Note: Descriptions are shown in the official language in which they were submitted.
AN IMPROVED PROCESS TO MANUFACTURE ETHYLENE INTERPOLYMER
PRODUCTS
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 produced. 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 80 C to 300 C while pressures generally range from 3MPag to 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 1 second to 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,
the
deactivated solution may be 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 a-
olefin(s).
In solution polymerization there is a need for improved processes that produce
ethylene interpolymers at higher production rates, i.e. the pounds of ethylene
interpolymer produced per hour is increased. Higher production rates increase
the
profitability of the solution polymerization plant. The catalyst formulations
and solution
polymerization processes disclosed herein satisfy this need.
In solution polymerization there is also a need 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 solution polymerization there is a need for catalyst
formulations that produce high molecular weight ethylene interpolymers at high
CA 2984838 2019-06-25'017066Canada revised disclosure and claims pages.docx
reactor temperatures (or lower reactor viscosities). The 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] weight 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. One non-limiting end-use application includes packaging films
containing the disclosed ethylene interpolymer products. Non-limiting examples
of
desirable film properties include improved optical properties, lower seal
initiation
temperature and improved hot tack performance. Films prepared from the
ethylene
interpolymer products, disclosed herein, have improved properties.
SUMMARY OF THE DISCLOSURE
One embodiment of this disclosure is an ethylene interpolymer product
comprising at
least one ethylene interpolymer, where the ethylene interpolymer product has:
a
dimensionless Long Chain Branching Factor, LCBF, greater than or equal to
0.001; a
residual catalytic metal of from 0.03 to 5 5 ppm of hafnium and a
dimensionless
unsaturation ratio, UR, of from ?_ -0.40 to 5 0.06. The ethylene interpolymer
product
may have a melt index (12) from 0.3 to 500 dg/minute, a density from 0.855 to
0.975
g/cc and from 0 to 25 mole percent of one or more a-olefins. Suitable a-
olefins
include one or more C3 to C10 a-olefins. Further embodiments of the ethylene
interpolymer product have a polydispersity, Mw/Mn, from 1.7 to 25, where Mw
and Mn
are the weight and number average molecular weights, respectively, as
determined by
conventional size exclusion chromatography (SEC). Additional embodiments of
2
-2984838-201:9-=06_2e017066Canada revised disclosure and claims pages.docx
ethylene interpolymer products have a CDBI50 from 1% to 98%, where CDB150 is
measured using CTREF.
Additional embodiments include the manufacture of said ethylene interpolymer
products using a continuous solution polymerization process employing at least
one
homogeneous catalyst formulation. One embodiment of a suitable homogeneous
catalyst formulation is a bridged metallocene catalyst formulation comprising
a
component A defined by Formula (I)
6:2 /X (R6)
R4
(I) 6 m¨x(Ft6)
R5 R3
R2
3
CA 2984838 2019-0 6-25Z017066Canada revised disclosure and claims pages.docx
where M is a metal selected from titanium, hafnium and zirconium; G is the
element
carbon, silicon, germanium, tin or lead; X represents a halogen atom, R6
groups are
independently selected from a hydrogen atom, a 01-20 hydrocarbyl radical, a C1-
20
alkoxy radical or a 06-10 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, a C6_10 aryl oxide radical or
alkylsilyl
radicals containing at least one silicon atom and C3-30 carbon atoms; R2 and
R3 are
independently selected from a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-
20
alkoxy radical, a C6-10 aryl oxide radical or alkylsilyl radicals containing
at least one
silicon atom and C3-30 carbon atoms, and; R4 and R5 are independently selected
from
a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical a C6-10
aryl oxide
radical, or alkylsilyl radicals containing at least one silicon atom and C3-30
carbon
atoms.
Further embodiments include an improved continuous solution polymerization
process
where the improved process comprises: polymerizing ethylene and optionally at
least
one a-olefin, in a process solvent, in one or more reactors using a bridged
metallocene catalyst to form the ethylene interpolymer product; where the
improved
process has an increased production rate, PR', defined by the following
formula;
PR' = 100 x (PRA- PRe) / PRc 10%
where PRA is the production rate of the improved process and PRc is a
comparative
production rate of a comparative continuous solution polymerization process
where
the bridged metallocene catalyst formulation has been replaced with an
unbridged
single site catalyst formulation.
Additional embodiments include a bridged metallocene catalyst formulation
comprising: an alumoxane co-catalyst (component M); a boron ionic activator
(component B), and; optionally, a hindered phenol (component P). Non-limiting
examples of components M, B and P include: methylalumoxane (MMAO-7), trityl
tetrakis (pentafluoro-phenyl) borate and 2,6-di-tert-butyl-4-ethylphenol,
respectively.
Additional embodiments include an improved process employing: a process
solvent
comprising one or more C5 to C12 alkanes and one or more reactors operating at
4
CA 2984838 2019-06 ¨25017066Canada revised disclosure and claims pages.docx
temperatures from 80 C to 300 C and pressures from 3 MPag to 45 MPag.
Embodiments may include reactor conditions such that the process solvent in
one or
more reactors has an average reactor residence time from 10 seconds to 720
seconds. Further embodiments may include reactor conditions such that the
catalyst
inlet temperature employed in one or more reactors may vary from 20 C to 180
C.
Other embodiments include an improved continuous solution polymerization
process
where an ethylene interpolymer product is formed by polymerizing ethylene, and
optionally at least one a-olefin, in a process solvent, in one or more
reactors, using a
bridged metallocene catalyst formulation and the improved process is
characterized
by (a) and/or (b):
(a) the ethylene interpolymer product has at least a 10% improved (higher)
weight
average molecular weight, Mw, as defined by the following formula
% Improved Mw = 100 x (mwa_mwc)/mwc 2 10%
where MwA is a weight average molecular weight of the ethylene interpolymer
product
produced using the improved process and Mwc is a comparative weight average
molecular weight of a comparative ethylene interpolymer product; where the
comparative ethylene interpolymer product is produced in a comparative process
by
replacing the bridged metallocene catalyst formulation with an unbridged
single site
catalyst formulation;
(b) an [a-olefin/ethylene] weight ratio, employed in the improved process, is
reduced
(improved) by at least 70% as defined by the following formula
((a ¨ olefin (a ¨
% Reduced [a ¨ ole f in ethylene) ethylene)
1= 100 X A <-70%
ethylene ( a ¨ olefin\c
ethylene)
where (u-olefin/ethylene)' represents the weight of the a-olefin added to the
improved
process divided by the weight of ethylene added to the improved process, where
the
ethylene interpolymer product having a target density is produced by a bridged
metallocene catalyst formulation, and; (a-olefin/ethylene)c represents a
comparative
weight ratio required to produce a comparative ethylene interpolymer product
having
the target density, where the comparative ethylene interpolymer product is
5
CA 2984838 2019-06-25M17066canada revised disclosure and claims pages.doex
synthesized in a comparative process by replacing the bridged metallocene
catalyst
formulation with an unbridged single site catalyst formulation.
Embodiments of the ethylene interpolymer product may comprise a first ethylene
interpolymer. Other embodiments of the ethylene interpolymer product may
comprise
a first ethylene interpolymer and a third ethylene interpolymer. Other
embodiments of
the ethylene interpolymer product may comprise a first ethylene interpolymer
and a
second ethylene interpolymer. Other embodiments of the ethylene interpolymer
product may comprise a first ethylene interpolymer, a second ethylene
interpolymer
and a third ethylene interpolymer.
The first ethylene interpolymer has a melt index from 0.01 to 200 