comparative
ethylene interpolymer was produced with an unbridged single site catalyst
formulation.
Films disclosed herein also had improved dart impact. For example, the dart
impact
of a film prepared from an ethylene interpolymer product was about 100%
higher,
relative to a film prepared from the comparative ethylene interpolymer.
Further embodiments include polyethylene films comprising at least one layer,
where
the layer comprises at least one ethylene interpolymer product and at least
one
second polymer. Non-limiting examples of second polymers include ethylene
polymers, propylene polymers or a mixture of ethylene polymers and propylene
polymers.
Additional embodiments include a polyethylene films having a thickness from
about
0.5 mil to about 10 mil. Embodiments also include multilayer films comprises
from 2
to 11 layers, where at least one layer comprises at least one of the ethylene
interpolymer products disclosed herein.
Brief Description of Figures
The following Figures are presented for the purpose of illustrating selected
embodiments of this disclosure; it being understood, that the embodiments in
this
disclosure are not limited to the precise arrangement of, or the number of,
vessels
shown.
Figure 1 shows the determination of the Long Chain Branching Factor (LCBF).
The
abscissa plotted was the log of the corrected Zero Shear Viscosity (log(ZSVc))
and the
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ordinate plotted was the log of the corrected Intrinsic Viscosity (log(IVc)).
Ethylene
polymers that do not have LCB, or undetectable LOB, fall on the reference
line.
Ethylene polymers having LOB deviate from the reference line and were
characterized
by the dimensionless Long Chain Branching Factor (LCBF). LCBF = (Sh x Sv)/2;
where Sh and Sv are horizontal and vertical shift factors, respectively.
Figure 2 illustrates a continuous solution polymerization process where a
first
homogeneous catalyst formulation and a second homogeneous catalyst formulation
were employed in reactors 11a and 12a, respectively. Optionally (dotted lines)
an in-
line Ziegler-Natta catalyst formulation or a batch Ziegler-Natta catalyst
formulation
was employed in reactor 17.
Figure 3 illustrates the nomenclature used to identify various carbon atoms
that give
rise to signals in 130 NMR spectra.
Figure 4 deconvolution of ethylene interpolymer product Example 51 into a
first,
second and third ethylene interpolymer.
Definition of Terms
Other than in the examples or where otherwise indicated, all numbers or
expressions
referring to quantities of ingredients, extrusion conditions, etc., used in
the
specification and claims are to be understood as modified in all instances by
the term
"about." Accordingly, unless indicated to the contrary, the numerical
parameters set
forth in the following specification and attached claims are approximations
that can
vary depending upon the desired properties that the various embodiments desire
to
obtain. At the very least, and not as an attempt to limit the application of
the doctrine
of equivalents to the scope of the claims, each numerical parameter should at
least be
construed in light of the number of reported significant digits and by
applying ordinary
rounding techniques. The numerical values set forth in the specific examples
are
reported as precisely as possible. Any numerical values, however, inherently
contain
certain errors necessarily resulting from the standard deviation found in
their
respective testing measurements.
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It should be understood that any numerical range recited herein is intended to
include
all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended
to
include all sub-ranges between and including the recited minimum value of 1
and the
recited maximum value of 10; that is, having a minimum value equal to or
greater than
1 and a maximum value of equal to or less than 10. Because the disclosed
numerical
ranges are continuous, they include every value between the minimum and
maximum
values. Unless expressly indicated otherwise, the various numerical ranges
specified
in this application are approximations.
All compositional ranges expressed herein are limited in total to and do not
exceed
100 percent (volume percent or weight percent) in practice. Where multiple
components can be present in a composition, the sum of the maximum amounts of
each component can exceed 100 percent, with the understanding that, and as
those
skilled in the art readily understand, that the amounts of the components
actually used
will conform to the maximum of 100 percent.
In order to form a more complete understanding of this disclosure the
following terms
are defined and should be used with the accompanying figures and the
description of
the various embodiments throughout.
As used herein, the term "monomer" refers to a small molecule that may
chemically
react and become chemically bonded with itself or other monomers to form a
polymer.
As used herein, the term "a-olefin" is used to describe a monomer having a
linear
hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at
one
end of the chain; an equivalent term is "linear a-olefin".
As used herein, the term "ethylene polymer", refers to macromolecules produced
from
ethylene monomers and optionally one or more additional monomers; regardless
of
the specific catalyst or specific process used to make the ethylene polymer.
In the
polyethylene art, the one or more additional monomers are called
"comonomer(s)" and
often include a-olefins. The term "homopolymer" refers to a polymer that
contains
only one type of monomer. Common ethylene polymers include high density
polyethylene (HDPE), medium density polyethylene (MDPE), linear low density
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polyethylene (LLDPE), very low density polyethylene (VLDPE), ultralow density
polyethylene (ULDPE), plastomer and elastomers. The term ethylene polymer also
includes polymers produced in a high pressure polymerization processes; non-
limiting
examples include low density polyethylene (LDPE), ethylene vinyl acetate
copolymers
(EVA), ethylene alkyl acrylate copolymers, ethylene acrylic acid copolymers
and
metal salts of ethylene acrylic acid (commonly referred to as ionomers). The
term
ethylene polymer also includes block copolymers which may include 2 to 4
comonomers. The term ethylene polymer also includes combinations of, or blends
of,
the ethylene polymers described above.
The term "ethylene interpolymer" refers to a subset of polymers within the
"ethylene
= polymer" group that excludes polymers produced in high pressure
polymerization
processes; non-limiting examples of polymer produced in high pressure
processes
include LDPE and EVA (the latter is a copolymer of ethylene and vinyl
acetate).
The term "heterogeneous ethylene interpolymers" refers to a subset of polymers
in the
ethylene interpolymer group that are produced using a heterogeneous catalyst
formulation; non-limiting examples of which include Ziegler-Natta or chromium
catalysts.
The term "homogeneous ethylene interpolymer" refers to a subset of polymers in
the
ethylene interpolymer group that are produced using homogeneous catalyst
formulations. Typically, homogeneous ethylene interpolymers have narrow
molecular
weight distributions, for example Size Exclusion Chromatography (SEC) Mw/Mn
values
of less than 2.8; Mw and Mn refer to weight and number average molecular
weights,
respectively. In contrast, the Mw/Mn of heterogeneous ethylene interpolymers
are
typically greater than the Mw/Mn of homogeneous ethylene interpolymers. In
general,
homogeneous ethylene interpolymers also have a narrow comonomer distribution,
i.e.
each macromolecule within the molecular weight distribution has a similar
comonomer
content. Frequently, the composition distribution breadth index "CDBI" is used
to
quantify how the comonomer is distributed within an ethylene interpolymer, as
well as
to differentiate ethylene interpolymers produced with different catalysts or
processes.
The "CDBI50" is defined as the percent of ethylene interpolymer whose
composition is
within 50% of the median comonomer composition; this definition is consistent
with
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that described in U.S. Patent 5,206,075 assigned to Exxon Chemical Patents
Inc. The
CDBI50 of an ethylene interpolymer can be calculated from TREF curves
(Temperature Rising Elution Fractionation); the TREF method is described in
Wild, et
al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455.
Typically the
CDBI50 of homogeneous ethylene interpolymers are greater than about 70%. In
contrast, the CDBI50 of a-olefin containing heterogeneous ethylene
interpolymers are
generally lower than the CDBI50 of homogeneous ethylene interpolymers. A blend
of
two or more homogeneous ethylene interpolymers, that differ in comonomer
content,
may have a CDBI50 less than 70%; in this disclosure such a blend was defined
as a
homogeneous blend or homogeneous composition. Similarly, a blend of two or
more
homogeneous ethylene interpolymers, that differ in weight averge molecular
weight
(Mw), may have a Mw/Mn 2.8; in this disclosure such a blend was defined as a
homogeneous blend or homogeneous composition.
In this disclosure, the term "homogeneous ethylene interpolymer" refers to
both linear
homogeneous ethylene interpolymers and substantially linear homogeneous
ethylene
interpolymers. In the art, linear homogeneous ethylene interpolymers are
generally
assumed to have no long chain branches or an undetectable amount of long chain
branches; while substantially linear ethylene interpolymers are generally
assumed to
have greater than about 0.01 to about 3.0 long chain branches per 1000 carbon
atoms. A long chain branch is macromolecular in nature, i.e. similar in length
to the
macromolecule that the long chain branch is attached to.
In this disclosure the term homogeneous catalyst is used, for example to
describe a
first, a second, a third, a fourth and a fifth homogeneous catalyst
formulation. The
term catalyst refers to the chemical compound containing the catalytic metal,
which is
a metal-ligand complex. In this disclosure, the term 'homogeneous catalyst' is
defined
by the characteristics of the polymer produced by the homogeneous catalyst.
Specifically, a catalyst is a homogeneous catalyst if it produces a
homogeneous
ethylene interpolymer that has a narrow molecular weight distribution (SEC
Mw/Mn
values of less than 2.8) and a narrow comonomer distribution (CDBI50 > 70%).
Homogeneous catalysts are well known in the art. Two subsets of the
homogeneous
catalyst genus include unbridged metallocene catalysts and bridged metallocene
catalysts. Unbridged metallocene catalysts are characterized by two bulky
ligands
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bonded to the catalytic metal, a non-limiting example includes bis(isopropyl-
cyclopentadienyl) hafnium dichloride. In bridged metallocene catalysts the two
bulky
ligands are covalently bonded (bridged) together, a non-limiting example
includes
diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium
dichloride;
wherein the diphenylmethylene group bonds, or bridges, the cyclopentadienyl
and
fluorenyl bulky ligands together. Two additional subsets of the homogeneous
catalyst
genus include unbridged and bridged single site catalysts. In this disclosure,
single
site catalysts are characterized as having only one bulky ligand bonded to the
catalytic
metal. A non-limiting example of an unbridged single site catalyst includes
cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride. A non-
limiting
example of a bridged single site catalyst includes [C5(CH3)4 - Si(CH3)2 -
N(tBu)]
titanium dichloride, where the -Si(CH3)2- group functions as the bridging
group.
Herein, the term "polyolefin" includes ethylene polymers and propylene
polymers; non-
limiting examples of propylene polymers include isotactic, syndiotactic and
atactic
propylene homopolymers, random propylene copolymers containing at least one
comonomer (e.g. a-olefins) and impact polypropylene copolymers or heterophasic
polypropylene copolymers.
The term "thermoplastic" refers to a polymer that becomes liquid when heated,
will
flow under pressure and solidify when cooled. Thermoplastic polymers include
ethylene polymers as well as other polymers used in the plastic industry; non-
limiting
examples of other polymers commonly used in film applications include barrier
resins
(EVOH), tie resins, polyethylene terephthalate (PET), polyamides and the like.
As used herein the term ,"monolayer film" refers to a film containing a single
layer of
one or more thermoplastics.
As used herein, the terms "hydrocarbyl", "hydrocarbyl radical" or "hydrocarbyl
group"
refers to linear, branched, or cyclic, aliphatic, olefinic, acetylenic and
aryl (aromatic)
radicals comprising hydrogen and carbon that are deficient by one hydrogen.
As used herein, an "alkyl radical" includes linear, branched and cyclic
paraffin radicals
that are deficient by one hydrogen radical; non-limiting examples include
methyl (-
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CH3) and ethyl (-CH2CH3) radicals. The term "alkenyl radical" refers to
linear,
branched and cyclic hydrocarbons containing at least one carbon-carbon double
bond
that is deficient by one hydrogen radical.
As used herein, the term "aryl" group includes phenyl, naphthyl, pyridyl and
other
radicals whose molecules have an aromatic ring structure; non-limiting
examples
include naphthylene, phenanthrene and anthracene. An "arylalkyl" group is an
alkyl
group having an aryl group pendant there from; non-limiting examples include
benzyl,
phenethyl and tolylmethyl; an "alkylaryl" is an aryl group having one or more
alkyl
groups pendant there from; non-limiting examples include tolyl, xylyl, mesityl
and
cumyl.
As used herein, the phrase "heteroatom" includes any atom other than carbon
and
hydrogen that can be bound to carbon. A "heteroatom-containing group" is a
hydrocarbon radical that contains a heteroatom and may contain one or more of
the
same or different heteroatoms. In one embodiment, a heteroatom-containing
group is
a hydrocarbyl group containing from 1 to 3 atoms selected from the group
consisting
of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and
sulfur.
Non-limiting examples of heteroatom-containing groups include radicals of
imines,
amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics,
oxazolines,
thioethers, and the like. The term "heterocyclic" refers to ring systems
having a
carbon backbone that comprise from 1 to 3 atoms selected from the group
consisting
of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and
sulfur.
As used herein the term "unsubstituted" means that hydrogen radicals are
bounded to
the molecular group that follows the term unsubstituted. The term
"substituted" means
that the group following this term possesses one or more moieties that have
replaced
one or more hydrogen radicals in any position within the group; non-limiting
examples
of moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl
groups,
carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups,
naphthyl groups, Ci to Cio alkyl groups, C2 to Cio alkenyl groups, and
combinations
thereof. Non-limiting examples of substituted alkyls and aryls include: acyl
radicals,
alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,
dialkylamino
radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl
radicals, alkyl-
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and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,
arylamino
radicals and combinations thereof.
Herein the term "R1" and its superscript form "Rl" refers to a first reactor
in a
continuous solution polymerization process; it being understood that R1 is
distinctly
different from the symbol R1; the latter is used in chemical formula, e.g.
representing a
= hydrocarbyl group. Similarly, the term "R2" and it's superscript form
"R2" refers to a
second reactor, and; the term "R3" and it's superscript form "R3" refers to a
third
reactor.
As used herein, the term "oligomers" refers to an ethylene polymer of low
molecular
weight, e.g., an ethylene polymer with a weight average molecular weight (Mw)
of
about 2000 to 3000 daltons. Other commonly used terms for oligomers include
"wax"
or "grease". As used herein, the term "light-end impurities" refers to
chemical
compounds with relatively low boiling points that may be present in the
various
vessels and process streams within a continuous solution polymerization
process;
non-limiting examples include, methane, ethane, propane, butane, nitrogen,
CO2,
chloroethane, HCI, etc.
DETAILED DESCRIPTION
Catalysts
Catalyst formulations that are efficient in polymerizing olefins are well
known. In the
embodiments disclosed herein, at least two catalyst formulations were employed
in a
continuous solution polymerization process. One of the catalyst formulations
comprised a first homogeneous catalyst formulation that produces a homogeneous
first ethylene interpolymer in a first reactor, one embodiment of the first
homogeneous
catalyst formulation was a bridged metallocene catalyst formulation (Formula
(I)). The
other catalyst formulation comprised a second homogeneous catalyst formulation
that
produced a second ethylene interpolymer in a second reactor, one embodiment of
the
second homogeneous catalyst formulation was an unbridged single site catalyst
formulation (Formula (II)). Optionally a third ethylene interpolymer may be
produced
in a third reactor using one or more of: the first, the second, a third
homogeneous
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catalyst formulation, a fifth homogeneous catalyst formulation or a
heterogeneous
catalyst formulation. One embodiment of the third homogeneous catalyst
formulation
was an unbridged single site catalyst formulation (Formula (II)). The fifth
homogeneous catalyst formulation was selected from the first, the second, the
third
and/or a fourth homogeneous catalyst formulation; where the fourth homogeneous
catalyst formulation contains a bulky ligand-metal complex that was not a
species of
the chemical genera defined by Formula (I) or Formula (II). In the continuous
solution
process disclosed, at least two homogeneous ethylene interpolymers were
produced
and solution blended to produce an ethylene interpolymer product.
Bulky Ligand-Metal Complexes
Component A
The present disclosure included "a first homogeneous catalyst formulation".
One
embodiment of the first homogeneous catalyst formulation was "a bridged
metallocene
catalyst formulation" containing a bulky ligand-metal complex, hereinafter
"component
A", represented by Formula (I).
R1
162 X(R6)
R4
M-X(R6)
G
/ 3 (I)
R
R2 lb25
In Formula (I): non-limiting examples of M include Group 4 metals, i.e.
titanium,
zirconium and hafnium; non-limiting examples of G include Group 14 elements,
carbon, silicon, germanium, tin and lead; X represents a halogen atom,
fluorine,
chlorine, bromine or iodine; the R6 groups are independently selected from a
hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical or a C6-10
aryl oxide
radical (these radicals may be linear, branched or cyclic or further
substituted with
halogen atoms, Ci-io alkyl radicals, Ci-io alkoxy radicals, C6-10 aryl or
aryloxy radicals);
Ri represents a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy
radical or a
C6-10 aryl oxide radical; R2 and R3 are independently selected from a hydrogen
atom, a
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C1-20 hydrocarbyl radical, a 01-20 alkoxy radical or a 06-10 aryl oxide
radical, and; R4
and R5 are independently selected from a hydrogen atom, a 01-20 hydrocarbyl
radical,
a 01-20 alkoxy radical or a 06-10 aryl oxide radical.
In the art, a commonly used term for the X(R6) group shown in Formula (I) is
"leaving
group", i.e. any ligand that can be abstracted from Formula (I) forming a
catalyst
species capable of polymerizing one or more olefin(s). An equivalent term for
the
X(1:16) group is an "activatable ligand". Further non-limiting examples of the
X(1:16)
group shown in Formula (I) include weak bases such as amines, phosphines,
ethers,
carboxylates and dienes. In another embodiment, the two R6 groups may form
part of
a fused ring or ring system.
Further embodiments of component A include structural, optical or enantiomeric
isomers (meso and racemic isomers) and mixtures thereof of the structure shown
in
Formula (I).
In this disclosure, various species of component A (Formula (I)) were denoted
by the
terms "component Al", "component A2" and "component A3", etc. While not to be
construed as limiting, two species of component A were employed as examples in
this
disclosure. Specifically: "component Al" refers to
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dichloride
having
the molecular formula [(2,7-tBu2Flu)Ph20(Cp)HfC12], and; "component A2" refers
to
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dinnethyl
having
the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]. In this disclosure,
component
Al and component A2 were used to prepare examples of the bridged metallocene
catalyst formulation.
Long Chain Branching in Ethylene Interpolymer Products (via Component A)
In this disclosure, the firgt homogeneous catalyst formulation, comprising a
component A, produces ethylene interpolymer products that have long chain
branches, hereinafter `LOB'.
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LCB is a well-known structural phenomenon in polyethylenes and well known to
those
of ordinary skill in the art. Traditionally, there are three methods for LCB
analysis,
namely, nuclear magnetic resonance spectroscopy (NMR), for example see J.C.
Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201; triple
detection SEC equipped with a DRI, a viscometer and a low-angle laser light
scattering detector, for example see W.W. Yau and D.R. Hill, Int. J. Polym.
Anal.
Charact. 1996; 2:151; and rheology, for example see W.W. Graessley, Acc. Chem.
Res. 1977, 10, 332-339. In this disclosure, a long chain branch is
macromolecular in
nature, i.e. long enough to be seen in an NMR spectra, triple detector SEC
experiments or rheological experiments.
A limitation with LCB analysis via NMR is that it cannot distinguish branch
length for
branches equal to or longer than six carbon atoms (thus, NMR cannot be used to
characterize LCB in ethylene/1-octene copolymers, which have hexyl groups as
side
branches).
The triple detection SEC method measures the intrinsic viscosity GO (see
W.W. Yau, D. Gillespie, Analytical and Polymer Science, TAPPI Polymers,
Laminations, and Coatings Conference Proceedings, Chicago 2000; 2: 699 or F.
Beer,
G. Capaccio, L.J. Rose, J. Appl. Polym. Sci. 1999, 73: 2807 or P.M. Wood-
Adams,
J.M. Dealy, A.W. deGroot, O.D. Redwine, Macromolecules 2000; 33: 7489). By
referencing the intrinsic viscosity of a branched polymer (Mb) to that of a
linear one
(Hi) at the same molecular weight, the viscosity branching index factor g'
(g'Ir00/[r]I)
was used for branching characterization. However, both short chain branching
(SOB)
and long chain branching (LCB) make contribution to the intrinsic viscosity
arlp, effort
was made to isolate the SOB contribution for ethylene/1-butene and ethylene/1-
hexene copolymers but not ethylene/1-octene copolymers (see Lue et al.,
US6,870,010 B1). In this disclosure, a systematical investigation was
performed to
look at the SOB impact on the Mark-Houwink constant K for three types
ethylene/1-
olefin copolymers, i.e. octene, hexene and butene copolymers. After the
deduction of
SOB contribution, a Viscosity LCB Index was introduced for the
characterization of
ethylene/1-olefin copolymers containing LCB. The Viscosity LCB Index was
defined
as the measured Mark-Houwink constant (Km) in 1,2,4-trichlorobenzene (TCB) at
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140 C for the sample divided by the SCB corrected Mark-Houwink constant (Kw)
for
linear ethylene/1-olefin copolymer, Eq.(1).
[771/4"725
Viscosity LCB Index = ¨Km= Eq.(1)
K0(391.98¨A xscB)/n00000
Where [11] was the intrinsic viscosity (dL/g) determined by 3D-SEC, Mv was the
viscosity average molar mass (g/mole) determined using 3D-SEC; SCB was the
short
chain branching content (CH3#/1000C) determined using FTIR, and; A was a
constant
which depends on the a-olefin present in the ethylene/a-olefin interpolymer
under test,
specifically, A is 2.1626, 1.9772 and 1.1398 for 1-octene, 1-hexene and 1-
butene
respectively. In the case of an ethylene homopolymer no correction is required
for the
Mark-Houwink constant, i.e. SCB is zero.
In the art, rheology has also been an effective method to measure the amount
of LCB,
or lack of, in ethylene interpolymers. Several rheological methods to quantify
LCB
have been disclosed. One commonly-used method was based on zero-shear
viscosity (go) and weight-average molar mass (Mw) data. The 3.41 power
dependence
(go = KxMw3.41) has been established for monodisperse polyethylene solely
composed
of linear chains, for example see R.L. Arnett and C.P. Thomas, J. Phys. Chem.
1980,
84, 649-652. An ethylene polymer with a no exceeding what was expected for a
linear
ethylene polymer, with the same Mw, was considered to contain long-chain
branches.
However, there is a debate in the field regarding the influence of
polydispersity, e.g.
Mw/Mn. A dependence on polydispersity was observed in some cases (see M.
Ansari
et al., Rheol. Acta, 2011, 5017-27) but not in others (see T.P. Karjala et
al., Journal of
Applied Polymer Science 2011, 636-646).
Another example of LCB analysis via rheology was based on zero-shear viscosity
(no)
and intrinsic viscosity (m) data, for example see R.N. Shroff and H. Mavridis,
Macromolecules 1999, 32, 8454; which is applicable for essentially linear
polyethylenes (i.e. polyethylenes with very low levels of LCB). A critical
limitation of
this method is the contribution of the SCB to the intrinsic viscosity. It is
well known
that [n] decreases with increasing SCB content.
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In this disclosure, a systematical investigation was performed to look at the
impact of
both SCB and molar mass distribution. After the deduction of the contribution
of both
SOB and molar mass distribution (polydispersity), a Long Chain Branching
Factor
(LCBF) was introduced to characterize the amount of LOB in ethylene/a-olefin
copolymers, as described below.
Long Chain Branching Factor (LCBF)
In this disclosure the Long Chain Branching Factor, hereinafter LCBF, was used
to
characterize the amount of LOB in ethylene interpolymer products. The
disclosed
ethylene interpolymer products were in-situ blends of at least two ethylene
interpolymers produced with at least two different catalyst formulations.
Figure 1 illustrates the calculation of the LCBF. The solid 'Reference Line'
shown in
Figure 1 characterizes ethylene polymers that do not contain LOB (or
undetectable
LOB). Ethylene polymers containing LOB deviate from this Reference Line. For
example, the disclosed ethylene interpolymer products Examples 50-52 (the '+'
symbols Figure 1) deviate horizontally and vertically from the Reference Line.
LCBF calculation requires the polydispersity corrected Zero Shear Viscosity
(ZSVc)
and the SOB corrected Intrinsic Viscosity (IVO as fully described in the
following
paragraphs.
The correction to the Zero Shear Viscosity, ZSVc, having dimensions of poise,
was
performed as shown in equation Eq.(2):
1.8389 x
ZSV = ____________________________________________________ Eq.(2)
C 2.41 10"(Pd)
where no, the zero shear viscosity (poise), was measured by DMA as described
in the
'Testing Methods' section of this disclosure; Pd was the dimensionless
polydispersity
(Mw/Mn) as measured using conventional SEC (see 'Testing Methods') and 1.8389
and 2.4110 are dimensicinless constants.
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The correction to the Intrinsic Viscosity, IV, having dimensions of dL/g, was
performed as shown in equation Eq.(3):
A X SCB X 4325
= [ 1)] + Eq.(3)
n00000
where the intrinsic viscosity [i] (dL/g) was measured using 3D-SEC (see
'Testing
Methods'); SCB having dimensions of (CH3#/1000C) was determined using FTIR
(see
'Testing Methods'); Mv, the viscosity average molar mass (g/mole), was
determined
using 3D-SEC (see 'Testing Methods'), and; A was a dimensionless constant that
depends on the a-olefin in the ethylene/a-olefin interpolymer sample, i.e. A
was
2.1626, 1.9772 or 1.1398 for 1-octene, 1-hexene and 1-butene a-olefins,
respectively.
In the case of an ethylene homopolymer no correction is required for the Mark-
Houwink constant, i.e. SCB is zero.
As shown in Figure 1, linear ethylene/a-olefin interpolymers (which do not
contain
LOB or contain undetectable levels of LOB) fall on the Reference Line defined
by
Eq.(4).
Log(IV) ='0.2100 x Log(ZSI/c) ¨ 0.7879 Eq.(4)
Table 1A shows the Reference Resins had Mw/Mn values that ranged from 1.68 to
9.23 and contained 1-octene, 1-hexene or 1-butene a-olefins. Further,
Reference
Resins included ethylene polymers produced in solution, gas phase or slurry
processes with Ziegler-Natta, homogeneous and mixed (Ziegler-Natta +
homogeneous) catalyst formulations.
The ethylene interpolymer products, disclosed herein, contain long chain
branching as
evidenced by Table 2 and Figure 1. More specifically, Table 2 discloses that
the
LCBF of Examples 50 through 52 and Example 58 were 0.00845, 0.0369, 0.0484 and
0.0417, respectively. Example 50-52 (+ symbol) and Example 58 (open square)
deviate significantly from the Reference Line shown in Figure 1. Examples 50
through
52 and Example 58 were produced using a bridged metallocene catalyst
formulation
in the first reactor and an unbridged single site catalyst formulation in the
second
reactor. In contrast, as shown in Table 2, Comparatives 61, 67 had much lower
LCBF
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of 0.000330 and 0.000400, respectively, and these samples were well described
by
the linear Reference Line shown in Figure 1 (the open triangle symbols), i.e.
Comparatives 61 and 67 have not have LCB, or have an undetectable level of
LCB.
Comparative 61 was produced in a solution process pilot plant using an
unbridged
single site catalyst formulation (Formula (II)) in both the first and second
reactor,
where the reactors were configured in series. Comparative 67 was produced in a
commercial-scale solution process using an unbridged single site catalyst
formulation
in both the first and second reactor, where the reactors were configured in
series.
As shown in Figure 1, the calculation of the LCBF was based on the Horizontal-
Shift
(SO and Vertical-Shift (Sy) from the linear reference line, as defined by the
following
equations:
Sh = Log(ZSV,)¨ 4.7619 x Log(IV) ¨ 3.7519 Eq.(5)
Sv = 0.2100 x Log(ZSV,)¨ Log(110¨ 0.7879 Eq.(6).
In Eq. (5) and (6), it is required that ZSVc and IVc have dimensions of poise
and dLig,
respectively. The Horizontal-Shift (SO was a shift in ZSVc at constant
Intrinsic
Viscosity (IV), if one removes the Log function its physical meaning is
apparent, i.e. a
ratio of two Zero Shear Viscosities, the ZSVc of the sample under test
relative to the
ZSVc of a linear ethylene polymer having the same IVc. The Horizontal-Shift
(SO was
dimensionless. The Vertical-Shift (Sv) was a shift in IVc at constant Zero
Shear
Viscosity (ZSVc), if one removes the Log function its physical meaning is
apparent, i.e.
a ratio of two Intrinsic Viscosities, the IVc of a linear ethylene polymer
having the same
ZSVc relative to the IVc of the sample under test. The Vertical-Shift (Sv) was
dimensionless.
The dimensionless Long Chain Branching Factor (LCBF) was defined by Eq.(7):
LCBF = shxsv - Eq.(7)
2
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Given the data in Table 2, the LCBF of Examples and Comparatives were
calculated.
To be more clear, as shown in Table 2, the Si, and Sv of Example 51 were 0.593
and
0.124, respectively, thus the LCBF was 0.0368 ((0.593 x 0.124)/2). In
contrast, the Si,
and Sv of Comparative 61 were 0.0560 and 0.0118, respectively, thus the LCBF
was
0.00033 ((0.0560 x 0.0118)/2).
In this disclosure, resins having no LCB (or undetectable LCB) were
characterized by
a LCBF of less than 0.001 (dimensionless), as evidenced by Table 1B where the
reference resins had LCBF values ranging from 0.000426 to 1.47x10-9.
In this disclosure, resins having LCB were characterized by a LCBF of 0.001
(dimensionless), as evidenced by Examples 50-52 and Example 58 shown in Table
2
that had LCBF that ranged from 0.00845 and 0.0484.
Table 3 summarizes the LCBF of Comparatives A-C and Comparatives D-G.
Comparatives A-C (open diamond in Figure 1) were believed to be produced in a
solution process employing one reactor and a constrained geometry single site
catalyst formulation, i.e. AFFINITYTm PL 1880 (three different samples
(lots)).
AFFINITYTm products are ethylene/1-octene interpolymers available from The Dow
Chemical Company (Midland, Michigan, USA). It has been well documented in the
art
that the constrained geometry catalyst produces long chain branched ethylene/1-
octene copolymers, as evidenced by the LCBF values disclosed in Table 3, i.e.
from
0.0396 to 0.0423. Comparatives D-G (the open circles in Figure 1) were
believed to
be solution process series dual reactor and dual catalyst ethylene
interpolymers,
where a constrained geometry single site catalyst formulation was employed in
a first
reactor and a batch Ziegler-Natta catalyst formulation was employed in a
second
reactor, i.e. Elite 5401G and Elite 5100G (two different samples (lots)) and
Elite
5400G, respectively. Elite products are ethylene/1-octene interpolymers
available
from The Dow Chemical Company (Midland, Michigan, USA). As shown in Table 3,
Comparatives D-G had LCBF values from 0.00803 to 0.0130.
13C NMR Determination of Long Chain Branching in the First Ethylene
Interpolvmer
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Examples of ethylene interpolymer product, disclosed herein, contain a first
ethylene
interpolymer that was produced with a first homogeneous catalyst formulation.
One
embodiment of the first homogenous catalyst formulation was a bridged
metallocene
catalyst formulation, this catalyst formulation produced a long chain branched
(LOB)
first ethylene interpolymer. Pure samples of the first ethylene interpolymer
were
produced using the Continuous Polymerization Unit (CPU). The CPU was fully
described in the 'Continuous Polymerization Unit (CPU)' section of this
disclosure.
The CPU employs one reactor and one catalyst formulation was used. The CPU and
the bridged metallocene catalyst formulation containing Component A [(2,7-
tBu2Flu)Ph2C(Cp)HfMe2] were used to produce examples of the first ethylene
interpolymer and the amount of long chain branching in this interpolymer was
measured by 130 NMR. Table 13x illustrates typical CPU operating continues for
the
bridged metallocene catalyst formulating to produce a first ethylene
interpolymer at
three reactor temperatures (130 C, 160 C and 190 C) and two levels of ethylene
conversion, i.e. low ethylene conversion (about 75%) and high ethylene
conversion
(about 94%). No hydrogen was used.
Table 14 discloses the amount of LOB in Examples 010 to 015, i.e. pure samples
of
the first ethylene interpolymer, produced with the bridged metallocene
catalyst
formulation, as determined by 13C-NMR (nuclear magnetic resonance). Examples
010 to C15 were ethylene homopolymers produced on the CPU at three reactor
temperatures (190 C, 16.0 C and 130 C), three levels of ethylene conversions,
i.e.
about 95 wt%, about 85 wt% and about 75 wt% and no hydrogen was used. As
shown in Table 14, the amount of long chain branching in the first ethylene
interpolymer varied from 0.03 LOB/1000C to 0.23 LOB/1000C.
Component C
In this disclosure, at least two catalyst formulations were employed to
synthesize
embodiments of the ethylene interpolymer products. One catalyst formulation
was the
first homogeneous catalyst formulation; one embodiment of the first
homogeneous
catalyst was a bridged metallocene catalyst formulation containing component
A,
described above. The other catalyst formulation was the second homogeneous
catalyst formulation; one embodiment of the second homogeneous catalyst
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formulation was "an unbridged single site catalyst formulation" containing a
bulky
ligand-metal complex, hereinafter "component C", represented by Formula (II).
(LA)aM(PI)b(Q)n (II)
In Formula (II): (LA) represents a bulky ligand; M represents a metal atom; PI
represents a phosphinimine ligand; Q represents a leaving group; a is 0 or 1;
b is 1 or
2; (a+b) = 2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of the
metal M.
Non-limiting examples of M in Formula (II) include Group 4 metals, titanium,
zirconium
and hafnium.
Non-limiting examples of the bulky ligand LA in Formula (II) include
unsubstituted or
substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands,
heteroatom
substituted and/or heteroatom containing cyclopentadienyl-type ligands.
Additional
non-limiting examples include, cyclopentaphenanthreneyl ligands, unsubstituted
or
substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted
fluorenyl
ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,
cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene
ligands,
phosphoyl ligands, phosphinimine, pyrrolyl ligands, pyrozolyl ligands,
carbazolyl
ligands, borabenzene ligands and the like, including hydrogenated versions
thereof,
for example tetrahydroindenyl ligands. In other embodiments, LA may be any
other
ligand structure capable of q-bonding to the metal M, such embodiments include
both
q3-bonding and q5-bonding to the metal M. In other embodiments, LA 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 a
fused
ring, or ring system, for example, a heterocyclopentadienyl ancillary ligand.
Other
non-limiting embodiments for LA include bulky amides, phosphides, alkoxides,
aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines,
corrins and
other polyazomacrocycles.
The phosphinimine ligand, PI, is defined by Formula (III):
(RP)3 P = N - (III)
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wherein the RP groups are independently selected from: a hydrogen atom; a
halogen
atom; 01-20 hydrocarbyl radicals which are unsubstituted or substituted with
one or
more halogen atom(s); a C1-8 alkoxy radical; a C6-10 aryl radical; a 06-10
aryloxy radical;
an amido radical; a silyl radical of formula -Si(Rs)3, wherein the Rs groups
are
independently selected from, a hydrogen atom, a 01-8 alkyl or alkoxy radical,
a C6-10
aryl radical, a 06-10 aryloxy radical, or a germanyl radical of formula -
Ge(RG)3, wherein
the RG groups are defined as Rs is defined in this paragraph.
The leaving group Q is any ligand that can be abstracted from Formula (II)
forming a
catalyst species capable'of polymerizing one or more olefin(s). In some
embodiments, 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 1 or 2 such that
Formula (II)
represents a neutral bulky ligand-metal complex. Non-limiting examples of Q
ligands
include a hydrogen atom, halogens, 01-20 hydrocarbyl radicals, 01-20 alkoxy
radicals;
C5_10 aryl oxide radicals; these radicals may be linear, branched or cyclic or
further
substituted by halogen atoms, Ci_io alkyl radicals, Ci-io alkoxy radicals, C6-
10 arly or
aryloxy radicals. Further non-limiting examples of Q ligands include weak
bases such
as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals
having from
1 to 20 carbon atoms. In another embodiment, two Q ligands may form part of a
fused ring or ring system.
Further embodiments of component C include structural, optical or enantiomeric
isomers (meso and racemic isomers) and mixtures thereof of the bulky ligand-
metal
complex shown in FormOla (II).
In this disclosure, unique chemical species of component C (Formula (II)) are
denoted
by the terms "component Cl", "component C2" and "component 03", etc. While not
to
be construed as limiting, two species of component C were employed as examples
in
this disclosure. Specifically: "component Cl" refers to cyclopentadienyl
tri(tertiary
butyl) phosphinimine titanium dichloride having the molecular formula [Cp[(t-
Bu)3PN]TiC12] abbreviated "PIC-1" in Table 4A, and; "component 02" refers to
cyclopentadienyl tri(isopropyl)phosphinimine titanium dichloride having the
molecular
formula [CpRisopropy1)3PNIfiC12] abbreviated "I'10-2" in Table 4A. In this
disclosure,
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component Cl and component 02 were used as the source of bulky ligand-metal
complex to prepare two examples of the unbridged single site catalyst
formulation.
Comparative Ethylene Interpolymer Products
In this disclosure, Comparative ethylene interpolymer products were produced
by
replacing the first homogeneous catalyst formulation, responsible for
producing the
first ethylene interpolymer, with a third homogeneous catalyst formulation.
One
embodiment of the third homogeneous catalyst formulation was an unbridged
single
site catalyst formulation where the bulky ligand-metal complex was a member of
the
genus defined by Formula (II), for example component C described above. As
shown
in Table 4A, Comparative 60 was produced employing PIC-2 in both reactors 1
and 2,
where reactor 1 and 2 were configured in series. Comparative 61 was produced
employing PIC-1 in both reactors 1 and 2, where reactor 1 and 2 were
configured in
parallel. Comparative 67 was produced employing an unbridged single site
catalyst
formulation in both reactors 1 and 2, where reactor 1 and 2 were configured in
parallel. As shown in Table 2 and Figure 1, Comparatives 61 and 67 had
undetectable levels of LOB, as evidenced by the dimensionless Long Chain
Branching
Factor (LCBF) of less than 0.001, e.g. LCBF ranged from 0.00033 to 0.00040,
respectively.
Homogeneous Catalyst Formulations
In this disclosure the non-limiting "Examples" of ethylene interpolymer
product were
prepared by employing a bridged metallocene catalyst formulation in a first
reactor.
The bridged metallocene catalyst formulation contains a component A (defined
above), a component MA, a component BA and a component PA. Components M, B
and P are defined below and the superscript "A" denotes that fact that the
respective
component was part of the catalyst formulation containing component A, i.e.
the
bridged metallocene catalyst formulation.
In this disclosure "Comparative" ethylene interpolymers were prepared by
employing
an unbridged single site catalyst formulation in the first reactor. In other
words, in
Comparative samples, the unbridged single site catalyst formulation replaced
the
bridged metallocene catalyst formulation in the first reactor. The unbridged
single site
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catalyst formulation contains a component C (defined above), a component Mc, a
component BC and a component Pc. Components M, B and P are defined below and
the superscript "C" denoted that fact that the respective component was part
of the
catalyst formulation containing component C, i.e. the unbridged single site
catalyst
formulation.
The catalyst components M, B and P were independently selected for each
catalyst
formulation. To be more clear: components MA and Mc may, or may not be, the
same
chemical compound; components BA and BC may, or may not be, the same chemical
compound, and; components PA and Pc may, or may not be, the same chemical
compound. Further, catalyst activity was optimized by independently adjusting
the
mole ratios of the components in each catalyst formulation.
Components M, B and P were not particularly limited, i.e. a wide variety of
components can be used as described below.
Component M functioned as a co-catalyst that activated component A or
component
C, into a cationic complex that effectively polymerized ethylene, or mixtures
of
ethylene and a-olefins, producing high molecular weight ethylene
interpolymers. In
the bridged metallocene catalyst formulation and the unbridged single site
catalyst
formulation the respective component M was independently selected from a
variety of
compounds and those skilled in the art will understand that the embodiments in
this
disclosure are not limited to the specific chemical compound disclosed.
Suitable
compounds for component M included an alumoxane co-catalyst (an equivalent
term
for alumoxane is aluminoxane). Although the exact structure of an alumoxane co-
catalyst was uncertain, subject matter experts generally agree that it was an
oligomeric species that contain repeating units of the general Formula (IV):
(R)2A10-(Al(R)-0)n-Al(R)2 (IV)
where the R groups may be the same or different linear, branched or cyclic
hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about
50. A
non-limiting example of an alumoxane was methyl alum inoxane (or MMAO-7)
wherein
each R group in Formula (IV) is a methyl radical.
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Component B was an ionic activator. In general, ionic activators are comprised
of a
cation and a bulky anion; wherein the latter is substantially non-
coordinating.
In the bridged metallocene catalyst formulation and the unbridged single site
catalyst
formulation the respective component B was independently selected from a
variety of
compounds and those skilled in the art will understand that the embodiments in
this
disclosure are not limited to the specific chemical compound disclosed. Non-
limiting
examples of component B were boron ionic activators that are four coordinate
with
four ligands bonded to the boron atom. Non-limiting examples of boron ionic
activators included the following Formulas (V) and (VI) shown below;
[R5]+[B(R7)4]- (V)
where B represented a boron atom, R5 was an aromatic hydrocarbyl (e.g.
triphenyl
methyl cation) and each R7 was independently selected from phenyl radicals
which
were unsubstituted or substituted with from 3 to 5 substituents selected from
fluorine
atoms, C1-4 alkyl or alkoxy radicals which were unsubstituted or substituted
by fluorine
atoms; and a silyl radical of formula -Si(R9)3, where each R9 was
independently
selected from hydrogen atoms and C1-4 alkyl radicals, and; compounds of
formula (VI);
[(R8)IZH][B(R7)4]- (VI)
where B was a boron atom, H was a hydrogen atom, Z was a nitrogen or
phosphorus
atom, t was 2 or 3 and R8 was selected from C1-8 alkyl radicals, phenyl
radicals which
were unsubstituted or substituted by up to three C1-4 alkyl radicals, or one
R8 taken
together with the nitrogen atom may form an anilinium radical and R7 was as
defined
above in Formula (VI).
In both Formula (V) and (VI), a non-limiting example of R7 was a
pentafluorophenyl
radical. In general, boron ionic activators may be described as salts of
tetra(perfluorophenyl) boron; non-limiting examples include anilinium,
carbonium,
oxonium, phosphonium and sulfonium salts of tetra(perfluorophenyl)boron with
anilinium and trityl (or triphenylmethylium). Additional non-limiting examples
of ionic
activators included: triethylammonium tetra(phenyl)boron, tripropylammonium
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=
tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium
tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-
dimethylphenyl)boron,
tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-
trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron,
tri(n-
butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron,
N,N-
diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-
butylboron,
N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium
tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron,
triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium
tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron,
tropillium
tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl
borate,
benzene(diazonium)tetrakispentafluorophenyl borate, tropillium
tetrakis(2,3,5,6-
tetrafluorophenyl)borate,=triphenylmethylium tetrakis(2,3,5,6-
tetrafluorophenyl)borate,
benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium
tetrakis(3,4,5 -
trifluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-
trifluorophenyl)borate,
tropillium tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium
tetrakis(1 ,2,2-
trifluoroethenyl)borate, benzene(diazonium) tetrakis(1,2,2-
trifluoroethenyl)borate,
tropillium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylium
tetrakis(2,3,4,5-
tetrafluorophenyl)borate, and benzene(diazonium) tetrakis(2,3,4,5
tetrafluorophenyl)borate. Readily available commercial ionic activators
included N,N-
dimethylanilinium tetrakispentafluorophenyl borate, and triphenylmethylium
tetrakispentafluorophenyl borate.
Component P is a hindered phenol and is an optional component in the
respective
catalyst formulation. In the bridged metallocene catalyst formulation and the
unbridged single site catalyst formulation the respective component P was
independently selected from a variety of compounds and those skilled in the
art will
understand that the embodiments in this disclosure are not limited to the
specific
chemical compound disclosed. Non-limiting example of hindered phenols included
butylated phenolic antioxidants, butylated hydroxytoluene, 2,4-di-
tertiarybuty1-6-ethyl
phenol, 4,4'-methylenebis (2,6-di-tertiary-butylphenol), 1,3, 5-trimethy1-
2,4,6-tris (3,5-
di-tert-buty1-4-hydroxybenzyl) benzene and octadecy1-3-(3',5'-di-tert-buty1-4'-
hydroxyphenyl) propionate.
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As fully described below, a highly active first homogeneous catalyst
formulation, or in
one specific embodiment a highly active bridged metallocene catalyst
formulation was
produced by optimizing the quantity and mole ratios of the four components in
the
formulation; for example, component Al, component MA', component BA' and
component Pm. Where highly active means a very large amount of ethylene
interpolymer is produced from a very small amount of catalyst formulation.
Similarly, a
highly active third homogeneous catalyst formulation or an unbridged single
site
catalyst formulation (comparative catalyst formulations) were produced by
optimizing
the quantity and mole ratios of the four components in the formulation; e.g.,
one
embodiment comprises a component Cl, a component Mcl, a component 13c1 and a
component Pcl.
Heterogeneous Catalyst Formulations
A number of heterogeneous catalyst formulations are well known to those
skilled in
the art, including, as non-limiting examples, Ziegler-Natta and chromium
catalyst
formulations. In this disclosure, optionally a heterogeneous catalyst
formulation may
be employed to synthesize the third ethylene interpolymer in a third reactor.
The
catalytic metal in the heterogeneous catalyst formulation was identified by
the term
"metal Z".
In this disclosure, embodiments were described where the heterogeneous
catalyst
formulation was "an in-line Ziegler-Natta catalyst formulation" or "a batch
Ziegler-Natta
catalyst formation". The term "in-line" referred to the continuous synthesis
of a small
quantity of active Ziegler-Natta catalyst and immediately injecting this
catalyst into the
third reactor, wherein ethylene and one or more optional a-olefins were
polymerized to
form the optional third ethylene interpolymer. The term "batch" referred to
the
synthesis of a much larger quantity of catalyst or procatalyst in one or more
mixing
vessels that were external to, or isolated from, the continuously operating
solution
polymerization process. Once prepared, the batch Ziegler-Natta catalyst
formulation,
or batch Ziegler-Natta procatalyst, was transferred to a catalyst storage
tank. The
term "procatalyst" referred to an inactive catalyst formulation (inactive with
respect to
ethylene polymerization); the procatalyst was converted into an active
catalyst by
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adding an alkyl aluminum co-catalyst. As needed, the procatalyst was pumped
from
the storage tank to at least one continuously operating reactor, wherein an
active
catalyst polymerizes ethylene and one or more optional a-olefins to form an
ethylene
interpolymer. The procatalyst may be converted into an active catalyst in the
reactor
or external to the reactor.
A wide variety of chemical compounds can be used to synthesize an active
Ziegler-
Natta catalyst formulation. The following describes various chemical compounds
that
may be combined to produce an active Ziegler-Natta catalyst formulation. Those
skilled in the art will understand that the embodiments in this disclosure are
not limited
to the specific chemical compound disclosed.
An active Ziegler-Natta catalyst formulation may be formed from: a magnesium
compound, a chloride compound, a metal compound, an alkyl aluminum co-catalyst
and an aluminum alkyl. In this disclosure, the term "component (v)" is
equivalent to
the magnesium compound, the term "component (vi)" is equivalent to the
chloride
compound, the term "component (vii)" is equivalent to the metal compound, the
term
"component (viii)" is equiyalent to the alkyl aluminum co-catalyst and the
term
"component (ix)" is equivalent to the aluminum alkyl. As will be appreciated
by those
skilled in the art, Ziegler-Natta catalyst formulations may contain additional
components; a non-limiting example of an additional component is an electron
donor,
e.g. amines or ethers.
A non-limiting example of an active in-line Ziegler-Natta catalyst formulation
can be
prepared as follows. In the first step, a solution of a magnesium compound
(component (v)) is reacted with a solution of the chloride compound (component
(vi))
to form a magnesium chloride support suspended in solution. Non-limiting
examples
of magnesium compounds include Mg(R1)2; wherein the R1 groups may be the same
or different, linear, branched or cyclic hydrocarbyl radicals containing 1 to
10 carbon
atoms. Non-limiting examples of chloride compounds include R2CI; wherein R2
represents a hydrogen atom, or a linear, branched or cyclic hydrocarbyl
radical
containing 1 to 10 carbon atoms. In the first step, the solution of magnesium
compound may also contain an aluminum alkyl (component (ix)). Non-limiting
examples of aluminum alkyl include Al(R3)3, wherein the R3 groups may be the
same
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or different, linear, branched or cyclic hydrocarbyl radicals containing from
1 to 10
carbon atoms. In the second step a solution of the metal compound (component
(vii))
is added to the solution of magnesium chloride and the metal compound is
supported
on the magnesium chloride. Non-limiting examples of suitable metal compounds
include M(X) n or MO(X)n; where M represents a metal selected from Group 4
through
Group 8 of the Periodic Table, or mixtures of metals selected from Group 4
through
Group 8; 0 represents oxygen, and; X represents chloride or bromide; n is an
integer
from 3 to 6 that satisfies the oxidation state of the metal. Additional non-
limiting
examples of suitable metal compounds include Group 4 to Group 8 metal alkyls,
metal
alkoxides (which may be prepared by reacting a metal alkyl with an alcohol)
and
mixed-ligand metal compounds that contain a mixture of halide, alkyl and
alkoxide
ligands. In the third step a solution of an alkyl aluminum co-catalyst
(component (viii))
is added to the metal compound supported on the magnesium chloride. A wide
variety of alkyl aluminum co-catalysts are suitable, as expressed by Formula
(VII):
Al(R4)p(0R5)q(X)r (VII)
wherein the R4 groups may be the same or different, hydrocarbyl groups having
from
1 to 10 carbon atoms; the OR5 groups may be the same or different, alkoxy or
aryloxy
groups wherein R5 is a hydrocarbyl group having from 1 to 10 carbon atoms
bonded
to oxygen; X is chloride or bromide, and; (p+q+r) = 3, with the proviso that p
is greater
than 0. Non-limiting examples of commonly used alkyl aluminum co-catalysts
include
trimethyl aluminum, triethyl aluminum, tributyl aluminum, dimethyl aluminum
methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide, dimethyl
aluminum
chloride or bromide, diethyl aluminum chloride or bromide, dibutyl aluminum
chloride
or bromide and ethyl aluminum dichloride or dibromide.
The process described in the paragraph above, to synthesize an active in-line
Ziegler-
Natta catalyst formulation, can be carried out in a variety of solvents; non-
limiting
examples of solvents include linear or branched 05 to 012 alkanes or mixtures
thereof.
To produce an active in-line Ziegler-Natta catalyst formulation the quantity
and mole
ratios of the five components, (v) through (ix), are optimized as described
below.
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Additional embodiments of heterogeneous catalyst formulations include
formulations
where the "metal compound" is a chromium compound; non-limiting examples
include
say' chromate, chromium oxide and chromocene. In some embodiments, the
chromium compound is supported on a metal oxide such as silica or alumina.
Heterogeneous catalyst formulations containing chromium may also include co-
catalysts; non-limiting ex4mples of co-catalysts include trialkylaluminum,
alkylaluminoxane and dialkoxyalkylaluminum compounds and the like.
Solution Polymerization Process
The disclosed continuous solution polymerization process is improved by having
one
or more of: 1) at least a 70% reduced [a-olefin/ethylene] weight ratio as
defined by the
following formula,
(a ¨ olefin\A (a ¨ olefin\c
[
a ¨ olefin ethylene) ethylene)
% Reduced _______ = 100 x ______________________ < ¨70%
ethylene I (a ¨ olefin )C
ethylene
wherein (a-olefin/ethylene)' is calculated by dividing the weight of the a-
olefin added
to the first reactor by the weight of ethylene added to the first reactor,
wherein a first
ethylene interpolymer is produced having "a target density" using a first
homogeneous
catalyst formulation, and; (a-olefin/ethylene)c is calculated by dividing the
weight of
the a-olefin added to the first reactor by the weight of the ethylene added to
the first
reactor, wherein a control ethylene interpolymer having the target density is
produced
by replacing the first homogeneous catalyst formulation with a third
homogeneous
catalyst formulation, and/or; 2) the first ethylene interpolymer at least a 5%
improved
weight average molecular weight as defined by the following formula
% Improved Mw = 100% x (Mv/\-Mwc)/Mwc 5%
wherein MwA is a weight average molecular weight of the first ethylene
interpolymer
and Mwc is a weight average molecular weight of a comparative ethylene
interpolymer;
wherein said comparative ethylene interpolymer is produced in the first
reactor by
replacing the first homogeneous catalyst formulation with the third
homogeneous
catalyst formulation.
=
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Embodiments of the improved continuous solution polymerization process are
shown
in Figure 2. Figure 2 is not to be construed as limiting, it being understood,
that
embodiments are not limited to the precise arrangement of, or the number of,
vessels
shown.
In an embodiment of the continuous solution polymerization process, process
solvent,
monomer(s) and a catalyst formulation are continuously fed to a reactor
wherein the
desired ethylene interpolymer is formed in solution. In Figure 2, process
solvent 1,
ethylene 2 and optional a-olefin 3 are combined to produce reactor feed stream
RF1
which flows into reactor 11a. In Figure 2 optional streams, or optional
embodiments,
are denoted with dotted lines. It is not particularly important that combined
reactor
feed stream RF1 be formed; i.e. reactor feed streams can be combined in all
possible
combinations, including an embodiment where streams 1 through 3 are
independently
injected into reactor 11a. Optionally hydrogen may be injected into reactor
lla
through stream 4; hydrogen may be added to control (reduce) the molecular
weight of
the first ethylene interpolymer produced in reactor 11a. Reactor lla is
continuously
stirred by stirring assembly llb which includes a motor external to the
reactor and an
agitator within the reactor. In the art, such a reactor is frequently called a
CSTR
(Continuously Stirred Tank Reactor).
A first homogeneous catalyst formulation is injected into reactor lla through
stream
5e. An embodiment of the first homogeneous catalyst formulation is a bridged
metallocene catalyst formulation. The bridged metallocene catalyst formulation
(described above) was employed in reactor 11 a to produce all of the Examples
in this
disclosure. In contrast, a third homogeneous catalyst formulation was employed
in
reactor lla to produce all of the Comparatives in this disclosure. As
described above,
one embodiment of the third homogeneous catalyst formulation was an unbridged
single site catalyst formulation.
Referring to Figure 2, the bridged metallocene catalyst formulation was
prepared by
combining: stream 5a, containing a component Pm dissolved in a catalyst
component
solvent; stream 5b, containing a component MA1 dissolved in a catalyst
component
solvent; stream 5c, containing a bulky ligand-metal complex component Al
dissolved
in a catalyst component solvent, and; stream 5d, containing component Bm
dissolved
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in a catalyst component solvent. The bridged metallocene catalyst formulation
was
then injected into reactor lla via process stream 5e. Any combination of the
streams
employed to prepare and deliver the bridged metallocene catalyst formulation
may be
heated or cooled, i.e. streams 5a through 5e.
The "R1 catalyst inlet temperature", defined as the temperature of the
solution
containing the bridged metallocene catalyst formulation (stream 5e) prior to
injection
into reactor 11a, was controlled. In some cases the upper temperature limit on
the R1
catalyst inlet temperature may be about 180 C, in other cases about 160 C and
in still
other cases about 150 C, and; in some cases the lower temperature limit on the
R1
catalyst inlet temperature may be about 80 C, in other cases 100 C and in
still other
cases about 120 C. In still other cases the upper temperature limit on the R1
catalyst
inlet temperature may be about 70 C, in other cases about 60 C and in still
other
cases about 50 C, and; in some cases the lower temperature limit on the R1
catalyst
inlet temperature may be about 0 C, in other cases 10 C and in still other
cases about
C.
Each catalyst component was dissolved in a catalyst component solvent. The
catalyst
component solvent used.for each catalyst component may be the same or
different.
20 Catalyst component solvents are selected such that the combination of
catalyst
components does not produce a precipitate in any process stream; for example,
precipitation of a catalyst components in stream 5e. The optimization of the
catalyst
formulations are described below.
Reactor 11a produces a first exit stream, stream 11c, containing the first
ethylene
interpolymer dissolved in process solvent, as well as unreacted ethylene,
unreacted a-
olefins (if present), unreacted hydrogen (if present), active first
homogeneous catalyst,
deactivated catalyst, residual catalyst components and other impurities (if
present).
Melt index ranges and density ranges of the first ethylene interpolymer
produced are
described below.
The continuous solution polymerization process shown in Figure 2 includes two
embodiments where reaCtors 11a and 12a can be operated in series or parallel
modes. In series mode 100% of stream 11c (the first exit stream) passes
through flow
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controller 11d forming stream 11e which enters reactor 12a. In contrast, in
parallel
mode 100% of stream 11c passes through flow controller 11f forming stream 11g.
Stream llg by-passes reactor 12a and is combined with stream 12c (the second
exit
stream) forming stream 12d (the third exit stream).
Fresh reactor feed streams are injected into reactor 12a; process solvent 6,
ethylene 7
and optional a-olefin 8 are combined to produce reactor feed stream RF2. It is
not
important that stream RF2 is formed; i.e. reactor feed streams can be combined
in all
possible combinations, including independently injecting each stream into the
reactor.
Optionally hydrogen may be injected into reactor 12a through stream 9 to
control
(reduce) the molecular weight of the second ethylene interpolymer. Reactor 12a
is
continuously stirred by stirring assembly 12b which includes a motor external
to the
reactor and an agitator within the reactor.
A second homogeneous catalyst formulation was injected in reactor 12a through
stream 10e, one embodiment of the second homogeneous catalyst formulation is
an
unbridged single site catalyst formulation which produces a second ethylene
interpolymer in reactor 12a. The components that comprise the unbridged single
site
catalyst formulation are introduced through streams 10a, 10b, 10c and 10d. The
unbridged single site catalyst formulation was prepared by combining: stream
10a,
containing a component Pc1 dissolved in a catalyst component solvent; stream
10b,
containing a component Mcl dissolved in a catalyst component solvent; stream
10c,
containing a bulky ligand-metal complex component Cl dissolved in a catalyst
component solvent, and; stream 10d, containing component I3c1 dissolved in a
catalyst component solvent. The unbridged single site catalyst formulation was
then
injected into reactor 12a via process stream 10e. Any combination of the
streams
employed to prepare and deliver the unbridged single site catalyst formulation
may be
heated or cooled, i.e. streams 10a through 10e. Each catalyst component was
dissolved in a catalyst component solvent. The catalyst component solvents
used to
synthesize the unbridged single site catalyst formulation may be the same or
different.
Catalyst component solvents are selected such that the combination of catalyst
components does not produce a precipitate in any process stream; for example,
precipitation of a catalyst components in stream 10e. The optimization of the
catalyst
formulations are described below. The "R2 catalyst inlet temperature", defined
as the
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temperature of the solution containing the bridged metallocene catalyst
formulation
(stream 10e) prior to injection into reactor 12a, was controlled. In some
cases the
upper temperature limit on the R2 catalyst inlet temperature may be about 70
C, in
other cases about 60 C and in still other cases about 50 C, and; in some cases
the
lower temperature limit on the R2 catalyst inlet temperature may be about 0 C,
in
other cases 10 C and in still other cases about 20 C. Any combination of the
streams
employed to prepare and deliver the second homogeneous catalyst formulation to
the
second reactor (R2) may be heated or cooled, i.e. streams 10a through 10e.
Injection of the second homogeneous catalyst formulation into reactor 12a
produces a
second ethylene interpolymer and a second exit stream 12c.
If reactors lla and 12a are operated in a series mode, the second exit stream
12c
contains the second ethylene interpolymer and the first ethylene interpolymer
dissolved in process solvent; as well as unreacted ethylene, unreacted a-
olefins (if
present), unreacted hydrogen (if present), active catalysts, deactivated
catalysts,
catalyst components and other impurities (if present). Optionally the second
exit
stream 12c is deactivated by adding a catalyst deactivator A from catalyst
deactivator
tank 18A forming a deactivated solution A, stream 12e; in this case, Figure 2
defaults
to a dual reactor solution process. If the second exit stream 12c is not
deactivated the
second exit stream enters tubular reactor 17. Catalyst deactivator A is
discussed
below.
If reactors lla and 12a are operated in parallel mode, the second exit stream
12c
contains the second ethylene interpolymer dissolved in process solvent. The
second
exit stream 12c is combined with stream llg forming a third exit stream 12d,
the latter
contains the second ethylene interpolymer and the first ethylene interpolymer
dissolved in process solvent; as well as unreacted ethylene, unreacted a-
olefins (if
present), unreacted hydrogen (if present), active catalyst, deactivated
catalyst,
catalyst components and other impurities (if present). Optionally the third
exit stream
12d is deactivated by adding catalyst deactivator A from catalyst deactivator
tank 18A
forming deactivated solution A, stream 12e; in this case, Figure 2 defaults to
a dual
reactor solution process. If the third exit stream 12d is not deactivated the
third exit
stream 12d enters tubular reactor 17.
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The term "tubular reactor" is meant to convey its conventional meaning, namely
a
simple tube; wherein the length/diameter (L/D) ratio is at least 10/1.
Optionally, one or
more of the following reactor feed streams may be injected into tubular
reactor 17;
process solvent 13, ethylene 14 and a-olefin 15. As shown in Figure 2, streams
13,
14 and 15 may be combined forming reactor feed stream RF3 and the latter is
injected
into reactor 17. It is not particularly important that stream RF3 be formed;
i.e. reactor
feed streams can be combined in all possible combinations. Optionally hydrogen
may
be injected into reactor 17 through stream 16.
Optionally, the first and/or the second homogeneous catalyst formulations may
be
injected into reactor 17 (not shown in Figure 2). This could be accomplished
by
feeding a portion of stream 5e to reactor 17 and/or feeding a portion of
stream 10e to
reactor 17. Alternatively, a non-limiting embodiment includes a fifth
homogenous
catalyst assembly (not shown in Figure 2) that manufactures and injects a
fifth
homogeneous catalyst formulation into reactor 17. The fifth homogeneous
catalyst
assembly refers to a combination of tanks, conduits and flow controllers
similar to 5a
through 5e shown in Figure 2 (i.e. the first homogeneous catalyst assembly) or
similar
to 10a through 10e shown in Figure 2 (i.e. the second homogeneous catalyst
assembly). The fifth homogeneous catalyst formulation may be the first
homogeneous catalyst formulation, the second homogeneous catalyst formulation
or
the fourth homogeneous.catalyst formulation.
Optionally, a heterogeneous catalyst formulation may be injected into reactor
17. One
embodiment of a heterogeneous catalyst formulation includes an in-line Ziegler-
Natta
catalyst formulation. Figure 2 illustrates an in-line heterogeneous catalyst
assembly,
defined by conduits and flow controllers 34a through 34h, that manufactures
and
injects an in-line Ziegler-Natta catalyst formulation into tubular reactor 17.
The in-line heterogeneous catalyst assembly generates a high activity catalyst
by
optimizing hold-up-times and the following molar ratios: (aluminum
alkyl)/(magnesium
compound), (chloride compound)/(magnesium compound), (alkyl aluminum co-
catalyst/(metal compound, and (aluminum alkyl)/(metal compound). To be clear:
stream 34a contains a binary blend of magnesium compound (component (v)) and
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aluminum alkyl (component (ix)) in process solvent; stream 34b contains a
chloride
compound (component (vi)) in process solvent; stream 34c contains a metal
compound (component (vii)) in process solvent, and; stream 34d contains an
alkyl
aluminum co-catalyst (component (viii)) in process solvent. To produce a
highly active
in-line Ziegler-Natta catalyst (highly active in olefin polymerization), the
(chloride
compound)/(magnesium compound) molar ratio is optimized. The upper limit on
the
(chloride compound)/(magnesium compound) molar ratio may be about 4, in some
cases about 3.5 and is other cases about 3Ø The lower limit on the (chloride
compound)/(magnesium compound) molar ratio may be about 1.0, in some cases
about 1.5 and in other cases about 1.9. The time between the addition of the
chloride
compound and the addition of the metal compound (component (vii)) via stream
34c is
controlled; hereinafter HUT-1 (the first Hold-Up-Time). HUT-1 is the time for
streams
34a and 34b to equilibrate and form a magnesium chloride support. The upper
limit
on HUT-1 may be about 70 seconds, in some cases about 60 seconds and is other
cases about 50 seconds. The lower limit on HUT-1 may be about 5 seconds, in
some
cases about 10 seconds and in other cases about 20 seconds. HUT-1 is
controlled by
adjusting the length of the conduit between stream 34b injection port and
stream 34c
injection port, as well as controlling the flow rates of streams 34a and 34b.
The time
between the addition of component (vii) and the addition of the alkyl aluminum
co-
catalyst, component (viii), via stream 34d is controlled; hereinafter HUT-2
(the second
Hold-Up-Time). HUT-2 is the time for the magnesium chloride support and stream
34c to react and equilibrate. The upper limit on HUT-2 may be about 50
seconds, in
some cases about 35 seconds and is other cases about 25 seconds. The lower
limit
on HUT-2 may be about 2 seconds, in some cases about 6 seconds and in other
cases about 10 seconds. HUT-2 is controlled by adjusting the length of the
conduit
between stream 34c injection port and stream 34d injection port, as well as
controlling
the flow rates of streams 34a, 34b and 34c. The quantity of the alkyl aluminum
co-
catalyst added is optimized to produce an efficient catalyst; this is
accomplished by
adjusting the (alkyl aluminum co-catalyst)/(metal compound) molar ratio, or
(viii)/(vii)
molar ratio. The upper limit on the (alkyl aluminum co-catalyst)/(metal
compound)
molar ratio may be about 10, in some cases about 7.5 and is other cases about
6Ø
The lower limit on the (alkyl aluminum co-catalyst)/(metal compound) molar
ratio may
be 0, in some cases about 1.0 and in other cases about 2Ø In addition, the
time
between the addition of the alkyl aluminum co-catalyst and the injection of
the in-line
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Ziegler-Natta catalyst formulation into reactor 17 is controlled; hereinafter
HUT-3 (the
third Hold-Up-Time). HUT-3 is the time for stream 34d to intermix and
equilibrate to
form the in-line Ziegler Natta catalyst formulation. The upper limit on HUT-3
may be
about 15 seconds, in some cases about 10 seconds and is other cases about 8
seconds. The lower limit on HUT-3 may be about 0.5 seconds, in some cases
about 1
seconds and in other cases about 2 seconds. HUT-3 is controlled by adjusting
the
length of the conduit between stream 34d injection port and the catalyst
injection port
in reactor 17, and by controlling the flow rates of streams 34a through 34d.
As shown
in Figure 2, optionally, 100% of stream 34d, the alkyl aluminum co-catalyst,
may be
injected directly into reactor 17 via stream 34h. Optionally, a portion of
stream 34d
may be injected directly into reactor 17 via stream 34h and the remaining
portion of
stream 34d injected into reactor 17 via stream 34f. In Figure 2, the in-line
heterogeneous catalyst assembly supplies 100% of the catalyst to reactor 17.
Any
combination of the streams that comprise the in-line heterogeneous catalyst
assembly
may be heated or cooled, i.e. streams 34a-34e and 34h; in some cases the upper
temperature limit of streams 34a-34e and 34h may be about 90 C, in other cases
about 80 C and in still other cases about 70 C and; in some cases the lower
temperature limit may be about 20 C; in other cases about 35 C and in still
other
cases about 50 C. The quantity of the in-line Ziegler-Natta catalyst
formulation added
to reactor 17 was expressed as the parts-per-million (ppm) of metal compound
(component (vii)) in the reactor solution. The upper limit on component (vii)
in reactor
17 may be about 10 ppm, in some cases about 8 ppm and in other cases about 6
ppm; while the lower limit may be about 0.5 ppm, in other cases about 1 ppm
and in
still other cases about 2 ppm. The (aluminum alkyl)/(metal compound) molar
ratio in
reactor 17, or the (ix)/(vii) molar ratio, is also controlled. The upper limit
on the
(aluminum alkyl)/(metal compound) molar ratio in the reactor may be about 2,
in some
cases about 1.5 and is other cases about 1Ø The lower limit on the (aluminum
alkyl)/(metal compound) molar ratio may be about 0.05, in some cases about
0.075
and in other cases about 0.1.
Optionally, an additional embodiment of a heterogeneous catalyst formulation
includes
a batch Ziegler-Natta catalyst formulation. Figure 2 illustrates a batch
heterogeneous
catalyst assembly, defined by conduits and flow controllers 90a through 90f.
The
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batch heterogeneous catalyst assembly manufactures and injects the batch
Ziegler-
Natta catalyst formulation, or a batch Ziegler-Natta procatalyst, into tubular
reactor 17.
Processes to prepare batch Ziegler-Natta procatalysts are well known to those
skilled
in the art. A non-limiting formulation useful in the disclosed polymerization
process
may be prepared as follows. A batch Ziegler-Natta procatalyst may be prepared
by
sequentially added the following components to a stirred mixing vessel: (a) a
solution
of a magnesium compound (an equivalent term for the magnesium compound is
"component (v)"); (b) a solution of a chloride compound (an equivalent term
for the
chloride compound is "component (vi)"; (c) optionally a solution of an
aluminum alkyl
halide, and; (d) a solution of a metal compound (an equivalent term for the
metal
compound is "component (vii)"). Suitable, non-limiting examples of aluminum
alkyl
halides are defined by the formula (R6)vAIX3_v; wherein the R6 groups may be
the
same or different hydrocarbyl group having from 1 to 10 carbon atoms, X
represents
chloride or bromide, and; v is 1 or 2. Suitable, non-limiting examples of the
magnesium compound, the chloride compound and the metal compound were
described earlier in this disclosure. Suitable solvents within which to
prepare the
procatalyst include linear or branched C5 to C12 alkanes or mixtures thereof.
Individual mixing times and mixing temperatures may be used in each of steps
(a)
through (d). The upper limit on mixing temperatures for steps (a) through (d)
in some
case may be 160 C, in other cases 130 C and in still other cases 100 C. The
lower
limit on mixing temperatures for steps (a) through (d) in some cases may be 10
C, in
other cases 20 C and in still other cases 30 C. The upper limit on mixing time
for
steps (a) through (d) in some case may be 6 hours, in other cases 3 hours and
in still
other cases 1 hour. Thelower limit on mixing times for steps (a) through (d)
in some
cases may be 1 minute, in other cases 10 minutes and in still other cases 30
minutes.
Batch Ziegler-Natta procatalyst may have various catalyst component mole
ratios.
The upper limit on the (chloride compound)/(magnesium compound) molar ratio in
some cases may be about 3, in other cases about 2.7 and is still other cases
about
2.5; the lower limit in some cases may be about 2.0, in other cases about 2.1
and in
still other cases about 2.2. The upper limit on the (magnesium
compound)/(metal
compound) molar ratio in some cases may be about 10, in other cases about 9
and in
still other cases about 8; the lower limit in some cases may be about 5, in
other cases
about 6 and in still other cases about 7. The upper limit on the (aluminum
alkyl
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halide)/(magnesium compound) molar ratio in some cases may be about 0.5, in
other
cases about 0.4 and in still other cases about 0.3; the lower limit in some
cases may
be 0, in other cases about 0.1 and in still other cases about 0.2. An active
batch
Ziegler-Natta catalyst formulation is formed when the procatalyst is combined
with an
alkyl aluminum co-catalyst. Suitable co-catalysts were described earlier in
this
disclosure. The procatalyst may be activated external to the reactor or in the
reactor;
in the latter case, the procatalyst and an appropriate amount of alkyl
aluminum co-
catalyst are independently injected R2 and optionally R3.
Once prepared the batch Ziegler-Natta procatalyst is pumped to procatalyst
storage
tank 90a shown in Figure 2. Tank 90a may, or may not, be agitated. Storage
tank
90c contains an alkyl aluminum co-catalyst. A batch Ziegler Natta catalyst
formulation
stream 90e, that is efficient in converting olefins to polyolefins, is formed
by combining
the batch Ziegler Natta procatalyst stream 90b with alkyl aluminum co-catalyst
stream
90d. Stream 90e is optionally injected into reactor 17, wherein an optional
third
ethylene interpolymer may be formed. Figure 2 includes additional embodiments
where: (a) the batch Ziegler-Natta procatalyst is injected directly into
reactor 17
through stream 90e and the procatalyst is activated inside reactor 17 by
injecting
100% of the aluminum co-catalyst directly into rector 17 via stream 90f, or;
(b) a
portion of the aluminum co-catalyst may flow through stream 90e with the
remaining
portion flowing through stream 90f. Any combination of tanks or streams 90a
through
90f may be heated or cooled. The time between the addition of the alkyl
aluminum
co-catalyst and the injection of the batch Ziegler-Natta catalyst formulation
into reactor
17 is controlled. Referring to Figure 2, HUT-4 is the time for stream 90d to
intermix
and equilibrate with stream 90b (batch Ziegler-Natta procatalyst) to form the
batch
Ziegler Natta catalyst formulation prior to injection into reactor 17 via in
stream 90e.
The upper limit on HUT-4 may be about 300 seconds, in some cases about 200
seconds and in other cases about 100 seconds. The lower limit on HUT-4 may be
about 0.1 seconds, in some cases about 1seconds and in other cases about 10
seconds. The quantity of batch Ziegler-Natta procatalyst or batch Ziegler-
Natta
catalyst formulation added to reactor 17 was expressed the parts-per-million
(ppm) of
metal compound (component (vii)) in the reactor solution. The upper limit on
component (vii) may be about 10 ppm, in some cases about 8 ppm and in other
cases
about 6 ppm; while the lower limit may be about 0.5 ppm, in some cases about 1
ppm
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and in other cases about 2 ppm. The quantity of the alkyl aluminum co-catalyst
added
to reactor 17 is optimized to produce an efficient catalyst; this is
accomplished by
adjusting the (alkyl aluminum co-catalyst)/(metal compound) molar ratio. The
upper
limit on the (alkyl aluminum co-catalyst)/(metal compound) molar ratio may be
about
10, in some cases about 8.0 and is other cases about 6Ø The lower limit on
the
(alkyl aluminum co-catalyst)/(metal compound) molar ratio may be 0.5, in some
cases
about 0.75 and in other cases about 1.
The quantity of batch Ziegler-Natta procatalyst produced and/or the size to
procatalyst
storage tank 90a is not particularly important with respect to this
disclosure. However,
the large quantity of procatalyst produced allows one to operate the
continuous
solution polymerization plant for an extended period of time: the upper limit
on this
time in some cases maybe about 3 months, in other cases for about 2 months and
in
still other cases for about 1 month; the lower limit on this time in some
cases may be
about 1 day, in other cases about 1 week and in still other cases about 2
weeks.
In reactor 17 a third ethylene interpolymer may, or may not, form. A third
ethylene
interpolymer will not form if catalyst deactivator A is added upstream of
reactor 17 via
catalyst deactivator tank 18A (as shown in Figure 2). In contrast, A third
ethylene
interpolymer will be formed if catalyst deactivator B is added downstream of
reactor 17
via catalyst deactivator tank 18B.
The optional third ethylene interpolymer produced in reactor 17 may be formed
using
a variety of operational modes; with the proviso that catalyst deactivator A
is not
added upstream of reactor 17. Non-limiting examples of operational modes
include:
(a) residual ethylene, residual optional a-olefin and residual active catalyst
entering
reactor 17 react to form the optional third ethylene interpolymer, or; (b)
fresh process
solvent 13, fresh ethylene 14 and optionally fresh a-olefin 15 are added to
reactor 17
and the residual active catalyst entering reactor 17 forms the optional third
ethylene
interpolymer, or; (c) a fifth homogeneous catalyst formulation is added to
reactor 17 to
polymerize residual ethylene and residual optional a-olefin to form the third
ethylene
interpolymer, or; (d) an in-line Ziegler-Natta catalyst formulation is added
to reactor
17 via stream 34e (Figure 2) to polymerize residual ethylene and residual
optional a-
olefin to form the third ethylene interpolymer, or; (e) a batch Ziegler-Natta
catalyst
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formulation is added to reactor 17 via stream 90e (Figure 2) to polymerize
residual
ethylene and residual optional a-olefin to form the third ethylene
interpolymer, or; (d)
fresh process solvent (stream 13), ethylene (stream 14), optional a-olefin
(stream 15)
and a fifth homogeneous catalyst formulation, or an in-line Ziegler-Natta
catalyst
formulation or a batch Ziegler-Natta catalyst formulation are added to reactor
17 to
form the third ethylene interpolymer. Optionally fresh hydrogen (stream 16)
may be
added to control (reduce) the molecular weight of the third optional ethylene
interpolymer.
In series mode, Reactor 17 produces a third exit stream 17b containing the
first
ethylene interpolymer, the second ethylene interpolymer and optionally a third
ethylene interpolymer. As shown in Figure 2, catalyst deactivator B may be
added to
the third exit stream 17b via catalyst deactivator tank 18B producing a
deactivated
solution B, stream 19; with the proviso that catalyst deactivator B is not
added if
catalyst deactivator A was added upstream of reactor 17. Deactivated solution
B may
also contain unreacted ethylene, unreacted optional a-olefin, unreacted
optional
hydrogen and impurities if present. As indicated above, if catalyst
deactivator A was
added, deactivated solution A (stream 12e) exits tubular reactor 17 as shown
in Figure
2.
In parallel mode operation, reactor 17 produces a fourth exit stream 17b
containing
the first ethylene interpolymer, the second ethylene interpolymer and
optionally a third
ethylene interpolymer. As described above, in parallel mode stream 12d was the
third
exit stream. As shown in Figure 2, in parallel mode catalyst deactivator B is
added to
the fourth exit stream 17b via catalyst deactivator tank 18B producing a
deactivated
solution B, stream 19; with the proviso that catalyst deactivator B is not
added if
catalyst deactivator A was added upstream of reactor 17.
In Figure 2, deactivated solution A (stream 12e) or B (stream 19) passes
through
pressure let down device 20, heat exchanger 21 and optionally a passivator was
added via tank 22 forming a passivated solution stream 23; the passivator is
described below. The passivator was added, and stream 23 was formed, only if a
heterogeneous catalyst formulation was added to reactor 1,7. Stream 19, or
optional
stream 23, passes through pressure let down device 24 and entered a first
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vapor/liquid separator 25. Hereinafter, "V/L" is equivalent to vapor/liquid.
Two
streams were formed in the first V/L separator: a first bottom stream 27
comprising a
solution that was rich in ethylene interpolymers and also contains residual
ethylene,
residual optional a-olefins and catalyst residues, and; a first gaseous
overhead stream
26 comprising ethylene, process solvent, optional a-olefins, optional
hydrogen,
oligomers and light-end impurities if present.
The first bottom stream entered a second V/L separator 28. In the second V/L
separator two streams were formed: a second bottom stream 30 comprising a
solution
that was richer in ethylene interpolymer and leaner in process solvent
relative to the
first bottom stream 27, and; a second gaseous overhead stream 29 comprising
process solvent, optional a-olefins, ethylene, oligomers and light-end
impurities if
present.
The second bottom stream 30 flowed into a third V/L separator 31. In the third
V/L
separator two streams were formed: a product stream 33 comprising an ethylene
interpolymer product, deactivated catalyst residues and less than 5 weight %
of
residual process solvent, and; a third gaseous overhead stream 32 comprised
essentially of process solvent, optional a-olefins and light-end impurities if
present.
Product stream 33 proceeded to polymer recovery operations. Non-limiting
examples
of polymer recovery operations include one or more gear pump, single screw
extruder
or twin screw extruder that forces the molten ethylene interpolymer product
through a
pelletizer. A devolatilizing extruder may be used to remove small amounts of
residual
process solvent and optional a-olefin, if present. Once pelletized the
solidified
ethylene interpolymer product is typically dried and transported to a product
silo.
The first, second and third gaseous overhead streams shown in Figure 2
(streams 26,
29 and 32, respectively) were sent to a distillation column where solvent,
ethylene and
optional a-olefin were separated for recycling, or; the first, second and
third gaseous
overhead streams were recycled to the reactors, or; a portion of the first,
second and
third gaseous overhead streams were recycled to the reactors and the remaining
portion was sent to a distillation column.
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Comparatives
In this disclosure Comparative ethylene interpolymer samples were produced by
replacing the first homogeneous catalyst formulation (used in the first
reactor (R1))
with a third homogeneous catalyst formulation. One embodiment of the first
homogeneous catalyst formulation was a bridged metallocene catalyst
formulation
containing component A (represented by Formula (I)) and one embodiment of the
third
homogeneous catalyst formulation was an unbridged single site catalyst
formulation
containing component C (represented by Formula (II)), as fully described
above.
To be more clear, referring to Figure 2, the third homogeneous catalyst
formulation or
the unbridged single site catalyst formulation was prepared by combining:
stream 5a,
containing component P dissolved in a catalyst component solvent; stream 5b,
containing component M dissolved in a catalyst component solvent; stream 5c,
containing component C'dissolved in a catalyst component solvent, and; stream
5d,
containing component B dissolved in a catalyst component solvent. The third
homogeneous catalyst formulation was then injected into reactor lla via
process
stream 5e producing a comparative first ethylene interpolymer in reactor 11a.
The
"R1 catalyst inlet temperature" was controlled. In the case of the unbridged
singe site
catalyst formulation the upper temperature limit on the R1 catalyst inlet
temperature
may be about 70 C, in other cases about 60 C and in still other cases about 50
C,
and; in some cases the lower temperature limit on the R1 catalyst inlet
temperature
may be about 0 C, in other cases about 10 C and in still other cases about 20
C. The
same catalyst component solvents were used to prepare both the first and third
homogeneous catalyst formulations.
For all Comparative ethylene interpolymer products disclosed, the second
homogeneous catalyst formulation (described above) was injected into reactor
12a
(R2), wherein the second ethylene interpolymer was formed. Comparative
ethylene
interpolymer products were an in-situ solution blend of: 1) the comparative
first
ethylene interpolymer (produced with the third homogeneous catalyst
formulation); 2)
the second ethylene interpolymer, and; 3) optionally the third ethylene
interpolymer.
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Optimization of Homogeneous Catalyst Formulations
Referring to the first homogeneous catalyst formulation, one embodiment being
the
bridged metallocene catalyst formulation, a highly active formulation was
produced by
optimizing the proportion of each of the four catalyst components: component
A,
component M, component B and component P. The term "highly active" means the
catalyst formulation is very efficient in converting olefins to polyolefins.
In practice the
optimization objective is to maximize the following ratio: (pounds of ethylene
interpolymer product produced)/(pounds of catalyst consumed). The quantity of
the
bulky ligand-metal complex, component A, added to R1 was expressed as the
parts
per million (ppm) of component A in the total mass of the solution in R1, i.e.
"R1
catalyst (ppm)" as recited in Table 4A. The upper limit on the ppm of
component A
may be about 5, in some cases about 3 and is other cases about 2. The lower
limit on
the ppm of component A may be about 0.02, in some cases about 0.05 and in
other
cases about 0.1.
The proportion of catalyst component B, the ionic activator, added to R1 was
optimized by controlling the (ionic activator)/(component A) molar ratio,
([B]/[A]), in the
R1 solution. The upper limit on the R1 ([B]/[A]) may be about 10, in some
cases about
5 and in other cases about 2. The lower limit on R1 ([13]/[A]) may be about
0.3, in
some cases about 0.5 and in other cases about 1Ø The proportion of catalyst
component M was optimized by controlling the (alumoxane)/(component A) molar
ratio, ([M]/[A]), in the R1 solution. The alumoxane co-catalyst was generally
added in
a molar excess relative to component A. The upper limit on R1 ([M]/[A]), may
be
about 300, in some cases about 200 and is other cases about 100. The lower
limit on
R1 ([M]/[A]), may be about 1, in some cases about 10 and in other cases about
30.
The addition of catalyst component P (the hindered phenol) to R1 is optional.
If
added, the proportion of component P was optimized by controlling the
(hindered
phenol)/(alumoxane), ([P]/[1A), molar ratio in R1. The upper limit on R1
([P]/[M]) may
be about 1, in some cases about 0.75 and in other cases about 0.5. The lower
limit
on R1 ([P]/[M]) may be 0.0, in some cases about 0.1 and in other cases about
0.2.
Referring to the second homogeneous catalyst formulation, one embodiment being
the unbridged single site catalyst formulation, a highly active formulation
was
produced by optimizing the proportion of each of the four catalyst components:
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component C, component M, component B and component P. Catalyst components
M, B and P were independently selected for the second homogeneous catalyst
formulation, relative to the first homogeneous catalyst formulation. To be
more clear,
components M, B and P in the second homogeneous catalyst formulation may be
the
same chemical compound, or a different chemical compound, that was used to
formulate the first homogeneous catalyst formulation.
The quantity of the bulky ligand metal complex, component C, added to R2 was
expressed as the parts per million (ppm) of component C in the total mass of
the
solution in R2, i.e. "R2 catalyst (ppm)" shown in Table 4A. The upper limit on
the R2
ppm of component C may be about 5, in some cases about 3 and is other cases
about
2. The lower limit on the R2 ppm of component C may be about 0.02, in some
cases
about 0.05 and in other cases about 0.1. The proportion of catalyst component
B, the
ionic activator, added to R2 was optimized by controlling the (ionic
activator)/(bulky
ligand-metal complex) molar ratio, ([6]/[C]), in the R2 solution. The upper
limit on R2
([13]/[C]) may be about 10, in some cases about 5 and in other cases about 2.
The
lower limit on R2 ([B]/[C]) may be about 0.3, in some cases about 0.5 and in
other
cases about 1Ø The proportion of catalyst component M was optimized by
controlling the (alumoxane)/(bulky ligand-metal complex) molar ratio,
([M]/[C]), in the
R2 solution. The alumoxane co-catalyst was generally added in a molar excess
relative to the bulky ligand-metal complex. The upper limit on the ([M]/[C])
molar ratio
may be about 1000, in some cases about 500 and is other cases about 200. The
lower limit on the ([M]/[C]) molar ratio may be about 1, in some cases about
10 and in
other cases about 30. The addition of catalyst component P to R2 is optional.
If
added, the proportion of component P was optimized by controlling the
(hindered
phenol)/(alumoxane) molar ratio, ([P]/[M]), in R2. The upper limit on the R2
([P]/[M])
molar ratio may be about 1.0, in some cases about 0.75 and in other cases
about 0.5.
The lower limit on the R2 ([P]/[M]) molar ratio may be 0.0, in some cases
about 0.1
and in other cases about 0.2.
In the case of the third homogeneous catalyst formulation that was used to
synthesize
Comparative ethylene interpolymer products a highly active formulation was
produced
by optimizing the proportion of each of the four catalyst components:
component C,
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component M, component B and component P; in a similar fashion to that
described
above for the second homogeneous catalyst formulation.
Additional Solution Polymerization Process Parameters
In the continuous solution processes embodiments shown in Figure 2 a variety
of
solvents may be used as the process solvent; non-limiting examples include
linear,
branched or cyclic 05 to 012 alkanes. Non-limiting examples of a-olefins
include 1-
propene, 1-butene, 1-pentene, 1-hexene and 1-octene. Suitable catalyst
component
solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of
aliphatic catalyst component solvents include linear, branched or cyclic C5-12
aliphatic
hydrocarbons, e.g. pentane, methyl pentane, hexane, heptane, octane,
cyclohexane,
methylcyclohexane, hydrogenated naphtha or combinations thereof. Non-limiting
examples of aromatic catalyst component solvents include benzene, toluene
(methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-
dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures of xylene isomers,
hemellitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene),
mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzene isomers,
prehenitene (1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene),
mixtures of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene
and combinations thereof.
It is well known to individuals experienced in the art that reactor feed
streams (solvent,
monomer, a-olefin, hydrogen, catalyst formulation etc.) must be essentially
free of
catalyst deactivating poisons; non-limiting examples of poisons include trace
amounts
of oxygenates such as water, fatty acids, alcohols, ketones and aldehydes.
Such
poisons were removed from reactor feed streams using standard purification
practices; non-limiting examples include molecular sieve beds, alumina beds
and
oxygen removal catalysts for the purification of solvents, ethylene and a-
olefins, etc.
Referring to the first and second reactors in Figure 2 any combination of the
CSTR
reactor feed streams may be heated or cooled: more specifically, streams 1 ¨ 4
(reactor 11a) and strearris 6 ¨ 9 (reactor 12a). The upper limit on reactor
feed stream
temperatures may be about 90 C; in other cases about 80 C and in still other
cases
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about 70 C. The lower limit on reactor feed stream temperatures may be about 0
C;
in other cases about 10 C and in still other cases about 20 C.
Any combination of the streams feeding the tubular reactor may be heated or
cooled;
specifically, streams 13 7 16 in Figure 2. In some cases, tubular reactor feed
streams
are tempered, i.e. the tubular reactor feed streams are heated to at least
above
ambient temperature. The upper temperature limit on the tubular reactor feed
streams
in some cases are about 200 C, in other cases about 170 C and in still other
cases
about 140 C; the lower temperature limit on the tubular reactor feed streams
in some
cases are about 60 C, in other cases about 90 C and in still other cases about
120 C;
with the proviso that the temperature of the tubular reactor feed streams are
lower
than the temperature of the process stream that enters the tubular reactor.
In the embodiments shown in Figure 2 the operating temperatures of the
solution
polymerization reactors (vessels 11a (R1) and 12a (R2)) can vary over a wide
range.
For example, the upper limit on reactor temperatures in some cases may be
about
300 C, in other cases about 280 C and in still other cases about 260 C; and
the lower
limit in some cases may be about 80 C, in other cases about 100 C and in still
other
cases about 125 C. The second reactor, reactor 12a (R2), is operated at a
higher
temperature than the first reactor 11a (R1). The maximum temperature
difference
between these two reactors (TR2- TR1) in some cases is about 120 C, in other
cases
about 100 C and in still other cases about 80 C; the minimum (TR2 - TR1) in
some
cases is about 1 C, in other cases about 5 C and in still other cases about 10
C. The
optional tubular reactor, reactor 17 (R3), may be operated in some cases about
100 C
higher than R2; in other cases about 60 C higher than R2, in still other cases
about
10 C higher than R2 and in alternative cases 0 C higher, i.e. the same
temperature as
R2. The temperature within optional R3 may increase along its length. The
maximum
temperature difference between the inlet and outlet of R3 in some cases is
about
100 C, in other cases about 60 C and in still other cases about 40 C. The
minimum
temperature difference between the inlet and outlet of R3 is in some cases may
be
0 C, in other cases about 3 C and in still other cases about 10 C. In some
cases R3
is operated an adiabatic fashion and in other cases R3 is heated.
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The pressure in the polymerization reactors should be high enough to maintain
the
polymerization solution as a single phase solution and to provide the upstream
pressure to force the polymer solution from the reactors through a heat
exchanger and
on to polymer recovery operations. Referring to the embodiments shown in
Figure 2,
the operating pressure of the solution polymerization reactors can vary over a
wide
range. For example, the' upper limit on reactor pressure in some cases may be
about
45 MPag, in other cases about 30 MPag and in still other cases about 20 MPag;
and
the lower limit in some cases may be about 3 MPag, in other some cases about 5
MPag and in still other cases about 7 MPag.
Referring to the embodiments shown in Figure 2, prior to entering the first
V/L
separator, stream 19, or optionally passivated stream 23 (if a heterogeneous
catalyst
formulation was employed in reactor 17) may have a maximum temperature in some
cases of about 300 C, in other cases about 290 C and in still other cases
about
280 C; the minimum temperature may be in some cases about 150 C, in other
cases
about 200 C and in still other cases about 220 C. Immediately prior to
entering the
first V/L separator stream 19, or optionally passivated stream 23, may have a
maximum pressure of about 40 MPag, in other cases about 25 MPag and in still
cases
about 15 MPag; the minimum pressure in some cases may be about 1.5 MPag, in
other cases about 5 MPag and in still other cases about 6 MPag.
The first V/L separator (vessel 25 in Figure 2) may be operated over a
relatively broad
range of temperatures and pressures. For example, the maximum operating
temperature of the first V/L separator in some cases may be about 300 C, in
other
cases about 285 C and in still other cases about 270 C; the minimum operating
temperature in some cases may be about 100 C, in other cases about 140 C and
in
still other cases 170 C. The maximum operating pressure of the first V/L
separator in
some cases may be about 20 MPag, in other cases about 10 MPag and in still
other
cases about 5 MPag; the minimum operating pressure in some cases may be about
1
MPag, in other cases about 2 MPag and in still other cases about 3 MPag.
The second V/L separator (vessel 28 in Figure 2) may be operated over a
relatively
broad range of temperatures and pressures. For example, the maximum operating
temperature of the second V/L separator in some cases may be about 300 C, in
other
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cases about 250 C and in still other cases about 200 C; the minimum operating
temperature in some cases may be about 100 C, in other cases about 125 C and
in
still other cases about 150 C. The maximum operating pressure of the second
V/L
separator in some cases may be about 1000 kPag, in other cases about 900 kPag
and in still other cases about 800kPag; the minimum operating pressure in some
cases may be about 10 kPag, in other cases about 20 kPag and in still other
cases
about 30 kPag.
The third V/L separator (vessel 31 in Figure 2) may be operated over a
relatively
broad range of temperatures and pressures. For example, the maximum operating
temperature of the third V/L separator in some cases may be about 300 C, in
other
cases about 250 C, and in still other cases about 200 C; the minimum operating
temperature in some cases may be about 100 C, in other cases about 125 C and
in
still other cases about 150 C. The maximum operating pressure of the third V/L
separator in some cases may be about 500 kPag, in other cases about 150 kPag
and
in still other cases about 100 kPag; the minimum operating pressure in some
cases
may be about 1 kPag, in other cases about 10 kPag and in still other cases 25
about
kPag.
Embodiments of the continuous solution polymerization process shown in Figure
2
show three V/L separators. However, continuous solution polymerization
embodiments may include configurations comprising at least one V/L separator.
The ethylene interpolymer product produced in the continuous solution
polymerization
process may be recovered using conventional devolatilization systems that are
well
known to persons skilled in the art, non-limiting examples include flash
devolatilization
systems and devolatilizing extruders.
Any reactor shape or design may be used for reactor lla (R1) and reactor 12a
(R2) in
Figure 2; non-limiting examples include unstirred or stirred spherical,
cylindrical or
tank-like vessels, as well as tubular reactors or recirculating loop reactors.
At
commercial scale the maximum volume of R1 in some cases may be about 20,000
gallons (about 75,710 L), in other cases about 10,000 gallons (about 37,850 L)
and in
still other cases about 5,000 gallons (about 18,930 L). At commercial scale
the
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minimum volume of R1 in some cases may be about 100 gallons (about 379 L), in
other cases about 500 gallons (about 1,893 L) and in still other cases about
1,000
gallons (about 3,785 L). At pilot plant scales reactor volumes are typically
much
smaller, for example the volume of R1 at pilot scale could be less than about
2 gallons
(less than about 7.6 L). In this disclosure the volume of reactor R2 was
expressed as
a percent of the volume of reactor R1. The upper limit on the volume of R2 in
some
cases may be about 600% of R1, in other cases about 400% of R1 and in still
other
cases about 200% of R1, For clarity, if the volume of R1 is 5,000 gallons and
R2 is
200% the volume of R1, then R2 has a volume of 10,000 gallons. The lower limit
on
the volume of R2 in some cases may be about 50% of R1, in other cases about
100%
of R1 and in still other cases about 150% of R1. In the case of continuously
stirred
tank reactors the stirring rate can vary over a wide range; in some cases from
about
10 rpm to about 2000 rpm, in other cases from about 100 to about 1500 rpm and
in
still other cases from about 200 to about 1300 rpm. In this disclosure the
volume of
R3, the tubular reactor, was expressed as a percent of the volume of reactor
R2. The
upper limit on the volume of R3 in some cases may be about 500% of R2, in
other
cases about 300% of R2 and in still other cases about 100% of R2. The lower
limit
on the volume of R3 in some cases may be about 3% of R2, in other cases about
10%
of R2 and in still other cases about 50% of R2.
The "average reactor residence time", a commonly used parameter in the
chemical
engineering art, is defined by the first moment of the reactor residence time
distribution; the reactor residence time distribution is a probability
distribution function
that describes the amount of time that a fluid element spends inside the
reactor. The
average reactor residence time can vary widely depending on process flow rates
and
reactor mixing, design and capacity. The upper limit on the average reactor
residence
time of the solution in R1 in some cases may be about 600 seconds, in other
cases
about 360 seconds and in still other cases about 180 seconds. The lower limit
on the
average reactor residence time of the solution in R1 in some cases may be
about 10
seconds, in other cases about 20 seconds and in still other cases about 40
seconds.
The upper limit on the average reactor residence time of the solution in R2 in
some
cases may be about 720 seconds, in other cases about 480 seconds and in still
other
cases about 240 seconds. The lower limit on the average reactor residence time
of
the solution in R2 in some cases may be about 10 seconds, in other cases about
30
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seconds and in still other cases about 60 seconds. The upper limit on the
average
reactor residence time of the solution in R3 in some cases may be about 600
seconds, in other cases about 360 seconds and in still other cases about 180
seconds. The lower limit on the average reactor residence time of the solution
in R3
in some cases may be about 1 second, in other cases about 5 seconds and in
still
other cases about 10 seconds.
Optionally, additional reactors (e.g. CSTRs, loops or tubes, etc.) could be
added to the
continuous solution polymerization process embodiments shown in Figure 2. In
this
disclosure, the number of reactors was not particularly important; with the
proviso that
the continuous solution polymerization process comprises at least two reactors
that
employ a first homogeneous catalyst formulation and a second homogeneous
catalyst, respectively.
In operating the continuous solution polymerization process embodiments shown
in
Figure 2 the total amount of ethylene supplied to the process can be portioned
or split
between the three reactors R1, R2 and R3. This operational variable was
referred to
as the Ethylene Split (ES), i.e. "ESR1", "ESR2" and "ESR3" refer to the weight
percent of
ethylene injected in R1, R2 and R3, respectively; with the proviso that ESR1+
ESR2+
ESR3 = 100%. This was accomplished by adjusting the ethylene flow rates in the
following streams: stream 2 (R1), stream 7 (R2) and stream 14 (R3). The upper
limit
on ESR1 in some cases is about 60%, in other cases about 55% and in still
other
cases about 50%; the loWer limit on ESR1 in some cases is about 5%, in other
cases
about 8% and in still other cases about 10%. The upper limit on ESR2 in some
cases
is about 95%, in other cases about 92% and in still other cases about 90%; the
lower
limit on ESR2 in some cases is about 20%, in other cases about 30% and in
still other
cases about 40%. The upper limit on ESR3 in some cases is about 30%, in other
cases about 25% and in still other cases about 20%; the lower limit on ESR3 in
some
cases is 0%, in other cases about 5% and in still other cases about 10%.
In operating the continuous solution polymerization process embodiments shown
in
Figure 2 the ethylene concentration in each reactor was also controlled. The
ethylene
concentration in reactor 1, hereinafter ECR1, is defined as the weight of
ethylene in
reactor 1 divided by the total weight of everything added to reactor 1; ECR2
and ECR3
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are defined similarly. Ethylene concentrations in the reactors (ECR1 or ECR2
or ECR3)
in some cases may vary from about 7 weight percent (wt %) to about 25 wt %, in
other
cases from about 8 wt % to about 20 wt % and in still other cases from about 9
wt %
to about 17 wt %.
In operating the continuous solution polymerization process embodiments shown
in
Figure 2 the total amount of ethylene converted in each reactor was monitored.
The
term "QR1" refers to the percent of the ethylene added to R1 that was
converted into
an ethylene interpolymer by the catalyst formulation. Similarly 0' and 0R3
represent
the percent of the ethylene added to R2 and R3 that was converted into
ethylene
interpolymer, in the respective reactor. Ethylene conversions can vary
significantly
depending on a variety of process conditions, e.g. catalyst concentration,
catalyst
formulation, impurities and poisons. The upper limit on both QR1 and 0R2 in
some
cases is about 99%, in other cases about 95% and in still other cases about
90%; the
lower limit on both QR1 and 0R2 in some cases is about 65%, in other cases
about
70% and in still other cases about 75%. The upper limit on QR3 in some cases
is
about 99%, in other cases about 95% and in still other cases about 90%; the
lower
limit on QR3 in some cases is 0%, in other cases about 5% and in still other
cases
about 10%. The term "QT" represents the total or overall ethylene conversion
across
the entire continuous solution polymerization plant; i.e. QT = 100 x [weight
of ethylene
in the interpolymer product]/([weight of ethylene in the interpolymer
productHweight
of unreacted ethylene]). The upper limit on QT in some cases is about 99%, in
other
cases about 95% and in still other cases about 90%; the lower limit on QT in
some
cases is about 75%, in other cases about 80% and in still other cases about
85%.
Optionally, a-olefin may be added to the continuous solution polymerization
process.
If added, a-olefin may be proportioned or split between Al, R2 and R3. This
operational variable was referred to as the Comonomer Split (CS), i.e. "CSR1",
"CSR2"
and "CSR3" refer to the weight percent of a-olefin comonomer that is injected
in R1, R2
and R3, respectively; with the proviso that CSR 1+ CSR2 CSR3 = 100%. This is
accomplished by adjusting a-olefin flow rates in the following streams: stream
3 (R1),
stream 8 (R2) and stream 15 (R3). The upper limit on CSR1 in some cases is
100%
(i.e. 100% of the a-olefin is injected into R1), in other cases about 95% and
in still
other cases about 90%. The lower limit on CSR1 in some cases is 0% (ethylene
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homopolymer produced in R1), in other cases about 5% and in still other cases
about
10%. The upper limit on CSR2 in some cases is about 100% (i.e. 100% of the a-
olefin
is injected into reactor 2), in other cases about 95% and in still other cases
about
90%. The lower limit on CSR2 in some cases is 0%, in other cases about 5% and
in
still other cases about 10%. The upper limit on CSR3 in some cases is 100%, in
other
cases about 95% and in still other cases about 90%. The lower limit on CSR3 in
some
cases is 0%, in other cases about 5% and in still other cases about 10%.
First Ethylene Interpolymer
The first ethylene interpolymer was synthesized using the first homogeneous
catalyst
formulation. One embodiment of the first homogeneous catalyst formulation was
a
bridged metallocene catalyst formulation. Referring to the embodiments shown
in
Figure 2, if the optional a-olefin was not added to reactor 1 (R1), then the
ethylene
interpolymer produced in R1 was an ethylene homopolymer. If an a-olefin is
added,
the following weight ratio was one parameter to control the density of the
first ethylene
interpolymer: ((a-olefin)/(ethylene))R1 . The upper limit on ((a-
olefin)/(ethylene))R1 may
be about 3; in other cases about 2 and in still other cases about 1. The lower
limit on
((a-olefin)/(ethylene))R1 may be 0; in other cases about 0.25 and in still
other cases
about 0.5. Hereinafter, the symbol "al" refers to the density of the first
ethylene
interpolymer produced in R1. The upper limit on al may be about 0.975 g/cm3;
in
some cases about 0.965 g/cm3 and; in other cases about 0.955 g/cm3. The lower
limit
on al may be about 0.855 g/cm3, in some cases about 0.865 g/cm3, and; in other
cases about 0.875 g/cm3.
Methods to determine the CDBI50 (Composition Distribution Branching Index) of
an
ethylene interpolymer are well known to those skilled in the art. The CDBI50,
expressed as a percent, was defined as the percent of the ethylene
interpolymer
whose comonomer composition is within 50% of the median comonomer composition.
It is also well known to those skilled in the art that the CDBI50 of ethylene
interpolymers produced with homogeneous catalyst formulations are higher
relative to
the CDBI50 of a-olefin containing ethylene interpolymers produced with
heterogeneous
catalyst formulations. The upper limit on the CDBI50 of the first ethylene
interpolymer
may be about 98%, in other cases about 95% and in still other cases about 90%.
The
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lower limit on the CDB150 of the first ethylene interpolymer may be about 70%,
in other
cases about 75% and in still other cases about 80%.
The upper limit on the Mw/Me (the SEC determined weight average molecular
weight
(Mw) divided by the number average molecular weight (Me)) of the first
ethylene
interpolymer may be about 2.8, in other cases about 2.5 and in still other
cases about
2.2. The lower limit on the Mw/Me the first ethylene interpolymer may be about
1.7, in
other cases about 1.8 and in still other cases about 1.9.
The first ethylene interpolymer, produced with the bridged metallocene
catalyst
formulation, contains long chain branching characterized by the LCBF disclosed
herein. The upper limit on the LCBF of the first ethylene interpolymer may be
about
0.5, in other cases about 0.4 and in still other cases about 0.3
(dimensionless). The
lower limit on the LCBF of the first ethylene interpolymer may be about 0.001,
in other
cases about 0.0015 and in still other cases about 0.002 (dimensionless).
The first ethylene interpolymer contained catalyst residues that reflect the
chemical
composition of the first homogeneous catalyst formulation. Those skilled in
the art will
understand that catalyst residues are typically quantified by the parts per
million of
metal in the first ethylene interpolymer, where metal originates from the
metal in
catalyst component A (Formula (I)); hereinafter this metal will be referred to
"metal A".
As recited earlier in this disclosure, non-limiting examples of metal A
include Group 4
metals, titanium, zirconium and hafnium. The upper limit on the ppm of metal A
in the
first ethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppm
and in
still other cases about 1.5 ppm. The lower limit on the ppm of metal A in the
first
ethylene interpolymer may be about 0.03 ppm, in other cases about 0.09 ppm and
in
still other cases about 0.15 ppm.
The amount of hydrogen added to R1 can vary over a wide range allowing the
continuous solution process to produce first ethylene interpolymers that
differ greatly
in melt index, hereinafter 121 (melt index was measured at 190 C using a 2.16
kg load
following the procedures outlined in ASTM D1238). This was accomplished by
adjusting the hydrogen flow rate in stream 4 (as shown in Figure 2). The
quantity of
hydrogen added to R1 was expressed as the parts-per-million (ppm) of hydrogen
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R1 relative to the total mass in reactor R1; hereinafter H2R1 (ppm). In some
cases
H2R1 (ppm) ranges from about 100 ppm to 0 ppm, in other cases from about 50
ppm
to 0 ppm, in alternative cases from about 20 ppm to 0 ppm and in still other
cases
from about 2 ppm to 0 ppm. The upper limit on 121 may be about 200 dg/min, in
some
cases about 100 dg/min; in other cases about 50 dg/min, and; in still other
cases
about 1 dg/min. The lower limit on 121 may be about 0.01 dg/min, in some cases
about
0.05 dg/min; in other cases about 0.1 dg/min, and; in still other cases about
0.5
dg/min.
The upper limit on the weight percent (wt%) of the first ethylene interpolymer
in the
ethylene interpolymer product may be about 60 wt%, in other cases about 55 wt%
and
in still other cases about 50 wt%. The lower limit on the wt % of the first
ethylene
interpolymer in the ethylene interpolymer product may be about 5 wt%; in other
cases
about 8 wt% and in still other cases about 10 wt%.
Second Ethylene Interpolymer
The second ethylene interpolymer was synthesized using the second homogeneous
catalyst formulation. One embodiment of the second homogeneous catalyst
forumulation was an unbridged single site catalyst formulation. Referring to
the
embodiments shown in Figure 2, if optional a-olefin was not added to reactor
12a (R2)
either through fresh a-olefin stream 8 or carried over from reactor lla (R1)
in stream
11e (in series mode), then the ethylene interpolymer produced in reactor 12a
(R2)
was an ethylene homopolymer. If an optional a-olefin is present in R2, the
following
weight ratio was one parameter to control the density of the second ethylene
interpolymer produced in R2: ((a-olefin)/(ethylene))R2. The upper limit on ((a-
olefin)/(ethylene))R2 maybe about 3; in other cases about 2 and in still other
cases
about 1. The lower limit on ((a-olefin)/(ethylene))R2 may be 0; in other cases
about
0.25 and in still other cases about 0.5. Hereinafter, the symbol "02" refers
to the
density of the ethylene interpolymer produced in R2. The upper limit on 62 may
be
about 0.975 g/cm3; in some cases about 0.965 g/cm3 and; in other cases about
0.955
g/cm3. The lower limit on (32 may be about 0.855 g/cm3, in some cases about
0.865
g/cm3, and; in other cases about 0.875 g/cm3.
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The upper limit on the CDBI50 of the second ethylene interpolymer (that
contains an a-
olefin) may be about 98%, in other cases about 95% and in still other cases
about
90%. The lower limit on the CDBI50 of the second ethylene interpolymer may be
about
70%, in other cases about 75% and in still other cases about 80%. If an a-
olefin is not
added to the continuous solution polymerization process the second ethylene
interpolymer was an ethylene homopolymer. In the case of a homopolymer, which
does not contain a-olefin, one can still measure a CDBI50 using TREF. In the
case of
a homopolymer, the upper limit on the CDBI50 of the second ethylene
interpolymer
may be about 98%, in other cases about 96% and in still other cases about 95%,
and;
the lower limit on the CDBI50 may be about 88%, in other cases about 89% and
in still
other cases about 90%. It is well known to those skilled in the art that as
the a-olefin
content in the second ethylene interpolymer approaches zero, there is a smooth
transition between the recited CDBI50 limits for the second ethylene
interpolymers
(that contain an a-olefin) and the recited CDBI50 limits for the second
ethylene
interpolymers that are ethylene homopolymers.
The upper limit on the Mw/Mn of the second ethylene interpolymer may be about
2.8, in
other cases about 2.5 and in still other cases about 2.2. The lower limit on
the Mw/Mn
of the second ethylene interpolymer may be about 1.7, in other cases about 1.8
and in
still other cases about 1.9.
The second ethylene interpolymer produced with the second homogeneous catalyst
formulation was characterized by an undetectable level of long chain
branching, i.e.
LCBF of <0.001 (dimensionless).
The second ethylene interpolymer contains catalyst residues that reflect the
chemical
composition of the second homogeneous catalyst formulation. More specifically,
the
second ethylene interpolymer contains "a metal C" that originates from the
bulky
ligand-metal complex, i.e. component C (Formula (II)). Non-limiting examples
of metal
C include Group 4 metals, titanium, zirconium and hafnium. The upper limit on
the
ppm of metal C in the second ethylene interpolymer may be about 3.0 ppm, in
other
cases about 2.0 ppm and in still other cases about 1.5 ppm. The lower limit on
the
ppm of metal C in the second ethylene interpolymer may be about 0.03 ppm, in
other
cases about 0.09 ppm and in still other cases about 0.15 ppm.
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Referring to the embodiments shown in Figure 2, the amount of hydrogen added
to R2
can vary over a wide range which allows the continuous solution process to
produce
second ethylene interpolymers that differ greatly in melt index, hereinafter
122. This is
accomplished by adjusting the hydrogen flow rate in stream 9. The quantity of
hydrogen added was expressed as the parts-per-million (ppm) of hydrogen in R2
relative to the total mass in reactor R2; hereinafter H2R2 (ppm). In some
cases H2R2
(ppm) ranges from about 100 ppm to 0 ppm, in some cases from about 50 ppm to 0
ppm, in other cases from about 20 to 0 and in still other cases from about 2
ppm to 0
ppm. The upper limit on 122 may be about 1000 dg/min; in some cases about 750
dg/min; in other cases about 500 dg/min, and; in still other cases about 200
dg/min.
The lower limit on 122 may be about 0.3 dg/min, in some cases about 0.4
dg/min, in
other cases about 0.5 dg/min, and; in still other cases about 0.6 dg/min.
The upper limit on the weight percent (wt%) of the second ethylene
interpolymer in the
ethylene interpolymer product may be about 95 wt%, in other cases about 92 wt%
and
in still other cases about 90 wt%. The lower limit on the wt % of the second
ethylene
interpolymer in the ethylene interpolymer product may be about 20 wt%; in
other
cases about 30 wt% and in still other cases about 40 wt%.
Third Ethylene Interpolymer
Optionally, the disclosed ethylene interpolymer products contain a third
ethylene
interpolymer. Referring to the embodiments shown in Figure 2 a third ethylene
interpolymer was not produced in reactor 17 (R3) if catalyst deactivator A was
added
upstream of reactor 17 via catalyst deactivator tank 18A. If catalyst
deactivator A was
not added and optional a-olefin was not added to reactor 17 either through
fresh a-
olefin stream 15 or carried over from reactor 12a (R2) in stream 12c (series
mode) or
stream 12d (parallel mode) then the ethylene interpolymer produced in reactor
17 was
an ethylene homopolymer. If catalyst deactivator A was not added and optional
a-
olefin was present in R3, the following weight ratio was one parameter that
determined the density of the third ethylene interpolymer: ((a-
olefin)/(ethylene))R3.
The upper limit on ((a-olefin)/(ethylene))R3 may be about 3; in other cases
about 2 and
in still other cases about 1. The lower limit on ((a-olefin)/(ethylene))R3 may
be 0; in
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other cases about 0.25 and in still other cases about 0.5. Hereinafter, the
symbol "63"
refers to the density of the ethylene interpolymer produced in R3. The upper
limit on
cr3 may be about 0.975 g/cm3; in some cases about 0.965 g/cm3 and; in other
cases
about 0.955 g/cm3. Depending on the catalyst formulations used in R3, the
lower limit
on cy3 may be about 0.855 g/cm3, in some cases about 0.865 g/cm3, and; in
other
cases about 0.875 g/cm3.
Optionally, one or more of the following homogeneous or heterogeneous catalyst
formulations may be injected into R3: the first homogeneous catalyst
formulation, the
second homogeneous catalyst formulation, the fifth homogeneous catalyst
formulation
or the heterogeneous catalyst formulation. One embodiment of the first
homogeneous
catalyst formulation was the bridged metallocene catalyst formulation
containing
component A (Formula (I)), in this case the third ethylene interpolymer
contains metal
A. The upper limit on the ppm of metal A in the third ethylene interpolymer
may be
about 3.0 ppm, in other cases about 2.0 ppm and in still other cases about 1.5
ppm.
The lower limit on the ppm of metal A in the third ethylene interpolymer may
be about
0.03 ppm, in other cases about 0.09 ppm and in still other cases about 0.15
ppm.
One embodiment of the second homogeneous catalyst formulation was the
unbridged
single site catalyst formulation containing component C (Formula (II)), in
this case the
third ethylene interpolymer contains metal C. The upper limit on the ppm of
metal A in
the third ethylene interpolymer may be about 3.0 ppm, in other cases about 2.0
ppm
and in still other cases about 1.5 ppm. The lower limit on the ppm of metal A
in the
third ethylene interpolymer may be about 0.03 ppm, in other cases about 0.09
ppm
and in still other cases about 0.15 ppm. Embodiments of the heterogeneous
catalyst
formulation include an in-line Ziegler-Natta catalyst formulation or a batch
Ziegler-
Natta catalyst formulation; in this case the third ethylene interpolymer
contains metal Z
that originates from the transition metal compound (component (vii)) used to
fabricate
the Ziegler-Natta catalyst formulation. The upper limit on the ppm of metal Z
in the
third ethylene interpolymer may be about 12 ppm, in other cases about 10 ppm
and in
still other cases about 8 ppm. The lower limit on the ppm of metal Z in the
third
ethylene interpolymer may be about 0.5 ppm, in other cases about 1 ppm and in
still
other cases about 3 ppm. If the fifth homogeneous catalyst formulation is
employed,
comprising a bulky ligand-metal complex that is not a member of the genera
defined
by Formulas (I) or (II) the third ethylene interpolymer contains metal D. The
upper
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limit on the ppm of metal D in the third ethylene interpolymer may be about
3.0 ppm,
in other cases about 2.0 .ppm and in still other cases about 1.5 ppm. The
lower limit
on the ppm of metal D in the third ethylene interpolymer may be about 0.03
ppm, in
other cases about 0.09 ppm and in still other cases about 0.15 ppm.
The upper limit on the CDBI50 of the optional third ethylene interpolymer
(containing
an a-olefin) may be about 98%, in other cases about 95% and in still other
cases
about 90%. The lower limit on the CDBI50 of the optional third ethylene
interpolymer
may be about 35%, in other cases about 40% and in still other cases about 45%.
The upper limit on the Mw/Mn of the optional third ethylene interpolymer may
be about
5.0, in other cases about 4.8 and in still other cases about 4.5. The lower
limit on the
Mw/Mn of the optional third ethylene interpolymer may be about 1.7, in other
cases
about 1.8 and in still other cases about 1.9.
Referring to the embodiments shown in Figure 2, optional hydrogen may be added
to
the tubular reactor (R3) via stream 16. The amount of hydrogen added to R3 may
vary over a wide range. Adjusting the amount of hydrogen in R3, hereinafter
H2R3
(ppm), allows the continuous solution process to produce optional third
ethylene
interpolymers that differ widely in melt index, hereinafter l23. The amount of
optional
hydrogen added to R3 ranges from about 50 ppm to 0 ppm, in some cases from
about
ppm to 0 ppm, in other cases from about 10 to 0 and in still other cases from
about
2 ppm to 0 ppm. The upper limit on l23 may be about 2000 dg/min; in some cases
about 1500 dg/min; in other cases about 1000 dg/min, and; in still other cases
about
25 500 dg/min. The lower limit on l23 may be about 0.5 dg/min, in some
cases about 0.6
dg/min, in other cases about 0.7 dg/min, and; in still other cases about 0.8
dg/min.
The upper limit on the weight percent (wt%) of the optional third ethylene
interpolymer
in the ethylene interpolymer product may be about 30 wt%, in other cases about
25
wt% and in still other cases about 20 wt%. The lower limit on the wt % of the
optional
third ethylene interpolymer in the ethylene interpolymer product may be 0 wt%;
in
other cases about 5 wt% and in still other cases about 10 wt%.
Ethylene Interpolymer Product
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The upper limit on the density of the ethylene interpolymer product (pf) may
be about
0.975 g/cm3; in some cases about 0.965 g/cm3 and; in other cases about 0.955
g/cm3.
The lower limit on the density of the ethylene interpolymer product may be
about
0.855 g/cm3, in some cases about 0.865 g/cm3, and; in other cases about 0.875
g/cm3.
The upper limit on the CDBI50 of the ethylene interpolymer product may be
about 97%,
in other cases about 90% and in still other cases about 85%. An ethylene
interpolymer product with a CDBI50 of 97% may result if an a-olefin is not
added to the
continuous solution polymerization process; in this case, the ethylene
interpolymer
product is an ethylene homopolymer. The lower limit on the CDBI50 of an
ethylene
= interpolymer product may be about 1%, in other cases about 2% and in
still other
cases about 3%.
The upper limit on the Mw/Mn of the ethylene interpolymer product may be about
25, in
other cases about 15 and in still other cases about 9. The lower limit on the
Mw/Mn of
the ethylene interpolymer product may be 1.7, in other cases about 1.8 and in
still
other cases about 1.9.
The catalyst residues in the ethylene interpolymer product reflect the
chemical
compositions of: the first homogeneous catalyst formulation employed in R1;
the
second homogeneous catalyst formulation employed in R2, and; optionally one or
more catalyst formulations employed in R3. Catalyst residues were quantified
by
measuring the parts per million of catalytic metal in the ethylene
interpolymer products
using Neutron Activation Analysis (N.A.A.). As shown in Table 5, the ethylene
interpolymer product Example 52 contained 0.624 ppm hafnium and 0.208 ppm
titanium. As shown in Table 4A, Example 52 was produced with reactors 1 and 2
operating in parallel mode, a hafnium (Hf) containing bridged metallocene
catalyst
formulation was injected into reactor 1 and a titanium (Ti) containing
unbridged single
site catalyst formulation was injected into reactor 2 (catalysts were not
injected into
reactor 3). Further, in Example 52, Hf originated from CpF-2 (the [(2,7-
tBu2Flu)Ph2C(Cp)HfMe2] species of component A (Formula (I)) and Ti originated
from
PIC-1 (the [CpRisopropy1)3PNIfiC12] species of component C (Formula (II)).
Example
52 had a residual catalyst Hf/Ti ratio of 3.0 (0.624 ppm Hf/0.208 ppm Ti).
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As shown in Table 5, the Comparatives contained undetectable levels of hafnium
(0.0
ppm hafnium) and about 0.303 ppm of titanium, i.e. a residual catalyst Hf/Ti
ratio of
0Ø As shown in Table 4A, Comparative 60 was produced with reactors 1 and 2
operating in series mode., an unbridged single site catalyst formulation (Ti
containing)
was injected into both reactor 1 and reactor 2 (catalysts were not injected
into reactor
3). In Comparative 60 the Ti source was: PIC-2, the cyclopentadienyl
tri(isopropyl)
phosphinimine titanium dichloride species [CpRi-prop)3PNFiC12] of component C
(Formula (II))).
As shown in Table 5, ethylene interpolymer product Example 51 contained 0.530
ppm
Hf and 0.127 ppm Ti and the residual catalyst Hf/Ti ratio was 4.17. As shown
in Table
4A, Example 51 was produced with reactors 1 and 2 operating in series mode, a
Hf
containing (CpF-2) bridged metallocene catalyst formulation was injected into
reactor
1 and a Ti containing (PIC-1) unbridged single site catalyst formulation was
injected
into reactor 2 (catalysts were not injected into reactor 3).
Comparative 67 contained 0.0 ppm of Hf and about 0.303 ppm Ti and the residual
catalyst Hf/Ti ratio was 0:0. Comparative 67 was produced using the unbridged
single
site catalyst formulation in both reactors 1 and 2. Comparative 67 was a
commercially
available solution process ethylene/1-octene polymer produced by NOVA
Chemicals
Company (Calgary, Alberta, Canada) coded SURPASS FPs117-C.
The upper limit on the ppm of metal A in the ethylene interpolymer product was
determined by maximizing the weight fraction (i.e. 0.60) of the first ethylene
interpolymer, minimizing the weight fraction (i.e. 0.20) of the second
ethylene
interpolymer and the remaining weight fraction (i.e. 0.20) was the third
ethylene
interpolymer produced with catalytic metal A, i.e. the bridged metallocene
catalyst
formulation. Specifically, the upper limit on the ppm of metal A in the
ethylene
interpolymer product was 2.4 ppm: i.e. ((0.6 x 3 ppm) + (0.2 x 3 ppm)); where
3 ppm is
the upper limit on the ppm of metal A in the first and third ethylene
interpolymers. In
other cases, the upper limit on the ppm of metal A in the ethylene
interpolymer
product was 2 ppm and in still other cases 1.5 ppm. The lower limit on the ppm
of
metal A in the ethylene interpolymer product was determined by minimizing the
weight
fraction (i.e. 0.05) of the first ethylene interpolymer and maximizing the
weight fraction
(i.e. 0.95) of the second ethylene interpolymer. Specifically, the lower limit
on the ppm
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of metal A in the ethylene interpolymer product was 0.0015 ppm: i.e. (0.05 x
0.03
ppm), where 0.03 ppm was the lower limit of metal A in the first ethylene
interpolymer.
In other cases, the lower limit on the ppm of metal A in the ethylene
interpolymer
product was 0.0025 ppm and in still other cases 0.0035 ppm.
The upper limit on the ppm of metal C in the ethylene interpolymer product was
determined by maximizing the weight fraction (i.e. 0.95) of the second
ethylene
interpolymer, i.e. 2.9 ppm (0.95 x 3 ppm), where 3 ppm was the upper limit on
the
ppm of metal C in the second ethylene interpolymer. In other cases, the upper
limit on
the amount of metal C in the ethylene interpolymer product was 1.9 ppm and in
still
other cases 1.4 ppm. The lower limit on the ppm of metal C in the ethylene
interpolymer product was determined by minimizing the weight fraction (i.e.
0.20) of
the second ethylene interpolymer, i.e. 0.006 ppm (0.20 x 0.03 ppm), where 0.03
ppm
was the lower limit on the ppm of metal C in the second ethylene interpolymer.
In
other cases, the lower limit on the ppm of metal C in the ethylene
interpolymer product
was 0.02 ppm and in still other cases 0.03 ppm.
The upper limit on the ppm of metal D (originating from the fifth homogeneous
catalyst
formulation) in the ethylene interpolymer product was determined by maximizing
the
weight fraction (i.e. 0.30) of the third ethylene interpolymer, i.e. 0.9 ppm
(0.3 x 3 ppm),
where 3 ppm is the upper limit on the ppm of metal D in the third ethylene
interpolymer. In other cases, the upper limit on the ppm of metal D in the
ethylene
interpolymer product was 0.7 ppm and in still other cases 0.5 ppm. The lower
limit on
the ppm of metal D in the ethylene interpolymer product was determined by
minimizing the weight fraction (i.e. 0.0) of the third ethylene interpolymer,
i.e. 0.0
ppm. In other cases when the ethylene interpolymer product contains a small
fraction
of the third ethylene interpolymer the lower limit on the ppm of metal D in
the ethylene
interpolymer product may be 0.0015 ppm or 0.003 ppm, i.e. 5 and 10% of the
third
ethylene interpolymer, respectively.
The upper limit on the ppm of metal Z in the ethylene interpolymer product was
determined by maximizing the weight fraction (i.e. 0.30) of the third ethylene
interpolymer, i.e. 3.6 ppm (0.30 x 12 ppm), where 12 ppm was the upper limit
on the
ppm of metal Z in the third ethylene interpolymer. In other cases, the upper
limit on
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amount of metal Z in the ethylene interpolymer product was 3 ppm and in still
other
cases 2.4 ppm. The lower limit on the ppm of metal Z in the ethylene
interpolymer
product was determined by minimizing the weight fraction (i.e. 0.0) of the
third
ethylene interpolymer, i.e. 0.0 ppm. In other cases where the ethylene
interpolymer
product contains a small fraction of the third ethylene interpolymer the lower
limit on
ppm of metal Z in the ethylene interpolymer product may be 0.025 ppm and in
other
cases 0.05 ppm, i.e. 5 and 10% of the third ethylene interpolymer,
respectively.
The hafnium to titanium ratio (Hf/Ti) in the ethylene interpolymer product may
range
from 400 to 0.0005, as determined by Neutron Activation Analysis. A Hf/Ti
ratio of
400 may result in the case of an ethylene interpolymer product containing 80
weight%
of the a first and a third ethylene interpolymer containing 3 ppm of Hf (upper
limit) and
weight% of a second ethylene interpolymer containing 0.03 ppm of Ti (lower
limit).
A Hfai ratio of 0.0005 may result in the case of an ethylene interpolymer
product
15 containing 5 weight% of a first ethylene interpolymer containing 0.03
ppm of Hf (lower
limit) and 95 weight% of a second ethylene interpolymer containing 3 ppm of Ti
(upper
limit).
The upper limit on the total amount of catalytic metal (metal A and metal C;
and
20 optionally metals Z and D) in the ethylene interpolymer product may be 6
ppm, in
other cases 5 ppm and in still other cases 4 ppm. The lower limit on the total
amount
of catalytic metal in the ethylene interpolymer product may be 0.03 ppm, in
other
cases 0.09 ppm and in still other cases 0.15 ppm.
Embodiments of the ethylene interpolymer products disclosed herein have lower
catalyst residues relative the polyethylene polymers described in US
6,277,931.
Higher catalyst residues in U.S. 6,277,931 increase the complexity of the
continuous
solution polymerization process; an example of increased complexity includes
additional purification steps to remove catalyst residues from the polymer. In
contrast,
in the present disclosure, catalyst residues are not removed.
The upper limit on melt index of the ethylene interpolymer product may be
about 500
dg/min, in some cases about 400 dg/min; in other cases about 300 dg/min, and;
in still
other cases about 200 dg/min. The lower limit on the melt index of the
ethylene
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interpolymer product may be about 0.3 dg/min, in some cases about 0.4 dg/min;
in
other cases about 0.5 dg/min, and; in still other cases about 0.6 dg/min.
Catalyst Deactivation
In the continuous polymerization processes described in this disclosure,
polymerization is terminated by adding a catalyst deactivator. Embodiments in
Figure
2 show catalyst deactivation occurring either: (a) upstream of the tubular
reactor by
adding a catalyst deactivator A from catalyst deactivator tank 18A, or; (b)
downstream
of the tubular reactor by adding a catalyst deactivator B from catalyst
deactivator tank
18B. Catalyst deactivator tanks 18A and 18B may contain neat (100%) catalyst
deactivator, a solution of catalyst deactivator in a solvent, or a slurry of
catalyst
deactivator in a solvent. The chemical composition of catalyst deactivator A
and B
may be the same, or different. Non-limiting examples of suitable solvents
include
linear or branched C5 to 012 alkanes. In this disclosure, how the catalyst
deactivator is
added is not particularly important. Once added, the catalyst deactivator
substantially
stops the polymerization reaction by changing active catalyst species to
inactive
forms. Suitable deactivators are well known in the art, non-limiting examples
include:
amines (e.g. U.S. Pat. No. 4,803,259 to Zboril et al.); alkali or alkaline
earth metal
salts of carboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.);
water (e.g.
U.S. Pat. No. 4,731,438 to Bernier et al.); hydrotalcites, alcohols and
carboxylic acids
(e.g. U.S. Pat. No. 4,379882 to Miyata); or a combination thereof (U.S. Pat
No.
6,180,730 to Sibtain et al.). In this disclosure the quantify of catalyst
deactivator
added was determined by the following catalyst deactivator molar ratio: 0.3
(catalyst
deactivator)/((total catalytic metal)+(alkyl aluminum co-catalyst)+(aluminum
alkyl))
2.0; where the catalytic metal is the total moles of (metal A + metal C + any
optional
catalytic metals added the third reactor). The upper limit on the catalyst
deactivator
molar ratio may be about 2, in some cases about 1.5 and in other cases about
0.75.
The lower limit on the catalyst deactivator molar ratio may be about 0.3, in
some
cases about 0.35 and in still other cases about 0.4. In general, the catalyst
deactivator is added in a minimal amount such that the catalyst is deactivated
and the
polymerization reaction is quenched.
Solution Passivation
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If a heterogeneous catalyst formulation is employed in the third reactor,
prior to
entering the first V/L separator, a passivator or acid scavenger is added to
deactivated
solution A or B to form a passivated solution, i.e. passivated solution stream
23 as
shown in Figure 2. Passivator tank 22 may contain neat (100%) passivator, a
solution
of passivator in a solvent, or a slurry of passivator in a solvent. Non-
limiting examples
of suitable solvents include linear or branched 05 to 012 alkanes. In this
disclosure,
how the passivator is added is not particularly important. Suitable
passivators are well
known in the art, non-limiting examples include alkali or alkaline earth metal
salts of
carboxylic acids or hydrotalcites. The quantity of passivator added can vary
over a
wide range. The quantity of passivator added was determined by the total moles
of
chloride compounds added to the solution process, i.e. the chloride compound
"compound (vi)" plus the metal compound "compound (vii)" that was used to
manufacture the heterogeneous catalyst formulation. The upper limit on the
(passivator)/(total chlorides) molar ratio may be 15, in some cases 13 and in
other
cases 11. The lower limit on the (passivator)/(total chlorides) molar ratio
may be
about 5, in some cases about 7 and in still other cases about 9. In general,
the
passivator is added in the minimal amount to substantially passivate the
deactivated
solution.
Flexible Manufactured Articles
The ethylene interpolymer products disclosed herein may be converted into
flexible
manufactured articles such as monolayer or multilayer films. Non-limiting
examples of
processes to prepare such films include blown film processes, double bubble
processes, triple bubble processes, cast film processes, tenter frame
processes and
machine direction orientation (MDO) processes.
In the blown film extrusion process an extruder heats, melts, mixes and
conveys a
thermoplastic, or a thermoplastic blend. Once molten, the thermoplastic is
forced
through an annular die to produce a thermoplastic tube. In the case of co-
extrusion,
multiple extruders are employed to produce a multilayer thermoplastic tube.
The
temperature of the extrusion process is primarily determined by the
thermoplastic or
thermoplastic blend being processed, for example the melting temperature or
glass
transition temperature of the thermoplastic and the desired viscosity of the
melt. In
the case of polyolefins, typical extrusion temperatures are from 330 F to 550
F (166 C
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to 288 C). Upon exit from the annular die, the thermoplastic tube is inflated
with air,
cooled, solidified and pulled through a pair of nip rollers. Due to air
inflation, the tube
increases in diameter forming a bubble of desired size. Due to the pulling
action of
the nip rollers the bubble is stretched in the machine direction. Thus, the
bubble is
stretched in two directions: the transverse direction (TD) where the inflating
air
increases the diameter of the bubble; and the machine direction (MD) where the
nip
rollers stretch the bubble. As a result, the physical properties of blown
films are
typically anisotropic, i.e. the physical properties differ in the MD and TD
directions; for
example, film tear strength and tensile properties typically differ in the MD
and TD. In
some prior art documents, the terms "cross direction" or "CD" is used; these
terms are
equivalent to the terms "transverse direction" or "TD" used in this
disclosure. In the
blown film process, air is also blown on the external bubble circumference to
cool the
thermoplastic as it exits the annular die. The final width of the film is
determined by
controlling the inflating air or the internal bubble pressure; in other words,
increasing
or decreasing bubble diameter. Film thickness is controlled primarily by
increasing or
decreasing the speed of the nip rollers to control the draw-down rate. After
exiting
the nip rollers, the bubble or tube is collapsed and may be slit in the
machine direction
thus creating sheeting. Each sheet may be wound into a roll of film. Each roll
may be
further slit to create film of the desired width. Each roll of film is further
processed into
a variety of consumer products as described below.
The cast film process is similar in that a single or multiple extruder(s) may
be used;
however the various ther.moplastic materials are metered into a flat die and
extruded
into a monolayer or multilayer sheet, rather than a tube. In the cast film
process the
extruded sheet is solidified on a chill roll.
In the double bubble process a first blown film bubble is formed and cooled,
then the
first bubble is heated and re-inflated forming a second blown film bubble,
which is
subsequently cooled. The ethylene interpolymer products, disclosed herein, are
also
suitable for the triple bubble blown process. Additional film converting
processes,
suitable for the disclosed ethylene interpolymer products, include processes
that
involve a Machine Direction Orientation (MDO) step; for example, blowing a
film or
casting a film, quenching the film and then subjecting the film tube or film
sheet to a
MDO process at any stretch ratio. Additionally, the ethylene interpolymer
product
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films disclosed herein are suitable for use in tenter frame processes as well
as other
processes that introduce biaxial orientation.
Depending on the end-use application, the disclosed ethylene interpolymer
products
may be converted into films that span a wide range of thicknesses. Non-
limiting
examples include, food packaging films where thicknesses may range from about
0.5
mil (13 pm) to about 4 mil (102 pm), and; in heavy duty sack applications film
thickness may range from about 2 mil (51pm) to about 10 mil (254 pm).
The monolayer, in monolayer films, may contain more than one ethylene
interpolymer
product and/or one or more additional polymer; non-limiting examples of
additional
polymers include ethylene polymers and propylene polymers. The lower limit on
the
weight percent of the ethylene interpolymer product in a monolayer film may be
about
3 wt%, in other cases about 10 wt% and in still other cases about 30 wt%. The
upper
limit on the weight percent of the ethylene interpolymer product in the
monolayer film
may be 100 wt%, in other cases about 90 wt% and in still other cases about 70
wt%.
The ethylene interpolymer products disclosed herein may also be used in one or
more
layers of a multilayer film; non-limiting examples of multilayer films include
three, five,
seven, nine, eleven or more layers. The disclosed ethylene interpolymer
products are
also suitable for use in processes that employ micro-layering dies and/or
feedblocks,
such processes can produce films having many layers, non-limiting examples
include
from 10 to 10,000 layers.
The thickness of a specific layer (containing the ethylene interpolymer
product) within
a multilayer film may be about 5%, in other cases about 15% and in still other
cases
about 30% of the total multilayer film thickness. In other embodiments, the
thickness
of a specific layer (containing the ethylene interpolymer product) within a
multilayer
film may be about 95%, in other cases about 80% and in still other cases about
65%
of the total multilayer film thickness. Each individual layer of a multilayer
film may
contain more than one ethylene interpolymer product and/or additional
thermoplastics.
Additional embodiments include laminations and coatings, wherein mono or
multilayer
films containing the disclosed ethylene interpolymer products are extrusion
laminated
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or adhesively laminated or extrusion coated. In extrusion lamination or
adhesive
lamination, two or more substrates are bonded together with a thermoplastic or
an
adhesive, respectively. In extrusion coating, a thermoplastic is applied to
the surface
of a substrate. These processes are well known to those experienced in the
art.
Frequently, adhesive lamination or extrusion lamination are used to bond
dissimilar
materials, non-limiting examples include the bonding of a paper web to a
thermoplastic web, or the bonding of an aluminum foil containing web to a
thermoplastic web, or the bonding of two thermoplastic webs that are
chemically
incompatible, e.g. the bonding of an ethylene interpolymer product containing
web to a
polyester or polyamide web. Prior to lamination, the web containing the
disclosed
ethylene interpolymer product(s) may be monolayer or multilayer. Prior to
lamination
the individual webs may be surface treated to improve the bonding, a non-
limiting
example of a surface treatment is corona treating. A primary web or film may
be
laminated on its upper surface, its lower surface, or both its upper and lower
surfaces
with a secondary web. A secondary web and a tertiary web could be laminated to
the
primary web; wherein the secondary and tertiary webs differ in chemical
composition.
As non-limiting examples, secondary or tertiary webs may include; polyamide,
polyester and polypropylene, or webs containing barrier resin layers such as
EVOH.
Such webs may also contain a vapor deposited barrier layer; for example a thin
silicon
oxide (SiOx) or aluminum oxide (A10) layer. Multilayer webs (or films) may
contain
three, five, seven, nine, eleven or more layers.
The ethylene interpolymer products disclosed herein can be used in a wide
range of
manufactured articles comprising one or more films (monolayer or multilayer).
Non-
limiting examples of such manufactured articles include: food packaging films
(fresh
and frozen foods, liquids and granular foods), stand-up pouches, retortable
packaging
and bag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.)
and
modified atmosphere packaging; light and heavy duty shrink films and wraps,
collation
shrink film, pallet shrink film, shrink bags, shrink bundling and shrink
shrouds; light
and heavy duty stretch films, hand stretch wrap, machine stretch wrap and
stretch
hood films; high clarity films; heavy-duty sacks; household wrap, overvvrap
films and
sandwich bags; industrial and institutional films, trash bags, can liners,
magazine
overwrap, newspaper bags, mail bags, sacks and envelopes, bubble wrap, carpet
film,
furniture bags, garment bags, coin bags, auto panel films; medical
applications such
as gowns, draping and surgical garb; construction films and sheeting, asphalt
films,
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insulation bags, masking film, landscaping film and bags; geomembrane liners
for
municipal waste disposal and mining applications; batch inclusion bags;
agricultural
films, mulch film and green house films; in-store packaging, self-service
bags,
boutique bags, grocery bags, carry-out sacks and t-shirt bags; oriented films,
machine
direction oriented (MDO) films, biaxially oriented films and functional film
layers in
oriented polypropylene (OPP) films, e.g. sealant and/or toughness layers.
Additional
manufactured articles comprising one or more films containing at least one
ethylene
interpolymer product include laminates and/or multilayer films; sealants and
tie layers
in multilayer films and composites; laminations with paper; aluminum foil
laminates or
laminates containing vacuum deposited aluminum; polyamide laminates; polyester
laminates; extrusion coated laminates, and; hot-melt adhesive formulations.
The
manufactured articles summarized in this paragraph contain at least one film
(monolayer or multilayer) comprising at least one embodiment of the disclosed
ethylene interpolymer products.
Desired film physical properties (monolayer or multilayer) typically depend on
the
application of interest. Non-limiting examples of desirable film properties
include:
optical properties (gloss, haze and clarity), dart impact, Elmendorf tear,
modulus (1%
and 2% secant modulus), tensile properties (yield strength, break strength,
elongation
at break, toughness, etc.), heat sealing properties (heat seal initiation
temperature,
SIT, and hot tack). Specific hot tack and heat sealing properties are desired
in high
speed vertical and horizontal form-fill-seal processes that load and seal a
commercial
product (liquid, solid, paste, part, etc.) inside a pouch-like package.
In addition to desired film physical properties, it is desired that the
disclosed ethylene
interpolymer products are easy to process on film lines. Those skilled in the
art
frequently use the term "processability" to differentiate polymers with
improved
processability, relative to polymers with inferior processability. A commonly
used
measure to quantify processability is extrusion pressure; more specifically, a
polymer
with improved processability has a lower extrusion pressure (on a blown film
or a cast
film extrusion line) relative to a polymer with inferior processability.
The films used in the manufactured articles described in this section may
optionally
include, depending on its intended use, additives and adjuvants. Non-limiting
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examples of additives and adjuvants include, anti-blocking agents,
antioxidants, heat
stabilizers, slip agents, processing aids, anti-static additives, colorants,
dyes, filler
materials, light stabilizers, light absorbers, lubricants, pigments,
plasticizers,
nucleating agents and combinations thereof.
Rigid Manufactured Articles
The processes disclosed herein are also capable of making ethylene
interpolymer
products that have a useful combination of desirable physical properties for
use in
rigid manufactured articles. Non-limiting examples of rigid articles include:
deli
containers, margarine tubs, drink cups and produce trays; household and
industrial
containers, cups, bottles, pails, crates, tanks, drums, bumpers, lids,
industrial bulk
containers, industrial ves'sels, material handling containers, bottle cap
liners, bottle
caps, living hinge closures; toys, playground equipment, recreational
equipment,
boats, marine and safety equipment; wire and cable applications such as power
cables, communication cables and conduits; flexible tubing and hoses; pipe
applications including both pressure pipe and non-pressure pipe markets, e.g.
natural
gas distribution, water mains, interior plumbing, storm sewer, sanitary sewer,
corrugated pipes and conduit; foamed articles manufactured from foamed sheet
or
bun foam; military packaging (equipment and ready meals); personal care
packaging,
diapers and sanitary products; cosmetic, pharmaceutical and medical packaging,
and;
truck bed liners, pallets and automotive dunnage. The rigid manufactured
articles
summarized in this paragraph contain one or more of the ethylene interpolymer
products disclosed herein or a blend of at least one of the ethylene
interpolymer
products disclosed herein with at least one other thermoplastic.
Such rigid manufactured articles may be fabricated using the following non-
limiting
processes: injection molding, compression molding, blow molding, rotomolding,
profile
extrusion, pipe extrusion, sheet thermoforming and foaming processes employing
chemical or physical blowing agents.
The desired physical properties of rigid manufactured articles depend on the
application of interest. Non-limiting examples of desired properties include:
flexural
modulus (1% and 2% secant modulus); tensile toughness; environmental stress
crack
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resistance (ESCR); slow crack growth resistance (PENT); abrasion resistance;
shore
hardness; deflection temperature under load; VICAT softening point; IZOD
impact
strength; ARM impact resistance; Charpy impact resistance, and; color
(whiteness
and/or yellowness index).
The rigid manufactured articles described in this section may optionally
include,
depending on its intended use, additives and adjuvants. Non-limiting examples
of
additives and adjuvants include, antioxidants, slip agents, processing aids,
anti-static
additives, colorants, dyes, filler materials, heat stabilizers, light
stabilizers, light
absorbers, lubricants, pigments, plasticizers, nucleating agents and
combinations
thereof.
Testing Methods
Prior to testing, each specimen was conditioned for at least 24 hours at 23 2
C and
50 10% relative humidity and subsequent testing was conducted at 23 2 C and
50
10% relative humidity. Herein, the term "ASTM conditions" refers to a
laboratory that
is maintained at 23 2 C and 50 10% relative humidity; and specimens to be
tested
were conditioned for at least 24 hours in this laboratory prior to testing.
ASTM refers
to the American Society for Testing and Materials.
Density
Ethylene interpolymer product densities were determined using ASTM D792-13
(November 1,2013).
Melt Index
Ethylene interpolymer product melt index was determined using ASTM D1238
(August
1, 2013). Melt indexes, 12, 16, ho and 121 were measured at 190 C., using
weights of
2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively. Herein, the term "stress
exponent"
or its acronym "S.Ex.", is defined by the following relationship:
S.Ex.= log (16/12)/log(6480/2160)
wherein 16 and 12 are the melt flow rates measured at 190 C using 6.48 kg and
2.16 kg
loads, respectively.
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Conventional Size Exclusion Chromatography (SEC)
Ethylene interpolymer product samples (polymer) solutions (1 to 3 mg/mL) were
prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating
on a
wheel for 4 hours at 150 C in an oven. An antioxidant (2,6-di-tert-butyl-4-
methylphenol
(BHT)) was added to the mixture in order to stabilize the polymer against
oxidative
degradation. The BHT concentration was 250 ppm. Polymer solutions were
chromatographed at 140 C on a PL 220 high-temperature chromatography unit
equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB
as the mobile phase with a flow rate of 1.0 mL/minute, with a differential
refractive
index (DRI) as the concentration detector. BHT was added to the mobile phase
at a
concentration of 250 ppm to protect GPC columns from oxidative degradation.
The
sample injection volume was 200 pL. The GPC columns were calibrated with
narrow
distribution polystyrene standards. The polystyrene molecular weights were
converted to polyethylene molecular weights using the Mark-Houwink equation,
as
described in the ASTM standard test method D6474-12 (December 2012). The GPC
raw data were processed with the Cirrus GPC software, to produce molar mass
averages (Me, Mw, M) and molar mass distribution (e.g. Polydispersity, Mw/Me).
In the
polyethylene art, a commonly used term that is equivalent to SEC is GPC, i.e.
Gel
Permeation Chromatography.
Triple Detection Size Exclustion Chromatography (3D-SEC)
Ethylene interpolymer product samples (polymer) solutions (1 to 3 mg/mL) were
prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating
on a
wheel for 4 hours at 150 C in an oven. An antioxidant (2,6-di-tert-butyl-4-
methylphenol (BHT)) was added to the mixture in order to stabilize the polymer
against oxidative degradation. The BHT concentration was 250 ppm. Sample
solutions were chromatographed at 140 C on a PL 220 high-temperature
chromatography unit equipped with a differential refractive index (DRI)
detector, a
dual-angle light scattering detector (15 and 90 degree) and a differential
viscometer.
The SEC columns used were either four Shodex columns (HT803, HT804, HT805 and
HT806), or four PL Mixed ALS or BLS columns. TCB was the mobile phase with a
flow rate of 1.0 mL/minute, BHT was added to the mobile phase at a
concentration of
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250 ppm to protect SEC columns from oxidative degradation. The sample
injection
volume was 200 pL. The SEC raw data were processed with the Cirrus GPC
software,
to produce absolute molar masses and intrinsic viscosity (ND. The term
"absolute"
molar mass was used to distinguish 3D-SEC determined absolute molar masses
from
the molar masses determined by conventional SEC. The viscosity average molar
mass (Mu) determined by 3D-SEC was used in the calculations to determine the
Long
Chain Branching Factor (LCBF).
GPC-FTIR
Ethylene interpolymer product (polymer) solutions (2 to 4 mg/mL) were prepared
by
heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel
for 4
hours at 150 C in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol
(BHT) was
added to the mixture in order to stabilize the polymer against oxidative
degradation.
The BHT concentration was 250 ppm. Sample solutions were chromatographed at
140 C on a Waters GPC 150C chromatography unit equipped with four Shodex
columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a
flow rate of 1.0 mL/minute, with a FTIR spectrometer and a heated FTIR flow
through
cell coupled with the chromatography unit through a heated transfer line as
the
detection system. BHT was added to the mobile phase at a concentration of 250
ppm
to protect SEC columns from oxidative degradation. The sample injection volume
was
300 pL. The raw FTIR spectra were processed with OPUS FTIR software and the
polymer concentration and methyl content were calculated in real time with the
Chemometric Software (PLS technique) associated with the OPUS. Then the
polymer
concentration and methyl content were acquired and baseline-corrected with the
Cirrus GPC software. The SEC columns were calibrated with narrow distribution
polystyrene standards. The polystyrene molecular weights were converted to
polyethylene molecular weights using the Mark-Houwink equation, as described
in the
ASTM standard test method D6474. The comonomer content was calculated based
on the polymer concentration and methyl content predicted by the PLS technique
as
described in Paul J. DesLauriers, Polymer 43, pages 159-170 (2002); herein
incorporated by reference.
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The GPC-FTIR method measures total methyl content, which includes the methyl
groups located at the ends of each macromolecular chain, i.e. methyl end
groups. Thus,
the raw GPC-FTIR data must be corrected by subtracting the contribution from
methyl
end groups. To be more clear, the raw GPC-FTIR data overestimates the amount
of
short chain branching (SCB) and this overestimation increases as molecular
weight (M)
decreases. In this disclosure, raw GPC-FTIR data was corrected using the 2-
methyl
correction. At a given molecular weight (M), the number of methyl end groups
(NE) was
calculated using the following equation; NE = 28000/M, and NE (M dependent)
was
subtracted from the raw GPC-FTIR data to produce the SCB/1000C (2-Methyl
Corrected) GPC-FTIR data.
Composition Distribution Branching Index (CDBI)
The "Composition Distribution Branching Index", hereinafter CDBI, of the
disclosed
Examples and Comparative Examples were measured using a CRYSTAF/TREF 200+
unit equipped with an IR detector, hereinafter the CTREF. The acronym "TREF"
refers to Temperature Rising Elution Fractionation. The CTREF was supplied by
PolymerChAR S.A. (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-
46980
Valencia, Spain). The CTREF was operated in the TREF mode, which generates the
chemical composition of the polymer sample as a function of elution
temperature, the
Co/Ho ratio (Copolymer/Homopolymer ratio) and the CDBI (the Composition
Distribution Breadth Index), i.e. CDBI50 and CDBI25. A polymer sample (80 to
100 mg)
was placed into the reactor vessel of the CTREF. The reactor vessel was filled
with
35 ml of 1,2,4-trichlorobenzene (TCB) and the polymer was dissolved by heating
the
solution to 150 C for 2 hours. An aliquot (1.5 mL) of the solution was then
loaded into
the CTREF column which was packed with stainless steel beads. The column,
loaded
with sample, was allowed to stabilize at 110 C for 45 minutes. The polymer was
then
crystallized from solution, within the column, by dropping the temperature to
30 C at a
cooling rate of 0.09 C/minute. The column was then equilibrated for 30 minutes
at
C. The crystallized polymer was then eluted from the column with TCB flowing
30 through the column at 0.75 mL/minute, while the column was slowly heated
from 30 C
to 120 C at a heating rate of 0.25 C/minute. The raw CTREF data were processed
using Polymer ChAR software, an Excel spreadsheet and CTREF software developed
in-house. CDBI50 was defined as the percent of polymer whose composition is
within
50% of the median comonomer composition; CDBI50 was calculated from the
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composition distribution cure and the normalized cumulative integral of the
composition distribution curve, as described in United States Patent
5,376,439.
Those skilled in the art will understand that a calibration curve is required
to convert a
CTREF elution temperature to comonomer content, i.e. the amount of comonomer
in
the ethylene/a-olefin polymer fraction that elutes at a specific temperature.
The
generation of such calibration curves are described in the prior art, e.g.
Wild, et al., J.
Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455: hereby fully
incorporated by reference. CDBI25 as calculated in a similar manner; CDBI25 is
defined as the percent of polymer whose composition is with 25% of the median
comonomer composition. At the end of each sample run, the CTREF column was
cleaned for 30 minutes; specifically, with the CTREF column temperature at 160
C,
TCB flowed (0.5 mL/minute) through the column for 30 minutes. CTREF
deconvolutions were performed to determine the amount of branching (BrF
(#06/10000)) and density of the first ethylene interpolymer using the
following
equations: BrF (#06/10000) = 74.29¨ 0.7598 (TPcTREF), where TPCTREF is the
peak
elution temperature of the first ethylene interpolymer in the CTREF
chromatogram,
and BrF (#06/10000) = 9341.8 (p1)2 ¨ 17766 (p1) + 8446.8, where p1 was the
density
of the first ethylene interpolymer. The BrF (#06/10000) and density of the
second
ethylene interpolymer was determined using blending rules, given the overall
BrF
(#06/10000) and density of the ethylene interpolymer product. The BrF
(#06/10000)
and density of the second and third ethylene interpolymer was assumed to be
the
same.
Neutron Activation (Elemental Analysis)
Neutron Activation Analysis, hereinafter N.A.A., was used to determine
catalyst
residues in ethylene interpolymer products as follows. A radiation vial
(composed of
ultrapure polyethylene, 7 mL internal volume) was filled with an ethylene
interpolymer
product sample and the sample weight was recorded. Using a pneumatic transfer
system the sample was placed inside a SLOWPOKETM nuclear reactor (Atomic
Energy of Canada Limited, Ottawa, Ontario, Canada) and irradiated for 30 to
600
seconds for short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3 to 5
hours for long
half-life elements (e.g. Zr, Hf, Cr, Fe and Ni). The average thermal neutron
flux within
the reactor was 5x1011/cm2/s. After irradiation, samples were withdrawn from
the
reactor and aged, allowing the radioactivity to decay; short half-life
elements were
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aged for 300 seconds or long half-life elements were aged for several days.
After
aging, the gamma-ray spectrum of the sample was recorded using a germanium
semiconductor gamma-ray detector (Ortec model GEM55185, Advanced
Measurement Technology Inc., Oak Ridge, TN, USA) and a multichannel analyzer
(Ortec model DSPEC Pro). The amount of each element in the sample was
calculated from the gamma-ray spectrum and recorded in parts per million
relative to
the total weight of the ethylene interpolymer product sample. The N.A.A.
system was
calibrated with Specpure standards (1000 ppm solutions of the desired element
(greater than 99% pure)). One mL of solutions (elements of interest) were
pipetted
onto a 15 mm x 800 mm rectangular paper filter and air dried. The filter paper
was
then placed in a 1.4 mL polyethylene irradiation vial and analyzed by the
N.A.A.
system. Standards are used to determine the sensitivity of the N.A.A.
procedure (in
counts/pg).
Unsatu ration
The quantity of unsaturated groups, i.e. double bonds, in an ethylene
interpolymer
product was determined according to ASTM D3124-98 (vinylidene unsaturation,
published March 2011) and ASTM D6248-98 (vinyl and trans unsaturation,
published
July 2012). An ethylene interpolymer product sample was: a) first subjected to
a
carbon disulfide extraction to remove additives that may interfere with the
analysis; b)
the sample (pellet, film or granular form) was pressed into a plaque of
uniform
thickness (0.5 mm), and; c) the plaque was analyzed by FTIR.
Comonomer Content: Fourier Transform Infrared (FTIR) Spectroscopy
The quantity of comonomer in an ethylene interpolymer product was determine by
FTIR and reported as the Short Chain Branching (SCB) content having dimensions
of
CH3ii/1000C (number of methyl branches per 1000 carbon atoms). This test was
completed according to ASTM D6645-01 (2001), employing a compression molded
polymer plaque and a Thermo-Nicolet 750 Magna-IR Spectrophotometer. The
polymer plaque was prepared using a compression molding device (Wabash-Genesis
Series press) according to ASTM D4703-16 (April 2016).
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Dynamic Mechanical Analysis (DMA)
Oscillatory shear measurements under small strain amplitudes were carried out
to
obtain linear viscoelastic functions at 190 C under N2 atmosphere, at a strain
amplitude of 10% and over a frequency range of 0.02-126 rad/s at 5 points per
decade. Frequency sweep experiments were performed with a TA Instruments DH R3
stress-controlled rheometer using cone-plate geometry with a cone angle of 5 ,
a
truncation of 137 pm and a diameter of 25 mm. In this experiment a sinusoidal
strain
wave was applied and the stress response was analyzed in terms of linear
viscoelastic functions. The zero shear rate viscosity OA based on the DMA
frequency
sweep results was predicted by Ellis model (see R.B. Bird et al. "Dynamics of
Polymer
Liquids. Volume 1: Fluid Mechanics" Wiley-lnterscience Publications (1987)
p.228) or
Carreau-Yasuda model (see K. Yasuda (1979) PhD Thesis, IT Cambridge). In this
disclosure, the LCBF (Long Chain Branching Factor) was determined using the
DMA
determined 110.
Creep Test
Creep measurements were performed by an Anton Paar MCR 501 rheometer at
190 C using 25 mm parallel plate geometry under N2 atmosphere. In this
experiment,
a compression molded circular plaque with a thickness of 1.8 mm was placed
between the pre-heated upper and lower measurement fixtures and allowed to
come
to thermal equilibrium. The upper plate was then lowered to 50 pm above the
testing
gap size of 1.5 mm. At this point, the excess material was trimmed off and the
upper
fixture was lowered to the measurement gap size. A waiting time of 10 min
after
sample loading and trimming was applied to avoid residual stresses causing the
strain
to drift. In the creep experiment, the shear stress was increased instantly
from 0 to 20
Pa and the strain was recorded versus time. The sample continued to deform
under
the constant shear stress and eventually reached a steady rate of straining.
Creep
data was reported in terms of creep compliance (J(t)) which has the units of
reciprocal
modulus. The inverse of J(t) slope in the steady creeping regime was used to
calculate the zero shear rate viscosity based on the linear regression of the
data
points in the last 10% time window of the creep experiment.
In order to determine if the sample was degraded during the creep test,
frequency
sweep experiments under small strain amplitude (10%) were performed before and
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after creep stage over a frequency range of 0.1-100 rad/s. The difference
between
the magnitude of complex viscosity at 0.1 rad/s before and after the creep
stage was
used as an indicator of thermal degradation. The difference should be less
than 5% to
consider the creep determined zero shear rate viscosity acceptable.
Creep experiments confirmed that Reference Line, shown in Figure 1, for linear
ethylene interpolymers was also valid if the creep determined 110 was used
rather than
the DMA determined rio. In this disclosure, the LCBF (Long Chain Branching
Factor)
was determined using the DMA determined rio. To be absolutely clear, the zero
shear
viscosity (ZSV [poise]) data reported in Tables 1A, 2 and 3 were measured
using
DMA.
13C Nuclear Magnetic Resonance (NMR)
Between 0.21 and 0.30 g of polymer sample was weighed into lOmm NMR tubes.
The sample was then dissolved with deuterated ortho-dichlorobenzene (ODCB-d4)
and heated to 125 C; a heat gun was used to assist the mixing process. 13C NMR
spectra (24000 scans per spectra) were collected on a Bruker AVANCE III HD 400
MHz NMR spectrometer fitted with a 10 mm PABBO probehead maintained at 125 C.
Chemical shifts were referenced to the polymer backbone resonance, which was
assigned a value of 30.0 ppm. 13C spectra were processed using exponential
multiplication with a line broadening (LB) factor of 1.0 Hz. They were also
processed
using Gaussian multiplication with LB = -0.5 Hz and GB = 0.2 to enhance
resolution.
Short chain branching was calculated using the isolated method, where the
integral
area of peaks unique to that branch length are compared to the total integral
(standard
practice for branches up.to and including C5). Quantitative data for the C1,
C2, C3,
C4, (C6+LCB) and the Saturated Termini (Sat. Term.) carbons was presented in
Table
14, all values reported per 1000 total carbon atoms, data accuracy was 0.03
branches/1000C. Any values of 0.03 branches/1000C or less were assumed beyond
the ability to quantify and were marked with a 'D' to indicate that a peak was
detected
but not quantifiable in Table 14.
Figure 3 diagrams a long chain branched macromolecule on the left and a Cs
branched macromolecule on the right and the nomenclature, or code, used to
identify
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each carbon atom that appears in the 13C-NMR spectrum of these macromolecules.
Branchpoint carbons peaks (CH(L) and CH(6), 38.2 ppm), as well as the
1BL/1136,
213L/2B6 and 3BL/3136carbon peaks (at 14.1, 22.9, and 32.2 ppm, respectively)
are
close together in the spectrum. Additionally, the ends of a LCB are
functionally
equivalent to the ends of macromolecular chains. In ethylene-octene copolymers
there was separation between the 2136 and 3136 peaks and the 2s & 3s peaks in
the
chain termini. With the goal of deconvoluting the C6 and LCB contributions to
the
branchpoint peak (38.2 ppm), the spectra were reprocessed using a Gaussian
function (as opposed to an exponential function), specifically LB = -0.5 and
GB = 0.2.
The net effect of this reprocessing was to 'trade off' some signal/noise (SIN)
for
additional resolution without negatively impacting peak integration, i.e.
quantification
of the respective carbons. Using this technique, the values for C6, LCB and
saturated
termini were obtained using the following method: 1) the values for (C6 + LCB)
peak
at 38.2 ppm and the two (LCB + sat. term.) peaks at 32.2 and 22.9 ppm were
calculated from the 'standard' spectrum; 2) these three peak regions in the
Gaussian
reprocessed spectra (i.e. 38.2, 32.2 and 22.9 ppm) were integrated to obtain a
ratio
for each carbon within the respective peak; 3) these ratios were converted to
a value
per 1000 carbons by normalizing by the respective integrated area measured in
step
1); 4) the saturated termini was the average of that from 2s & 3s peaks; 5)
the C6
value was estimated from the integrals of the small peaks on the far left of
these three
regions, and; 6) the LCB value was estimated from the peak at 38.2 ppm.
Film Dart Impact
Film dart impact strength was determined using ASTM D1709-09 Method A (May 1,
2009). In this disclosure the dart impact test employed a 1.5 inch (38 mm)
diameter
hemispherical headed dart.
=
Film Puncture
Film "puncture", the energy (J/mm) required to break the film was determined
using
ASTM D5748-95 (originally adopted in 1995, reapproved in 2012).
Film Lubricated Puncture
The "lubricated puncture" test was performed as follows: the energy (J/mm) to
puncture a film sample was determined using a 0.75-inch (1.9-cm) diameter pear-
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shaped fluorocarbon coated probe travelling at 10-inch per minute (25.4-
cm/minute).
ASTM conditions were employed. Prior to testing the specimens, the probe head
was
manually lubricated with Muko Lubricating Jelly to reduce friction. Muko
Lubricating
Jelly is a water-soluble personal lubricant available from Cardinal Health
Inc., 1000
Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe was mounted in an lnstron
Models SL Universal Testing Machine and a 1000-N load cell as used. Film
samples
(1.0 mil (25 i_tm) thick, 5.5 inch (14 cm) wide and 6 inch (15 cm) long) were
mounted in
the lnstron and punctured.
Film Tensile
The following film tensile properties were determined using ASTM D882-12
(August 1,
2012): tensile break strength (MPa), elongation at break (%), tensile yield
strength
(MPa), tensile elongation at yield (%) and film toughness or total energy to
break
(ft-lb/in3). Tensile properties were measured in the both the machine
direction (MD)
and the transverse direction (TD) of the blown films.
Film Secant Modulus
The secant modulus is a measure of film stiffness. Secant moduli were
determined
according to ASTM D882. The secant modulus is the slope of a line drawn
between
two points on the stress-strain curve, i.e. the secant line. The first point
on the stress-
strain curve is the origin, i.e. the point that corresponds to the origin (the
point of zero
percent strain and zero stress), and; the second point on the stress-strain
curve is the
point that corresponds to a strain of 1%; given these two points the 1% secant
modulus is calculated and is expressed in terms of force per unit area (MPa).
The 2%
secant modulus is calculated similarly. This method is used to calculated film
modulus because the stress-strain relationship of polyethylene does not follow
Hook's
law; i.e. the stress-strain behavior of polyethylene is non-linear due to its
viscoelastic
nature. Secant moduli Were measured using a conventional lnstron tensile
tester
equipped with a 200 lbf load cell. Strips of monolayer film samples were cut
for
testing with following dimensions: 14 inch long, 1 inch wide and 1 mil thick;
ensuring
that there were no nicks or cuts on the edges of the samples. Film samples
were cut
in both the machine direction (MD) and the transverse direction (TD) and
tested.
ASTM conditions were used to condition the samples. The thickness of each film
was
accurately measured with a hand-held micrometer and entered along with the
sample
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name into the lnstron software. Samples were loaded in the Instron with a grip
separation of 10 inch and pulled at a rate of 1 inch/min generating the strain-
strain
curve. The 1% and 2% secant modulus were calculated using the lnstron
software.
Film Puncture-Propagation Tear
Puncture-propagation tear resistance of blown film was determined using ASTM
D2582-09 (May 1, 2009). This test measures the resistance of a blown film to
snagging, or more precisely, to dynamic puncture and propagation of that
puncture
resulting in a tear. Puncture-propagation tear resistance was measured in the
machine direction (MD) and the transverse direction (TD) of the blown films.
Film Elmendorf Tear
Film tear performance was determined by ASTM D1922-09 (May 1, 2009); an
equivalent term for tear is "Elmendorf tear". Film tear was measured in both
the
machine direction (MD) and the transverse direction (TD) of the blown films.
Film Opticals
Film optical properties were measured as follows: Haze, ASTM D1003-13
(November
15, 2013), and; Gloss ASTM D2457-13 (April 1,2013).
Film Dvnatup Impact
Instrumented impact testing was carried out on a machine called a Dynatup
Impact
Tester purchased from Illinois Test Works Inc., Santa Barbara, CA, USA; those
skilled
in the art frequently call this test the Dynatup impact test. Testing was
completed
according to the following procedure. Test samples are prepared by cutting
about 5
inch (12.7 cm) wide and about 6 inch (15.2 cm) long strips from a roll of
blown film;
film was about 1 mil thick. Prior to testing, the thickness of each sample was
accurately measured with a handheld micrometer and recorded. ASTM conditions
were employed. Test samples were mounted in the 9250 Dynatup Impact drop
tower/test machine using the pneumatic clamp. Dynatup tup #1, 0.5 inch (1.3
cm)
diameter, was attached to the crosshead using the Allen bolt supplied. Prior
to
testing, the crosshead is raised to a height such that the film impact
velocity is 10.9
0.1 ft/s. A weight was added to the crosshead such that: 1) the crosshead
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slowdown, or tup slowdown, was no more than 20% from the beginning of the test
to
the point of peak load and 2) the tup must penetrate through the specimen. If
the tup
does not penetrate through the film, additional weight is added to the
crosshead to
increase the striking velocity. During each test the Dynatup Impulse Data
Acquisition
System Software collected the experimental data (load (lb) versus time). At
least 5
film samples are tested and the software reports the following average values:
"Dynatup Maximum (Max) Load (lb)", the highest load measured during the impact
test; "Dynatup Total Energy (ft-lb)", the area under the load curve from the
start of the
test to the end of the test (puncture of the sample), and; "Dynatup Total
Energy at Max
Load (ft-lb)", the area under the load curve from the start of the test to the
maximum
load point.
Film Hot Tack
In this disclosure, the "Hot Tack Test" was performed as follows, using ASTM
conditions. Hot tack data was generated using a J&B Hot Tack Tester which is
commercially available frbm Jbi Hot Tack, Geloeslaan 30, B-3630 Maamechelen,
Belgium. In the hot tack test, the strength of a polyolefin to polyolefin seal
is
measured immediately after heat sealing two film samples together (the two
film
samples were cut from the same roll of 2.0 mil (51- m) thick film), i.e. when
the
polyolefin macromolecules that comprise the film are in a semi-molten state.
This test
simulates the heat sealing of polyethylene films on high speed automatic
packaging
machines, e.g., vertical or horizontal form, fill and seal equipment. The
following
parameters were used in the J&B Hot Tack Test: film specimen width, 1 inch
(25.4
mm); film sealing time, 0.5 second; film sealing pressure, 0.27 Nimm2; delay
time, 0.5
second; film peel speed, 7.9 in/second (200 mm/second); testing temperature
range,
203 F to 293 F (95 C to 145 C); temperature increments, 9 F (5 C); and five
film
samples were tested at each temperature increment to calculate average values
at
each temperature. The following data was recorded for the disclosed Example
films
and Comparative Example films: the "Tack Onset @ 1.0 N ( C)", the temperature
at
which a hot tack force of 1N was observed (average of 5-film samples); "Max
Hot tack
Strength (N)", the maximum hot tack force observed (average of 5-film samples)
over
the testing temperature range, and; "Temperature ¨ Max. Hot tack ( C)", the
temperature at which the maximum hot tack force was observed.
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Film Heat Seal Strength
In this disclosure, the "Heat Seal Strength Test" was performed as follows.
ASTM
conditions were employed. Heat seal data was generated using a conventional
lnstron Tensile Tester. In this test, two film samples are sealed over a range
of
temperatures (the two film samples were cut from the same roll of 2.0 mil (51-
m)
thick film). The following parameters were used in the Heat Seal Strength
Test: film
specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film sealing
pressure,
40 psi (0.28 N/mm2); temperature range, 212 F to 302 F (100 C to 150 C) and
temperature increment, 9 F (5 C). After aging for at least 24 hours at ASTM
conditions, seal strength was determined using the following tensile
parameters: pull
(crosshead) speed, 12 inch/min (2.54 cm/min); direction of pull, 900 to seal,
and; 5
samples of film were tested at each temperature increment. The Seal Initiation
Temperature, hereinafter S.I.T., is defined as the temperature required to
form a
commercially viable seal; a commercially viable seal has a seal strength of
2.0 lb per
inch of seal (8.8 N per 25.4 mm of seal).
Film Hexane Extractable's
Hexane extractables was determined according to the Code of Federal
Registration
21 CFR 177.1520 Para (c) 3.1 and 3.2; wherein the quantity of hexane
extractable
material in a film is determined gravimetrically. Elaborating, 2.5 grams of
3.5 mil (89
[tm) monolayer film was placed in a stainless steel basket, the film and
basket were
weighed (w1). While in the basket the film was: extracted with n-hexane at
49.5 C for
two hours; dried at 80 C in a vacuum oven for 2 hours; cooled in a desiccator
for 30
minutes, and; weighed (wf). The percent loss in weight is the percent hexane
extractables (wC6): wC6 = 100 x (w'-wf)/wi.
EXAMPLES
Pilot Plant Polymerizations
The following examples are presented for the purpose of illustrating selected
embodiments of this disclosure, it being understood that, the examples
presented
hereinafter do not limit the claims presented.
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Disclosed embodiments of the ethylene interpolymer products were prepared in a
continuous solution pilot plant operated in both series mode and parallel mode
as fully
described below. Comparative ethylene interpolymer products were also prepared
in
the same pilot plant.
Series Polymerization
Series mode Example 50 and Example 51 of ethylene interpolymer products and
series mode Comparative 60, shown in Tables 4A through 4C, were produced using
an R1 pressure from about 14 MPa to about 18 MPa; R2 was operated at a lower
pressure to facilitate continuous flow from R1 to R2. In series mode the first
exit
stream from Al flows directly into R2. Both CSTR's were agitated to give
conditions
in which the reactor contents were well mixed. The process was operated
continuously by feeding fresh process solvent, ethylene, 1-octene and hydrogen
to the
reactors. Methylpentane was used as the process solvent (a commercial blend of
methylpentane isomers). The volume of the first CSTR reactor (R1) was 3.2
gallons
(12 L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L) and
the
volume of the tubular reactor (R3) was 0.58 gallons (2.2 L).
The following components were used to prepare the first homogeneous catalyst
formulation that was injected into R1, i.e. the bridged metallocene catalyst
formulation
comprising: a component A, either diphenylmethylene(cyclopentadienyl)(2,7-di-t-
butylfuorenyl)hafnium dichloride [(2,7-tBu2Flu)Ph2C(Cp)HfC12] (abbreviated CpF-
1) or
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dimethyl,
[(2,7-
tBu2F1u)Ph2C(Cp)HfMe2] (abbreviated CpF-2); component M, methylaluminoxane
(M MAO-07); component B, trityl tetrakis(pentafluoro-phenyl)borate, and;
cornponent
P, 2,6-di-tert-butyl-4-ethylphenol. As shown in Table 4A, CpF-1 was used to
produce
Example 50 and CpF-2 was used to produce Examples 51 and 52. To prepare the
bridged metallocene catalyst formulation the following catalyst component
solvents
were used: methylpentane for components M and P, and; xylene for component A
and
B.
Comparative ethylene interpolymer products were prepare by injecting the third
homogeneous catalyst formulation into R1. In Comparative ethylene interpolymer
products the third homogeneous catalyst formulation replaces the first
homogeneous
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catalyst formulation. One embodiment of the third homogeneous catalyst
formulation
was an unbridged single site catalyst formulation comprising: component C,
either
cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride [Cp[(t-
Bu)3PN]TiC12] (abbreviated PIC-1) or cyclopentadienyl
tri(isopropyl)phosphinimine
titanium dichloride [Cp[(ikpropy1)3PN]TiC12] (abbreviated PI0-2); component M,
methylaluminoxane (M MAO-07); component B, trityl tetrakis(pentafluoro-
phenyl)borate, and; component P, 2,6-di-tert-butyl-4-ethylphenol. As shown in
Table
4A, PI0-2 was used to produce Comparative 60 and PIC-1 was used to produce
Comparative 61. To prepare the unbridged single site catalyst formulation the
following catalyst component solvents were used: methylpentane for components
M
and P, and; xylene for component A and B.
The quantity of CpF-1 or CpF-2 added to reactor 1 (R1) is shown in Table 4A,
e.g. "R1
catalyst (ppm)" was 0.72 ppm of CpF-1 in the case of Example 50. The
efficiency of
the first homogeneous catalyst formulation was optimized by adjusting the mole
ratios
of the catalyst components and the R1 catalyst inlet temperature. As shown in
Table
4A, the mole ratios optimized were: ([M]/[A]), i.e. [(MMA0-07)/(CpF-1)];
([P]/]M]), i.e.
[(2,6-di-tert-butyl-4-ethylphenol)/(MMA0-07)], and; ([13]/[A]), i.e. [(trityl
tetrakis(pentafluoro-pheriy1)borate)/(CpF-1)]. To be more clear, in Example 50
(Table
4A), the mole ratios in R1 were: ([M]/[A]) = 122; ([P]/[M]) = 0.40, and;
([B]/[A]) = 1.47.
As shown in Table 40, the catalyst inlet temperature of the bridged
metallocene
catalyst formulation was: about 145 C in the case of CpF-1, and; about 21 to
about
C in the case of CpF-2.
25 In the Comparatives the quantity of PIC-1 or PI0-2 added to reactor 1
(R1) is shown in
Table 4A, e.g. "R1 catalyst (ppm)" was 0.14 ppm of PI0-2 in the case of
Comparative
60. The efficiency of the third homogeneous catalyst formulation was optimized
by
adjusting the mole ratios of the catalyst components and the R1 catalyst inlet
temperature. As shown in Table 4A, the mole ratios optimized were: ([M]/[C]),
i.e.
(MMA0-07)/(P1C-2); ([P]/[M]), i.e. (2,6-di-tert-butyl-4-ethylphenol)/(MMA0-
07), and;
([13]/[C]), i.e. (trityl tetrakis(pentafluoro-phenyl)borate)/(PIC-2). To be
more clear, as
shown in Table 4A, in Comparative 60 the mole ratios in R1 were: ([M]/[C]) =
65;
([P]/[M]) = 0.30, and; ([13]/[C]) = 1.20. As shown in Table 40, the R1
catalyst inlet
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temperature of the unbridged single site catalyst formulation was about 30 to
about
32 C.
In both Examples and Comparatives a second homogeneous catalyst formulation
was
injected into the second reactor (R2), e.g. an unbridged single site catalyst
formulation, PIC-1 or PIO-2 as specified in Table 4A.
Average residence time of the solvent in a reactor is primarily influenced by
the
amount of solvent flowing through each reactor and the total amount of solvent
flowing
through the solution process, the following are representative or typical
values for the
Examples and Comparatives shown in Tables 4A-4C, as well as Examples shown in
Tables 6A-6C: average reactor residence times were: about 61 seconds in R1,
about
73 seconds in R2, about 7.3 seconds for an R3 volume of 0.58 gallons (2.2 L).
Polymerization in the continuous solution polymerization process was
terminated by
adding a catalyst deactivator to the third exit stream exiting the tubular
reactor (R3).
The catalyst deactivator used was octanoic acid (caprylic acid), commercially
available from P&G Chemicals, Cincinnati, OH, U.S.A. The catalyst deactivator
was
added such that the moles of fatty acid added were 50% of the total molar
amount of
hafnium, titanium and aluminum added to the polymerization process; to be
clear, the
moles of octanoic acid added = 0.5 x (moles hafnium + moles titanium + moles
aluminum); this mole ratio was consistently used in both Examples and
Comparatives.
A two-stage devolitizing process was employed to recover the ethylene
interpolymer
product from the process solvent, i.e. two vapor/liquid separators were used
and the
second bottom stream (from the second V/L separator) was passed through a gear
pump/pelletizer combination.
Prior to pelletization the ethylene interpolymer product was stabilized by
adding 500
ppm of Irganox 1076 (a primary antioxidant) and 500 ppm of lrgafos 168 (a
secondary
antioxidant), based on weight of the ethylene interpolymer product.
Antioxidants were
dissolved in process solvent and added between the first and second V/L
separators.
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Tables 4A-4C disclose additional process parameters, e.g. ethylene and 1-
octene
splits between the reactors, and reactor temperatures and ethylene
conversions, etc.
In Tables 4A-4C the targeted ethylene interpolymer product was about 1.0
dg/min
(melt index (12), as measured according to ASTM D1239, 2.16kg load,190 C) and
about 0.917 g/cm3 (as measured according to ASTM D792).
Tables 6A-6C disclose cOntinuous solution process parameters for Example 58
(about
4 dg/min (12) and about 0.928 g/cc) and Example 59 (about 0.24 dg/min (12) and
about
0.944 g/cc).
Parallel Polymerization
The pilot plant described above was reconfigured to operate in parallel mode.
In
parallel mode the first exit stream (exiting the first reactor) by-passes the
second
reactor and the first exit stream is combined with the second exit stream
(exiting the
second reactor) downstream of the second reactor. To be more clear, Figure 2
illustrates parallel mode operation where: the first exit stream llg (dotted
line) by-
passes the second reactor 12a, streams llg and stream 12c (second exit stream
from
reactor 12a) are combined to form a third exit stream 12d, and; the third exit
stream
flows into the tubular reactor 17. As shown in Tables 4A through 4C, Example
52 is
one embodiment of an ethylene interpolymer product synthesized using parallel
mode
operation. Catalyst optimization and additional process parameters for Example
52,
e.g. ethylene and 1-octene splits between the reactors, and reactor
temperatures and
ethylene conversions, etc., are summarized in Tables 4A-4C.
Given the continuous solution polymerization conditions shown in Table 4A
through
Table 4C, the physical properties of the resulting ethylene interpolymer
products are
summarized in Table 5, i.e. Examples 50-52. Table 5 also discloses the
physical
properties of Comparatives 60, 61 and 67. Comparative 67 was a commercially
available solution process ethylene/1-octene polymers produced by NOVA
Chemicals
Company (Calgary, Alberta, Canada) SURPASS FPs117-C, produced using the
unbridged single site catalyst formulation in rectors 1 and 2. As shown in
Table 5,
Neutron Activation Analysis results disclose catalyst residues in Examples 51
and 52
and Comparatives 60, 61 and 67. Given the continuous solution polymerization
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conditions shown in Tables 6A through 6C, the resulting ethylene interpolymer
products produced are summarized in Table 7, i.e. Examples 58 and 59.
Table 8 compares physical attributes of Example 51 with Comparative 67, i.e.
the
weight fractions, molecular weights (Me, Mw and Mw/Me), branching (#C6/1000C),
CDBI50, density, melt index and long chain branching factor (LDBF) of the
first
ethylene interpolymer, second ethylene interpolymer, third ethylene
interpolymer and
the ethylene interpolymer product are disclosed. Results in Table 8 were
generated
by deconvoluting the SEC and CTREF curves of Example 51 and Comparative 67
into
their respective components. Graphically, Figure 4 illustrates the
deconvolution of the
experimentally measured SEC of Example 51 into three components, i.e. the
first,
second and third ethylene interpolymer. In Example 51 the first ethylene
interpolymer
having a density of 0.8940 g/cm3 was produced using an ((1-
octene)/(ethylene))R1
weight ratio of 0.41. In contrast, in Comparative 67 the first ethylene
interpolymer
density having a density of 0.9141 g/cm3 was produced using an ((1-
octene)/(ethylene))R1 weight ratio of 1.43. Even though Example 51 was
produced
with a 71% lower octene/ethylene ratio, relative to Comparative 67, the first
ethylene
interpolymer in Example 51 was of lower density. Both of these trends shown by
Example 51 employing the bridged metallocene catalyst formulation, i.e. a
lower
(octene/ethylene) ratio and a lower density are advantageous, relative to
Comparative
67 employing the unbridged single site catalyst formulation. Table 8 also
discloses a
Ap, (p2 - p1) or [(the density of the second ethylene interpolymer) ¨ (the
density of the
first ethylene interpolymer)], was higher in Example 51 relative to
Comparative 67.
Specifically, Ap was 0.0473 and 0.0040 g/cm3 for Example 51 and Comparative
67,
respectively. Higher Ap's are advantageous in several end-use applications. In
Figure 4: the molecular weight distribution of the first, second and third
ethylene
interpolymers were assumed similar to Flory distributions. The weight percent
of the
third ethylene interpolymer was assumed to be 5%.
As shown in Table 8, the weight average molecular weights (Mw) of the first
ethylene
interpolymers in Example 51 and Comparative 67 were 141,247 and 165,552,
respectively. The lower Mw of the first ethylene interpolymer in Example 51
reflects
the fact that reactor 1 contained 5.35 ppm of hydrogen; in contrast, in
Comparative 67
the first ethylene interpolymer was synthesized using 0.60 ppm of hydrogen in
reactor
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1. Those of ordinary experience are cognizant of the fact that hydrogen is
used to
control Mw (or melt index) in olefin polymerization, i.e. hydrogen is very
effective in
terminating propagating macromolecules. Further, given Table 8, those of
ordinary
experience would have recognized the higher molecular weight capability of the
bridged metallocene catalyst relative to the unbridged single site catalyst.
Elaborating, relative to Comparative 67, the amount of hydrogen used to
synthesize
the first ethylene interpolymer in Example 51 was about an order of magnitude
higher,
and yet the Mw's differed by only 15%. This trend of higher hydrogen
concentration
for the bridged metallocene catalyst formulation, relative to the unbridged
single site
catalyst formulation, demonstrated the higher molecular weight capability of
the
former. Example 51 and Comparative 67 were produced at similar reactor
temperatures, i.e. 139.5 C and 140.0 C, respectively.
Blown Films: Ethylene Interpolymer Products
Monolayer blown films were produced on a Gloucester extruder, 2.5 inch (6.45
cm)
barrel diameter, 24/1 LID (barrel Length/barrel Diameter) equipped with: a
barrier
screw; a low pressure 4 inch (10.16 cm) diameter die with a 35 mil (0.089 cm)
die gap,
and; a Western Polymer Air ring. Blown films, 1.0 mil (25 m) thick, were
produced at
a constant output rate of 100 lb/hr (45.4 kg/hr) by adjusting extruder screw
speed,
and; the frost line height was maintained at about 16 inch (40.64 cm) by
adjusting the
cooling air. Blown film processing conditions for Examples 51 and 52 and
Comparative 67 are disclosed in Table 9. Monolayer blown film was also
produced at
2.0 mil (51 m) and 3.5 mil (89 p.m) to determine the seal initiation
temperature (SIT)
and hexane extractables, respectively. Processing aid, encapsulated in a
polyethylene masterbatch, was added to all resins prior to film extrusion; the
processing aid added was Dynamar FX 5920A (commercially available from The 3M
Company, St. Paul, MN, USA).
As shown in Table 9, in blown film processes, Examples 51 and 52 have improved
processability relative to Comparative 67, i.e. lower extrusion pressures and
lower
extruder current draw. Improved processability is desirable to the film
converter
because improved processability means higher production rates, e.g. an
increase in
the pounds of film produced per hour, or feet (meters) of film produced per
hour.
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As shown in Table 10A, relative to Comparative 67, blown films produced from
Examples 51 and 52 can be advantageously used in any film application where
improved film hexane extractables are desired, e.g. in food packaging
applications.
The hexane extractables of a blown film, Example 51F, prepared from Example 51
were: 65% lower relative to Comparative 67. The hexane extractables of a blown
film,
Example 52F, prepared from Example 52 were: 54% lower relative to Comparative
67.
As shown in Table 10A, the seal initiation temperature (SIT) of Example 51F
film
(produced in a series solution process) was 93.6 C; which was improved (i.e.
lower by
6%) relative to Comparative 67's SIT of 99.1 C. The seal initiation
temperature (SIT)
of Example 52F film (produced in a parallel solution process) was 89.1 C;
which was
improved (i.e. lower by 10%) relative to Comparative 67's SIT of 99.1 C. As
shown in
Table 10A, the Tack Onset (at 1.0N) of film Examples 51F and 52F were 90 and
86 C,
respectively; which were improved (i.e. lower by 11% and 15%, respectively)
relative
to film Comparative 67F's SIT of 101 C. As shown in Table 10A, the temperature
at
which the maximum Hot Tack was observed was 105 and 100 C for film Examples
51F and 52F, respectively, which can be compared to Comparative 67F's 115 C
value. To be clear, the temperature at maximum Hot Tack of film 51F was
improved
(lower) by 9%, relative to Comparative 67F; similarly the temperature at
maximum Hot
Tack of film 52F was improved by 13%, relative to Comparative 67F. Lower
SIT's,
lower Tack onset and a lower temperature at maximum Hot Tack are desirable in
food
packaging applications, e.g. high speed vertical form-fill-seal food packaging
lines.
As shown in Table 10A, the machine direction Elmendorf tear strength of film
Example
52F was 288 g was similar to film Comparative 67F machine direction Elmendorf
tear
strength of 282 g. The transverse direction Elmendorf tear strength of film
Example
52F was 568 g; i.e. improved (higher by 12%) relative to film Comparative 67F
transverse direction Elmendorf film tear strengths of 507 g. The dart impact
of
Example 51F (series configuration) was 800 g, i.e. improved by 100% relative
to
Comparative 67F dart impact of 400 g.
As shown in Table 10B, relative to Comparative 67F, blown films produced from
Examples 51F and 52F can be advantageously used in film application where
higher
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film moduli are desired. One of the desirable features of higher film moduli
is the
ability to reduce film thickness, reducing film thickness contributes to
source reduction,
sustainability and reduces overall costs. The machine direction 1% secant
modulus of
Example 51F (212 MPa) was 29% improved (higher) relative to Comparative 67F
(164
MPa), and; the transverse direction 1% secant modulus of Example 51F (255 MPa)
was 58% improved relative to Comparative 67F (161 MPa). The machine direction
1% secant modulus of Example 52F (228 MPa) was 39% improved (higher) relative
to
Comparative 67F, and; the transverse direction 1% secant modulus of Example
52F
(258 MPa) was 60% improved relative to Comparative 67F. This same trend was
also
evident in the 2% secant modulus. Specifically, the machine direction 2%
secant
modulus of Example 51F (178 MPa) was 25% improved (higher) relative to
Comparative 67F (142 MPa), and; the transverse direction 2% secant modulus of
Example 51F (211 MPa) was 54% improved relative to Comparative 67F (137 MPa).
Similarly, the machine direction 2% secant modulus of Example 52F (190 MPa) as
33% improved (higher) relative to Comparative 67F, and; the transverse
direction 2%
secant modulus of Example 52F (215 MPa) was 57% improved relative to
Comparative 67F. Table 10B also shows improved (higher) tensile yield strength
for
Examples 51F and 52F, relative to Comparative 67F. Higher yield strengths
reduce
the tendency of a loaded package to yielding, deform or distort under its own
weight.
The machine direction tensile yield strength of Example 51F was 10.2 MPa,
which
was 12% improved (higher) relative to Comparative 67F (9.1MPa), and; the
transverse direction tensile yield strength of Example 51F (11.4 MPa) was 31%
improved relative to Comparative 67F (8.7 MPa). The machine direction tensile
yield
strength of Example 52F.was 10.5 MPa, which was 15% improved (higher) relative
to
Comparative 67F, and; the transverse direction tensile yield strength of
Example 52F
(11.5 MPa) was 32% improved relative to Comparative 67F.
As shown in Table 10B, the blown film produced from Example 52 (parallel mode)
had
a higher (21% improved) film toughness (Total Energy to Break TD) of 1605
ft=lb/in3,
relative to the blown film produced from Comparative 67 (series mode) having a
film
toughness of 1327 ft=lb/in3.
Continuous Polymerization Unit (CPU)
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Comparison Of Catalyst Formulations In One Reactor
Small scale continuous solution polymerizations were conducted on a Continuous
Polymerization Unit, hereinafter CPU. The purpose of these experiments were to
directly compare the performance of the bridged metallocene catalyst
formulation
(containing component A, CpF-1) with the unbridged single site catalyst
formulation
(containing component C, PIC-1) in one reactor.
The single reactor of the CPU was a 71.5 mL continuously stirred CSTR,
polymerizations were conducted at 130 C, 160 C or 190 C and the reactor
pressure
was about 10.5 MPa. The CPU included a 20 mL upstream mixing chamber that was
operated at a temperature that was 5 C lower than the downstream
polymerization
reactor. The upstream mixing chamber was used to pre-heat the ethylene,
optional a-
olefin and a portion of the process solvent. Catalyst feeds and the remaining
solvent
were added directly to the polymerization reactor as a continuous process. The
total
flow rate to the polymerization reactor was held constant at 27 mL/minute. The
components of the bridged metallocene catalyst formulation (component A,
component M, component B and component P) were added directly to the
polymerization reactor to maintain the continuous polymerization process. More
specifically: component A and component B were premixed in xylene and injected
directly into the reactor, and; component M and optionally component P were
premixed in process solvent and injected directly into the reactor. In the
comparative
experiments, the components of the unbridged single site catalyst formulation
(component C, component M, component B and component P) were added directly to
the polymerization reactor to maintain the continuous polymerization process.
More
specifically: component C and component B were premixed in xylene and injected
directly into the reactor, and; component M and optionally component P were
premixed in process solvent and injected directly into the reactor. In the
examples,
the component A employed was CpF-1 [(2,7-tBu2F1u)Ph2C(Cp)HfC12]. In the
comparatives, the component C employed was PIC-1 ([Cp[(t-Bu)3PN]TiC12]).
Components M, B and P were methylaluminoxane (MMA0-07), trityl
tetrakis(pentafluoro-phenyl)borate, and 2,6-di-tert-butyl-4-ethylphenol,
respectively.
Upon injection, the catalyst was activated in situ (in the polymerization
reactor) in the
presence of ethylene and optional a-olefin comonomer. Component M was added
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such that the mole ratio of ([M]/[A]) or ([M]/[C]) was about 80; component B
was added
such that the mole ratio of ([M]/[A]) or ([M]/[C]) was about 1.0, and;
component P was
added such that the mole ratio of ([P]/[M]) was about 0.4.
Ethylene was supplied to the reactor by a calibrated thermal mass flow meter
and was
dissolved in the reaction solvent prior to the polymerization reactor.
Optional
comonomer (1-octene) was premixed with ethylene before entering the
polymerization
reactor, the (1-octene)/(ethylene) weight ratio varied from 0 to about 6Ø
Ethylene
was fed to the reactor such that the ethylene concentration in the reactor
varied from
about 7 to about 15 weight%; where weight % is the weight of ethylene divided
by the
total weight of the reactor contents. The internal reaction temperature was
monitored
by a thermocouple in the, polymerization medium and was controlled at the
target set
point to 0.5 C. Solvent, monomer, and comonomer streams were all purified by
the
CPU systems prior to entering the reactor.
The ethylene conversion, OcPu, i.e. the fraction of ethylene converted was
determined
by an online gas chromatograph (GC) and polymerization activity, KpcPu, having
dimensions of [U(mmol-min)] was defined as:
1 ¨ QcPU
vCPU = QCPU ( _____________
[catalyst] x HUTcPu)
where HUTcPu was a reciprocal space velocity (Hold Up Time) in the
polymerization
reactor having dimensions of minutes (min), and; [catalyst] was the
concentration of
catalyst in the polymerization reactor expressed in mmol/L of titanium or
hafnium. In
some CPU experiments,.QcPu was held constant at about 90% and the HUTcPu was
held constant at about 2.5 minutes. In other CPU experiments, QcPu was varied
from
about 75 to about 95%. Downstream of the reactor the pressure was reduced to
atmospheric pressure. The polymer product was recovered as a slurry in the
process
solvent and subsequently dried by evaporation in a vacuum oven prior to
characterization.
At a polymerization temperature of 130 C, the CPU conditions were adjusted to
synthesize ethylene interpolymers at approximately constant melt index and
density;
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specifically, a first ethylene interpolymer synthesized with the bridged
metallocene
catalyst formulation and a comparative ethylene interpolymer produced with the
unbridged single site catalyst formulation. As shown by each row in Table 11A,
at a
reactor temperature of 130 C, the bridged metallocene catalyst formulation
produced
an improved (higher) SEC weight average molecular weight (MwA), relative to
the
comparative unbridged single site catalyst formulation (Mwc). The percent
improvement in Mw was at least 5% as calculated using the following formula:
% Improved Mw = 100% x (Mv./'`-Mwc)/Mwc
Similarly, at a polymerization temperature of 160 C, each row of Table 11B
shows that
the bridged metallocene catalyst formulation produced an improved (higher) SEC
weight average molecular weight (MwA), relative to the comparative unbridged
single
site catalyst formulation (Mwc). The percent improvement in Mw was at least
10%.
As shown in Table 12A, at a polymerization temperature of 130 C, the (a-
olefin/ethylene) weight ratio in the reactor had to be adjusted such that
ethylene
interpolymers were produced having a target density. More specifically, (a-
olefin/ethylene)' was required to synthesize a first ethylene interpolymer,
having a
target density, using the bridged metallocene catalyst formulation. In
contrast, (a-
olefinlethylene)c was required to synthesize a control ethylene interpolymer,
having
the target density, using the unbridged single site catalyst formulation. As
shown by
each row in Table 12A, at 130 C, the bridged metallocene catalyst formulation
allows
the operation of the continuous solution polymerization process at an improved
(reduced) (a-olefin/ethylene) weight ratio, relative to the control unbridged
single site
catalyst formulation. The percent reduction in (a-olefin/ethylene) weight
ratio was at
least -70% as calculated using the following formula:
(a ¨ olefin\ A (a ¨ olefin\c
ra
% Reduced _________ ¨ ole fin = 100>< ] ethylene ethylene)
< ¨70%
ethylene I (a ¨
olefin C
ethylene
Similarly, at a polymerization temperature of 160 C, each row of Table 12B
shows that
the bridged metallocene catalyst formulation allows the operation of the
continuous
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solution polymerization process at an improved (reduced) (a-olefin/ethylene)
weight
ratio, relative to the control unbridged single site catalyst formulation. In
Table 12B,
the percent reduction in (a-olefin/ethylene) weight ratio was at least -70%.
CPU experiments were also conducted to collect samples of the first ethylene
interpolymer produced with the bridged metallocene catalyst formulation for
13C NMR
characterization to quantify the amount of long chain branching (LOB). Table
13
summarizes typical CPU process conditions at three reactor temperatures (130,
160
and 190 C) and two levels of ethylene conversion (about 75wt% and about 95
wt%).
Polymer characterization data (of the first ethylene interpolymer produced
with the
bridged metallocene catalyst formulation) is summarized in Table 14, the level
of long
chain branching in the ethylene interpolymers produced with the bridged
metallocene
catalyst formulation varied from 0.03 to 0.23 long chain branches (LOB) per
1000
carbon atoms.
=
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= TABLE 1A
Reference resins (linear ethylene polymers) containing undetectable levels of
Long Chain Branching (LCB)
Reference Mv [1} SCBD ZSV
Mw/Mn A
Resins (g/mole) (dL/g) CH3#/1000C (poise)
Resin 1 1.06E+05 1.672 2.14 1.9772 10.5 7.81E+04
Resin 2 1.11E+05 1.687 2.00 1.9772 11.2 7.94E+04
Resin 3 1.06E+05 1.603 1.94 1.9772 15.9 7.28E+04
Resin 4 1.07E+05 1.681 1.91 1.9772 11.0 8.23E+04
Resin 5 7.00E+04 1.192 2.11 1.9772 13.7 1.66E+04
Resin 6 9.59E+04 1.497 1.88 1.9772 12.6 5.73E+04
Resin 7 1.04E+05 1.592 1.85 1.9772 12.8 6.60E+04
Resin 8 5.09E+04 0.981 2.72 2.1626 0.0 6.42E+03
Resin 9 5.27E+04' 0.964 2.81 2.1626 0.0 6.42E+03
Resin 10 1.06E+05 1.663 1.89 1.1398 13.3 7.69E+04
Resin 11 1.10E+05 1.669 1.81 1.1398 19.3 7.31E+04
Resin 12 1.07E+05 1.606 1.80 1.1398 27.8 6.99E+04
Resin 13 6.66E+04 1.113 1.68 2.1626 17.8 1.39E+04
Resin 14 6.62E+04 1.092 1.76 2.1626 21.4 1.45E+04
Resin 15 6.83E+04 1.085 1.70 2.1626 25.3 1.44E+04
Resin 16 7.66E+04 1.362 2.51 2.1626 4.0 3.24E+04
Resin 17 6.96E+04 1.166 2.53 2.1626 13.9 2.09E+04
Resin 18 6.66E+04 1.134 2.54 2.1626 13.8 1.86E+04
Resin 19 5.81E+04 1.079 2.44 2.1626 5.8 1.10E+04
Resin 20 7.85E+04 1.369 2.32 2.1626 3.7 3.34E+04
Resin 21 6.31E+04 1.181 2.26 2.1626 4.3 1.61E+04
Resin 22 7.08E+04 . 1.277 2.53 2.1626 3.6 2.58E+04
Resin 23 9.91E+04 1.539 3.09 2.1626 14.0 8.94E+04
Resin 24 1.16E+05 1.668 3.19 2.1626 13.3 1.32E+05
Resin 25 1.12E+05 1.689 2.71 2.1626 12.8 ' 1.38E+05
Resin 26 1.14E+05 1.690 3.37 2.1626 8.0 1.48E+05
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Resin 27 9.55E+04 1.495 3.44 2.1626 13.8 8.91E+04
Resin 28 1.00E+05 ' 1.547 3.33 2.1626 14.1 9.61E+04
Resin 29 1.07E+05 1.565 3.52 2.1626 13.0 1.12E+05
Resin 30 1.04E+05 1.525 3.73 2.1626 13.4 1.10E+05
Resin 31 1.10E+05 1.669 3.38 2.1626 8.7 1.26E+05
Resin 32 1.09E+05 1.539 3.42 2.1626 13.4 1.07E+05
Resin 33 8.04E+04 1.474 5.29 2.1626 1.7 7.60E+04
Resin 34 8.12E+04 1.410 7.64 2.1626 0.9 9.11E+04
Resin 35 7.56E+04 1.349 9.23 2.1626 1.0 9.62E+04
Resin 36 7.34E+04 1.339 8.95 2.1626 1.1 1.00E+05
Resin 37 1.01E+05 1.527 3.76 2.1626 13.3 1.11E+05
=
103
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TABLE 1B
Long Chain Branching Factor (LCBF) of reference resins (linear ethylene
polymers) containing undetectable levels of Long Chain Branching (LCB)
Reference Log ZSVc Log IVc Sh Sy LCBF
Resins (log(poise)) log(dL/g) (dimensionless) (dimensionless) (dimensionless)
Resin 1 4.87E+00 2.46E-01 -5.77E-02 -1.21E-02 3.49E-04
Resin 2 4.90E+00 2.52E-01 -5.39E-02 -1.13E-02 3.05E-04
Resin 3 4.87E+00 2.41E-01 -2.46E-02 -5.16E-03 6.33E-05
Resin 4 4.93E+00 2.50E-01 -9.46E-03 -1.99E-03 9.41E-06
Resin 5 4.20E+00 1.07E-01 -6.37E-02 -1.34E-02 4.26E-04
Resin 6 4.78E+00 2.04E-01 5.83E-02 1.22E-02 3.57E-04
Resin 7 4.85E+00 2.31E-01 -1.73E-03 -3.65E-04 3.16E-07
Resin 8 3.69E+00 -8.43E-03 -2.17E-02 -4.55E-03 4.93E-05
Resin 9 3.68E+00 -1.58E-02 1.21E-04 2.44E-05 1.47E-09
Resin 10 4.91E+00 2.38E-01 2.19E-02 4.60E-03 5.04E-05
Resin 11 4.90E+00 2.48E-01 -2.96E-02 -6.21E-03 9.17E-05
Resin 12 ' 4.88E+00 2.42E-01 -1.99E-02 -4.19E-03 4.17E-05
Resin 13 4.21E+00 9.14E-02 2.36E-02 4.96E-03 5.86E-05
Resin 14 4.21E+00 9.22E-02 1.89E-02 3.97E-03 3.75E-05
Resin 15 4.22E+00 1.00E-01 -9.82E-03 -2.06E-03 1.01E-05
Resin 16 4.42E+00 1.44E-01 -1.23E-02 -2.59E-03 1.60E-05
Resin 17 4.23E+00 1.01E-01 -4.64E-03 -9.75E-04 2.26E-06
Resin 18 4.18E+00 8.91E-02 1.66E-03 3.47E-04 2.87E-07
Resin 19 3.97E+00 4.73E-02 -1.09E-02 -2.29E-03 1.25E-05
Resin 20 4.47E+00 1.45E-01 2.28E-02 4.78E-03 5.44E-05
Resin 21 4.16E+00 8.23E-02 1.78E-02 3.73E-03 3.31E-05
Resin 22 4.32E+00 1.15E-01 2.45E-02 5.14E-03 6.30E-05
Resin 23 4.78E+00 2.22E-01 -2.25E-02 -4.73E-03 5.31E-05
Resin 24 4.94E+00 2.56E-01 -3.13E-02 -6.57E-03 1.03E-04
Resin 25 5.02E+00 2.59E-01 3.91E-02 8.21E-03 1.60E-04
Resin 26 4.97E+00 2.48E-01 3.94E-02 8.27E-03 1.63E-04
104
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Resin 27 4.74E+00 2.09E-01 -2.83E-03 -5.95E-04 8.42E-07
Resin 28 4.79E+00 2.24E-01 -3.13E-02 -6.57E-03 1.03E-04
Resin 29 4.83E+00 . 2.28E-01 -2.96E-03 -6.22E-04
9.20E-07
Resin 30 4.80E+00 2.18E-01 1.47E-02 3.08E-03 2.26E-05
Resin 31 4.90E+00 2.44E-01 -1.40E-02 -2.94E-03 2.06E-05
Resin 32 4.82E+00 2.23E-01 1.27E-02 2.66E-03 1.69E-05
Resin 33 4.51E+00 1.72E-01 -6.37E-02 -1.34E-02 4.26E-04
Resin 34 4.45E+00 1.52E-01 -2.68E-02 -5.62E-03 7.52E-05
Resin 35 4.40E+00 1.33E-01 1.55E-02 3.26E-03 2.53E-05
Resin 36 4.43E+00 1.30E-01 5.82E-02 1.22E-02 3.55E-04
Resin 37 4.80E+00 2.17E-01 1.77E-02 3.71E-03 3.28E-05
105
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TABLE 2
Long Chain Branching Factor (LCBF) of ethylene interpolymer product
Examples 50-52 and 58 and Comparatives 60, 61 and 67
Example Example Example Example Comp. Comp. Comp.
50 51 52 58 60 61 67
Mv 1.05E+0 9.09E+0 9.07E+0 5.96E+0 1.00E+0
9.42E+0
(g/mole) 5 4 4 4 n/a 5 4
En]
(dL/g) 1.496 1.314 1.340 0.945 n/a 1.538 1.474
Mw/Mn 2.86 2.65 2.04 6.23 2.88 2.37 3.08
A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626
2.1626
SCB
(CH3#/1000
C) 16.1 15.8 16.2 12.6 13.5 12.1 14.6
ZSV 1.61E+0 1.65E+0 1.77E+0 7.33E+0 1.05E+0 8.06E+0 8.98E+0
(poise) 5 5 5 4 5 4 4
Log ZSVc 5.07E+0 5.11E+0 5.24E+0 4.43E+0 4.88E+0 4.84E+0 4.79E+0
(log(poise)) 0 = 0 0 0 0 0
Log IVc
(log(dL/g)) 2.17E-01 1.61E-01 1.70E-01 1.01E-02 n/a 2.17E-01 2.05E-01
Sh
(dimensionl
ess) 2.84E-01 5.93E-01 6.79E-01 6.30E-01 n/a 5.60E-02 6.17E-02
Sy
(dimensionl
ess) 5.96E-02 1.24E-01 1.43E-01 1.32E-01 n/a 1.18E-02 1.30E-02
LCBF
(dimension!
ess) 8.45E-03 3.68E-02 4.84E-02 4.17E-02 n/a 3.30E-04 4.00E-04
106
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TABLE 3
Long Chain Branching Factor (LCBF) of Comparative ethylene polymers:
Comparatives A-C and Comparatives D-G
Comp. Comp. Comp. Comp. Comp.
E Comp. F Comp.
A B C D G
Mv 8.79E+0 8.94E+0 8.70E+0 9.75E+0 1.02E+0 1.04E+0 9.76E+0
(g/mole) 4 4 4 4 5 5 4
[n]
1.300 1.314 1.293 1.441 1.488 1.507
1.448
(dL/g)
Mw/Mn 1.88 1.80 1.89 3.04 2.85 2.79 2.89
A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626
SCB
23.2 23.3 23.4 14.2 13.7 14.1 15.1
(CH3#/1000C)
ZSV 1.51E+0 1.51E+0 1.53E+0 1.56E+0 1.43E+0 1.55E+0 1.35E+0
(poise) 5 5 5 5 5 5 5
Log ZSVc 5.20E+0 5.22E+0
5.21E+0 5.03E+0 5.02E+0 5.06E+0 4.99E+0
(log(poise)) 0 0 0 0 0 0 0
Log IVc 1.74E- 1.79E- 1.72E- 1.95E- 2.08E- 2.15E-
2.00E-
(log(dL/g)) 01 = 01 01 01 01 01 01
Sh 6.22E- 6.14E- 6.35E- 3.51E- 2.76E- 2.90E-
2.87E-
(dimensionless) 01 01 01 01 01 01 01
Sy 1.31E- 1.29E- 1.33E- 7.38E- 5.81E- 6.09E-
6.03E-
(dimensionless) 01 01 01 02 02 02 02
LCBF 4.06E- 3.96E- 4.23E- 1.30E- 8.03E- 8.83E-
8.65E-
(dimensionless) 02 02 02 02 03 03 03
Ti (ppm) 0.33 0.018 1.5 2.2 2.2 2.0
Hf (ppm) b b b b b
Internal
Unsaturations/1 0.006 0.006 0.006 0.004 0.004 0.004 0.004
00C
Side Chain '
Unsaturations/1 0.001 0.025 0.025 0.002 0.003 0.002 0.004
00C
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Terminal
Unsaturations/1 0.008 0.007 0.007 0.025 0.020 0.021 0.03
00C
a average of AFFINITY (3 samples, but not Comp. A-C); via Neutron Activation
Analysis (N.A.A.)
b undetectable via Neutron Activation Analysis
=
108
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Table 4A
Continuous solution process catalyst parameters for Examples 50 through 52
and Comparatives 60 and 61
Process Parameter Example Example Example Comp. 60 Comp. 61
50 51 52
Reactor Mode Series Series Parallel Series
Parallel
R1 Catalysta
CpF-1 CpF-2 CpF-2 PIC-2 PIC-1
(component A, or
XH-DiCI XH-DiMe XH-DiMe XE303 XE304
component C)
PIC-1 PIC-1 PIC-1 PIC-2 PIC-1
R2 Catalystb
XE-304 XE-304 XE304 XE303 XE304
R1 catalyst (ppm) 0.72 0.40 0.44 0.14 0.26
R1 ([Mc]/[A]) or
122 45 45 100 65
R1 ([M]nC1) mole ratio
R1 ([Pd]/[M]) mole ratio 0.40 0.15 0.15 0.5 0.30
R1 ([81/[A]) or
1.47 1.21 1.21 1.2 1.20
R1 (MAC]) mole ratio
R2 catalyst (ppm) 0.15 0.17 0.59 0.38 0.27
R2 ([Mc]/[C]) mole ratio 25 25 65 30 65
R2 ([0]/[M]) mole ratio 0.30 0.30 0.30 0.5 0.30
R2 (MACH mole ratio 1.50 1.50 1.50 1.5 1.50
Prod. Rate (kg/h) 64.1 64.4 60.2 76.7 49.5
Catalysts: CpF-1 = [(2,7-tBu2Flu)Ph2C(Cp)HfC12]: CpF-2 = [(2,7-
tBu2Flu)Ph2C(Cp)HfMe2]; PIC-1 = [Cp[(t-
BO3PN]TiC121, and; PIC-2 = [Cp[(isopropy1)3PN]TiC121.
b in-line Ziegler-Natta catalyst formulation
methylaluminoxane (MMAO-7)
2,6-di-tert-butyl-4-ethylphenol
trityl tetrakis(pentafluoro-phenyl)borate
109
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TABLE 4B
Continuous solution process catalyst parameters for Examples 50 through 52
and Comparatives 60 and 61
Process Parameter Example Example Example Comp. 60 Comp. 61
50 51 52
R3 volume (L) 2.2 2.2 2.2 2.2 2.2
ESR1 (%) = 50.0 50.0 60.0 50.0 70
ESR2 (%) 50.0 50.0 40.0 50.0 30
ESR3 (%) 0.0 0.0 0.0 0.0 0.0
R1 ethylene concentration 9.8 11.1
8.6 9.1 8.3
(wt%)
R2 ethylene concentration
12.3 12.3 12.4 13.4 13.0
(wt%)
R3 ethylene concentration
12.3 12.3 12.4 13.4 13
(wt%)
((1-octene)/ (ethylene))R1
0.400 0.41 0.4 0.75 1.16
(wt/wt)
((1-octene)/ (ethylene))R2
0.00 0.00 0.00 0.00 0.00
(wt/wt)
(1-octene/ethylene)
0.200 0.205 0.240 0.37 0.817
(wt/wt) (total)
OSR1 (%) 100 100 100 100 100
O5R2 (%) 0 0 0 0 0
OS' (%) 0 0 0 0 0
H2" (ppm) 5.35 5.35 7.21 0.5 0.4
H2R2 (ppm) 0.5 0.5 0.54 0.5 0.47
H2R3 (ppm) 0.0 0.0 0.0 0.0 0.0
110
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TABLE 4C
Continuous solution process catalyst parameters for Examples 50 through 52
and Comparatives 60 and 61
Process Parameter Example Example Example Comp. 60
Comp. 61
50 51 52
R1 total solution rate
393.3 345.1 344 439.0 392.2
(kg/h)
R2 total solution rate =
156.7 204.9 344 160.2 107.8
(kg/h)
R3 solution rate (kg/h) 0 0 0 0 0
Total solution rate (kg/h) 550 550 688 600
500
R1 feed inlet temp ( C) 30 30 30 30 35
R2 feed inlet temp ( C) 50 50 50 30
54.9
R3 feed inlet temp( C) NA 131 131 130
130
R1 catalyst inlet temp ( C) 145.1 21.4 24.5 32.2
29.9
R2 catalyst inlet temp ( C) 41.7 30.4 30.4 31.1
40.3
R1 Mean temp ( C) 131.8 139.5 154.4 141.0
138.3
R2 Mean temp ( C) 189.9 189.8 196.0 191.0
195.4
R3 exit temp ( C) 192.7 191.1 180.6 193.0
162.6
ceti. (%) 80.0 80.6 80.0 89
89.0
0R2 (%) . 85.0 85.0 94.0 79
96.2
0(R2i-R3) (%) 86.3 86.6 NA 81.5 NA
0R3 (%) 8.5 10.4 38.1 12
27.26
oT (%) 91.8 92.0 90.8 89.7
93.4
= 5
111
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'
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TABLE 5
Physical properties of Examples and Comparatives
Comp. Comp. Comp.
60 E01 61 67
Example Example Example
Physical Property 09-44 E0115-
FPs117
50 51 52
PS- 52 PS- JS63416
89075 121039
Density (g/cc) 0.9181 0.9172 0.9172 0.9162 0.9193
0.9162
Melt Index, 12
1.02 1.06 0.92 0.96 0.99 0.99
(dg/min)
Stress Exponent 1.46 1.45 1.39 1.30 1.18 1.27
110/12 10.2 9.91 8.80 7.67 6.22 7.59
MFR, 121/12 43.7 41.9 30.7 28.5 19.7 30.8
SEC, Mw 96695 96238 93004 94536 99753 102603
SEC, Mw/Mn 2.86 2.65 2.04 2.88 2.37 3.08
SEC, M1/Mw 2.12 2.14 1.67 2.15 1.86 2.32
CDBIso 8.0 6.6 55.4 92.1 62.6 77.5
Branch Freq.
16.1 15.8 16.2 13.5 12.1 14.6
(C6/1000C)
Comonomer
3.2 3.2 3.2 2.7 2.4 2.9
mole %
Ti (ppm) n/a 0.127 0.208 0.303 0.056'
Hf (ppm) n/a 0.530 0.624 Undetectable'
Al (ppm) n/a 4.42 9.05 6.56 1.40'
Mg (ppm) n/a 0.165 0.286 0.160 0.089a
CI (ppm) n/a 0.370 0.503 0.496 0.038'
Internal
0.012 0.012 0.016 0.018 0.020 0.021
Unsaturation/100C
Side Chain
0.003 0.002 0.003 0.003 0.000 0.002
Unsaturation/100C
Terminal
0.005 0.005 0.006 0.007 0.006 0.006
Unsaturation/100C
a database average, historical catalyst residues unbridged single site
catalyst formulation
112
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TABLE 6A
Continuous solution process catalyst parameters for Examples 58 and 59
Process Parameter Example 58 Example 59
Reactor Mode Series Series
CpF-1 CpF-1
R1 Catalysta (component A)
PIC-1 PIC-1
R2 Catalystb
R1 catalyst (ppm) 1.08 0.97
R1 ([Mc]/[A]) mole ratio 136.0 136.1
R1 ([Pd]/[M]) mole ratio 0.40 0.40
R1 ([139/[A]) mole ratio 1.80 1.80
R2 catalyst (ppm) 0.31 1.32
R2 ([Mc]/[C]) mole ratio 30.01 25.00
R2 ([0]/[M]) mole ratio 0.30 0.30
R2 ([Bina mole ratio 1.28 1.27
Prod. Rate (kg/h) 89.7 70.6
a Catalysts: CpF-1 = [(2,7-tBu2Flu)Ph2C(Cp)HfC12]: CpF-2 = [(2,7-
tBu2Flu)Ph2C(Cp)HfMe2]; PIC-1 = [Cp[(t-
Bu)3PN]TiC12], and; PIC-2 = [Cp[(isopropy1)3PNITIC12].
b in-line Ziegler-Natta catalyst formulation
methylaluminoxane (MMAO-7)
d 2,6-di-tert-butyl-4-ethylphenol
trityl tetrakis(pentafluoro-phenyl)borate
=
113
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=
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TABLE 6B
Continuous solution process catalyst parameters for Examples 58 and 59
Process Parameter Example 58 Example 59
R3 volume (L) 2.2 2.2
ES' (%) 30 45
ES82 (%) 70 55
ES83 (%) 0 0
R1 ethylene concentration 8.83 10.18
(wt%)
R2 ethylene' concentration 15.02 14.67
(wt%)
R3 ethylene concentration 15.02 14.67
(wt%)
((1-octene)/ (ethylene))81 0.33 0.02
(wt/wt)
OS81 (%) 50 100
OS82 (%) 50 0
OS83 (%) 0 0
Fl2R1 (ppm) 0.22 0.75
H282 (ppm) 30.04 29.99
H283 (ppm) 0 0
114
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TABLE 6C
Continuous solution process catalyst parameters for Examples 58 and 59
Example 58 Example 59
Process Parameter
R1 total solution rate (kg/h) 268.9 175.6
R2 total solution rate (kg/h) 268.9 175.6
R3 solution rate (kg/h) 0 0
Total solution rate (kg/h) 537.8 351.2
R1 feed inlet temp ( C) 30.01 29.82
R2 feed inlet temp ( C) 29.97 28.88
R3 feed inlet temp( C) NA NA
R1 catalyst inlet temp ( C) 145 145
R2 catalyst inlet temp ( C) 30 30
R1 Mean temp ( C) 135.7 151.9
R2 Mean temp ( C) 206.1 211.3
QR1(%) 87.90 91.62
QR2 (%) 81.99 88.07
ce2+R3) (%) 85.72 90.62
=
115
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TABLE 7
Physical properties of Examples 58 and 59
Physical Property Example 58 Example 59
Density (g/cc) 0.9283 0.9440
Melt Index, 12 (dg/min) 4.03 0.24
Stress Exponent 1.85 1.95
110/12 21.12 n/a
MFR, 121/12 142 215.76
SEC, M, 72126 119964
SEC, Mw/Mn 6.23 10.41
SEC, Mz/Mw 3.68 3.89
CDB150 41.1 n/a
Branch Freq. (C6/1000C) 12.6 4.6
Comonomer 2.5 0.9
mole %
Internal Unsaturation/100C 0.010 n/a
Side Chain 0.006 n/a
Unsaturation/100C
Terminal Unsaturation/100C 0.009 n/a
116
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TABLE 8
Physical attributes of the first, second and third ethylene interpolymer in
Example 51, relative to Comparative 67
Example 51
Reactor 1 Reactor 2 Reactor 3
Physical Attribute Ex.
1st Interpoly rd Interpoly 3rd Interpoly
Weight Percent (%) 49.7 45.3 5.0% 100
Mn 72856 21935 21935 36278
M,, 141247 39575 39575 96238
Polydispersity (Mw/Mn) 1.94 1.80 1.80 2.65
BrF (#C6/1000C) 30.3' 1.48 g 1.48 15.8
CDBI50(%) (range) 85 - 90 80 - 95 80 -95 6.6
Density (g/cm3) 0.8940 b 0.9413 f 0.9413 0.9172
Melt Index (dg/min) 0.1 c 33.9 ` 33.9 1.06
LCBF (dimensionless) 0.0740 d e e 0.0368
Comparative 67
Reactor 1 Reactor 2 Reactor 3
Physical Attribute Comp.67
1st Interpoly rd Interpoly 3rd Interpoly
Weight Percent (%) 47.1 47.9 5% 100
Mn 48956 20045 20045 33358
Mw 165552 35917 25917 102603
Polydispersity (Mw/Mn) 1.95 1.79 1.79 3.08
BrF (#C6/1000C) 12.7 a 16.3 g 16.3 14.6
CDBI50(%) (range) 85 -97 80 -95 80 - 95 77.5
Density (g/cm3) 0.9141 b 0.9181 f 0.9181 0.9162
Melt Index (dg/min) 0.05 c 49.2 c 49.2 0.99
LCBF (dimensionless) e e e e
a BrF (#C6/1000C) = 120.32807-2.1647891(TPcTREF)+0.0118658(TPcTREF)2-
0.000022(TPcrRE03; where TPCTREF is the
peak elution temperature of the first ethylene interpolymer in the CTREF
chromatogram.
b BrF (#C6/1000C) = 9341.8 (02- 17766 (p1) + 8446.8, where p1 was the density
of the first ethylene
interpolymer.
117
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Melt Index (12, dg/min) = 5000[1 + (5.7e-5 x Mw)2. ]((-45-10 ) + 1.0e-6 where
Mw is the Mw of each slice of a
MWD with a weight defined by a (wt.fraction * sigmoid function); where the
sigmoid function = 1/(1 + exp(-
(logMw ¨ 4.2)/0.55))
d 0.0736 = LCBFExamPle51/(welf,), where wtglfr is the weight fraction of the
first ethylene interpolymer in Example
51.
LCBF < 0.0001 (undetectable levels of LCB)
f density of the second and third ethylene interpolymer given the linear
specific volume blending rule and p', pf
and weight fractions
g BrF(#C6/1000C) of second and third ethylene interpolymer given linear BrF
blending rule and weight fractions
TABLE 9
Blown film processing conditions targeting 1.0 mil (25 am) film and output
rate
of 100 lb/hr, Examples 51 and 52, relative to Comparative 67
Processing Units Example 51 Example 52 Comp. 67
Parameter
Density (g/cm3) 0.9172 0.9172 0.9162
Melt Index, 12 (dg/min) 1.06 0.92 0.99
Processing Aida ppm 800 800 800
Output (lbs/hr) lb/hr 100 100 100
Melt 422 472
F
Temperature 423
Extruder Pressure psi 3215 3465 3818
Extruder Current Amp 30.7 34.2 38
Extruder Voltage Volt 191 182 197
Screw Speed Rpm 40 38 41
Nip Roll Speed ft/min 131 131 131
Frost Line Height In 16 16 16
lb/(hrrpm 2.6 2.4
Specific Output
2.5
IbAhramp 2.9 2.7
Specific Power
3.3
Specific Energy W/lb/hr 58.6 62.2 74.1
a 800 ppm of FX5920A processing aid (available from 3M, St. Paul, MN, USA)
118
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TABLE 10A
Blown film physical properties of Examples and Comparatives; film thickness
1.0 mil (25 um) unless indicated otherwise
Physical Property Units Method Example Example Comp.
51F 52F 67F
Density (g/cm3) ASTM D792 0.9172 0.9172
0.9162
Melt Index, I2 (dg/min) ASTM D1238 1.06 0.92 0.99
Film Thickness mil Micrometer 1.0 1.0 1.0
Film Hexane 21 CFR
wt% 0.16 0.21 0.46
Extractablesa 177.1520
S.I.T. @
C In-house 93.6 89.1 99.1
4.4N/13me
Tack Onset @
C In-house 90 86 101
1.0Nb
Max Hot Tack =
In-house 3.2 3.62 5.53
Strengthb
Temperature at
C In-house 105 100 115
Max. Hot Tackb
Tear MD g/mil ASTM D1922 222 288 282
Tear TD g/mil ASTM D1922 468 568 507
ASTM D1709
Dart Impact 800 449 400
Method A
Lubricated
J/mm In-house 48 75 81
Puncture
Gloss at 450 ASTM D2457 26 43 46
Haze ASTM D1003 32.9 15.9 13.5
a = 3.5 mil film (89 jim)
b = 2.0 mil film (51 pm)
119
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TABLE 10B
Blown film physical properties of Examples and Comparatives; film thickness
1.0 mil (25 um) unless indicated otherwise
Example Example Comp.
Physical Property Units Method 51F 52F
67F
Density (g/cm3) ASTM D792 0.9172
0.9172 0.9162
Melt Index, I2 (dg/min) ASTM D1238 1.06 0.92 0.99
Film Thickness mil Micrometer 1.0 1.0 1.0
=
1% Sec ASTM
MPa 212 228
164
Modulus MD D882
1% Sec ASTM
MPa 255 258
161
Modulus TD D882
2% Sec ASTM
MPa 178 190
142
Modulus MD D882
2% Sec ASTM
MPa 211 215
137
Modulus TD ' D882
ASTM
Tensile Break Str MD MPa 45 48.8
49.7
D882
ASTM
Tensile Break Str TD MPa 40.4 48.1
29.5
D882
Elongation at Break ASTM
518 583 548
MD D882
ASTM
Elongation at Break TD % 735 791
665
D882
ASTM
Tensile Yield Str MD MPa 10.2 10.5
9.1
D882
ASTM
Tensile Yield Str TD MPa 11.4 11.5
8.7
D882
Tensile Elong ASTM
10 10 11
at Yield MD D882
Tensile Elong ASTM
9 9
10
at Yield TD D882
120
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Film Toughness, Total ASTM
Mb/in' 1286 1605 1327
Energy to Break TD D882
Film Toughness, Avg. ASTM
ft-lb/in3 1528 1870 1105
Total Energy to Break D882
=
121
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TABLE 11A
Percent (%) improved SEC weight average molecular weight (Mw) at a reactor
temperature of 130 C and 90% ethylene conversion for the bridged metallocene
catalyst formulation relative to the unbridged single site catalyst
formulation
Weight % 1-octene Bridged Metallocene Unbridged Single
Site
in Catalyst Formulation Catalyst
Formulation % Improved
ethylene Mw
Component MA Component Mc
interpolymers (see3)
A (seel) C (see2)
0.1 CpF-1 520658 PIC-1 493848 5.4
2.5 CpF-1 216926 PIC-1 165308 31
5.0 CpF-1 179652 PIC-1 130600 38
7.5 CpF-1 160892 PIC-1 113782 41
10.0 CpF-1 148783 PIC-1 103179 44
12.5 CpF-1 140021 PIC-1 95641 46
15.0 CpF-1 133246 PIC-1 89892 48
17.5 CpF-1 127775 PIC-1 85302 50
20.0 CpF-1 123217 PIC-1 81516 51
22.5 CpF-1 119332 PIC-1 78316 52
25.0 CpF-1 115961 PIC-1 75560 53
27.5 CpF-1 112994 PIC-1 73151 54
30.0 CpF-1 110351 PIC-1 71019 55
32.5 CpF-1 107974 PIC-1 69112 56
35.0 CpF-1 105820 PIC-1 67392 57
37.5 CpF-1 103852 PIC-1 65830 58
40.0 CpF-1 102045 PIC-1 64401 58
42.5 CpF-1 100376 PIC-1 63087 59
45.0 CpF-1 98828 PIC-1 61873 60
1 MA = 278325 x (Octenewt%) -0 222; where (Octenewt%) is the weight % of
octene in the ethylene/1-octene
interpolymer
2 NAC = 225732 x (OctenewN -0.340
3 1.00% X (MWA - MwC)/MwC
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TABLE 11B
Percent (%) improved SEC weight average molecular weight (Mw) at a reactor
temperature of 160 C and 90% ethylene conversion for the bridged metallocene
catalyst formulation relative to the unbridged single site catalyst
formulation.
Weight % 1-octene Bridged Metallocene
Unbridged Single Site % Improved
in Catalyst Formulation
Catalyst Formulation Mw
ethylene
(see3)
= Component M,A Component Mc
interpolymers
A (see') C (see2)
0.1 CpF-1 293273 PIC-1 248166 18
2.5 CpF-1 ' 130734 PIC-1 91198 43
5.0 CpF-1 109858 PIC-1 73513 49
7.5 CpF-1 99227 PIC-1 64804 53
10.0 CpF-1 92315 PIC-1 59257 56
12.5 CpF-1 87287 PIC-1 55285 58
15.0 CpF-1 83382 PIC-1 52237 60
17.5 CpF-1 80217 PIC-1 49792 61
20.0 CpF-1 77573 PIC-1 47766 62
22.5 CpF-1 75314 PIC-1 46048 64
25.0 CpF-1 73348 PIC-1 44564 65
27.5 CpF-1 71614 PIC-1 43262 66
30.0 CpF-1 70067 PIC-1 42107 66
32.5 CpF-1 68673 PIC-1 41072 67
35.0 CpF-1 67408 PIC-1 40136 68
37.5 CpF-1 66251 PIC-1 39284 69
40.0 CpF-1 65186 PIC-1 38504 69
42.5 CpF-1 64202 PIC-1 37784 70
45.0 CpF-1 63287 PIC-1 37119 70
1 MwA = 164540 x (Octenewt%) '251; where (Octenewt%) is the weight % of octene
in the ethylene/1-octene
interpolymer
2 MC = 121267 x (Octenewt%) "0.311
3 1.00% X (MwA- Mwc)/mwc
123
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TABLE 12A
Percent (%) improvement (reduction) in (a-olefin/ethylene) weight ratio in the
reactor feed, for the bridged metallocene catalyst formulation relative to the
unbridqed single site catalyst formulation, to produce ethylene interpolymers
at
the densities shown (130 C reactor temperature and about 90% ethylene
conversion).
Bridged Meta llocene Unbridged Single Site
Weight % 1-octene Catalyst Formulation Catalyst Formulation
% Reduced
in (a-olefin
(a-olefin/
ethylene / (a-olefin /
Component Component
ethylene)
interpolymers ethylene) ethylene)c
A C Ratio (see3)
A (see2)
(seel)
0.0 CpF-1 0.000 PIC-1 0.00 n/a
2.5 CpF-1 0.0075 PIC-1 0.174 -96%
5.0 CpF-1 0.045 PIC-1 0.422 -89%
7.5 CpF-1 0.088 PIC-1 0.690 -87%
10.0 CpF-1 0.136 PIC-1 0.980 -86%
12.5 CpF-1 0.188 PIC-1 1.29 -85%
15.0 , CpF-1 0.246 PIC-1 1.62 -85%
17.5 CpF-1 0.309 PIC-1 1.98 -84%
20.0 CpF-1 0.377 PIC-1 2.35 -84%
22.5 CpF-1 0.449 PIC-1 2.75 -84%
25.0 CpF-1 0.527 PIC-1 3.17 -83%
27.5 CpF-1 0.610 PIC-1 3.60 -83%
30.0 CpF-1 0.698 PIC-1 4.06 -83%
32.5 CpF-1 0.790 PIC-1 4.55 -83%
35.0 CpF-1 0.888 PIC-1 5.05 -82%
37.5 CpF-1 0.991 PIC-1 5.57 -82%
40.0 CpF-1 1.10 PIC-1 6.12 -82%
42.5 CpF-1 1.21 PIC-1 6.68 -82%
45.0 CpF-1 1.33 PIC-1 7.27 -82%
=
124
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1 (a-olefin/ethylene)A = 0.0004 x (Octenewt%)2 0.0121 x (OctenewN ¨ 0.0253;
where (Octenewt%) is the weight %
of octene in the ethylene/1-octene interpolymer
2 (ct-olefin/ethylene)c= 0.0017 x (Octenewt%)2+ 0.0862 x (Octene') ¨ 0.0517
3 100% x ((ix-olefin/ethylene)A- (cc-olefin/ethylene)9/(ct-olefin/ethylene)c
=
125
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TABLE 12B
Percent (%) improvement (reduction) in (a-olefin/ethylene) weight ratio in the
reactor feed, for the bridged metallocene catalyst formulation relative to the
unbridqed single site catalyst formulation, to produce ethylene interpolymers
at
the densities shown (160 C reactor temperature and about 90% ethylene
conversion)
Bridged Meta llocene Unbridged Single Site
Weight % 1-octene Catalyst Formulation Catalyst
Formulation % Reduced
in (a-olefin (a-
olefin/
ethylene / (a-olefin /
ethylene)
Component Component
interpolymers ethylene) ethylene)c Ratio
A C
A (see2) (see3)
(seel)
0.0 CpF-1 0.00 PIC-1 0.00 n/a
2.5 CpF-1 0.0078 PIC-1 0.183 -96%
5.0 CpF-1 0.031 PIC-1 0.407 -92%
7.5 CpF-1 0.066 PIC-1 0.653 -90%
10.0 CpF-1 0.112 PIC-1 0.920 -88%
12.5 CpF-1 0.170 PIC-1 1.21 -86%
15.0 CpF-1 0.238 PIC-1 1.52 -84%
17.5 CpF-1 0.318 PIC-1 1.85 -83%
20.0 . CpF-1 0.409 PIC-1 2.20 -81%
22.5 CpF-1 0.512 PIC-1 2.57 -80%
25.0 CpF-1 0.625 PIC-1 2.97 -79%
27.5 CpF-1 0.750 PIC-1 3.39 -78%
30.0 CpF-1 0.886 PIC-1 3.82 _77%
32.5 CpF-1 1.03 PIC-1 4.28 -76%
35.0 CpF-1 1.19 PIC-1 4.76 -75%
37.5 CpF-1 1.36 PIC-1 5.26 -74%
40.0 CpF-1 1.54 PIC-1 5.78 _73%
42.5 CpF-1 1.74 PIC-1 6.33 -73%
45.0 CpF-1 1.94 PIC-1 6.89 -72%
126
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(a-olefin/ethylene)A= 0.0009 x (Octene')2 + 0.0027 x (Octenewt%) ¨ 0.0046;
where (Octenewt%) is the weight %
of octene in the ethylene/1-octene interpolymer
2 (a-olefin/ethylene)' = 0.0017 x (Octene"")2+ 0.0771 x (Octenewt%) ¨ 0.0208
3100% x ((a-olefin/ethylene)1-(a-olefin/ethylene)C/(a-olefin/ethylene)C
=
127
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TABLE 13
CPU continuous solution phase, one reactor, ethylene homopolymerization
using the bridged metallocene catalyst formulation
Polymerization
130 160 190
Temp. ( C)
Example Example Example Example Example Example
Sample Code Cl C2 C3 C4 C5 C6
Component
Concentration
0.15 0.47 0.19 0.82 0.22 0.93
in Reactor
[mM/L]
([1\V[Ai)
100 100 100 100 100 100
mole ratio
([11/[1VI])
0.40 0.40 0.40 0.40 0.40 0.40
mole ratio
DMA])
1.20 1.20 1.20 1.20 1.20 1.20
mole ratio
HUTcPu (min) 119 119 109 109 99 99
Qcpu (%) 74.5 94.2 74.9 94.4 75.5 94.8
Kpcl'u
12731 22328 11727 15704 13116 17761
(1j(mM=min)
1 CpF-2 = [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]
128
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TABLE 14
13C-NMR determined long chain branching (LCB) in the first ethylene
interpolymer (ethylene homopolymer) produced using the bridged metallocene
catalyst formulationl on the CPU
Example Example Example Example Example Example
Sample
C10 C11 C12 C13 C14
C15
CPU Reactor
190 190 160 160 130
130
Temp. ( C)
CPU Ethylene
95.6 85.3 95.0 75.3 93.6
85.1
Conversion (wt%)
CPU [ethylene] out
0.62 2.10 0.57 2.80 0.53
1.23
(wt.%)
13C
0.23 0.09 0.09 0.03 0.07
0.03
LCB/1000C
GPC NI, (g/mol) 46337 93368 107818 255097 234744
305005
Pd (Mw/Mn) 1.88 1.88 1.85 1.9 2.02
2.29
=
13C-NMR,
2.37 1.68 1.64 0.98 0.94
0.73
C1/1000C
13C-NMR,
0.2 0.14 0.17 0.10 0.12
0.09
C2/1000C
13C-NMR,
0.08 0.05 0.05 D2 D D
C3/1000C
13C-NMR,
0.07 0.05 0.05 D D D
C4/1000C
13C-NMR,
0.3 0.12 0.12 D 0.07 D
(C6 + LCB)/1000C
13C-NMR,
1.1 0.52 0.47 0.22 0.23
0.21
Sat.Term./1000C
Mn (g/mol) 24640 49615 58131 118329 116035
133001
M, (g/mol) 73219 152320 176254 383637 447833
567658
12 (dg/min) 16.6 n/a 0.15 n/a n/a
n/a
121 (dg/min) 380 n/a 10 0.54 0.53
0.12
121/12 22.9 n/a 66.1 n/a n/a
n/a
129
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1 Component A = [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]
D = detectable but not quantifiable
130
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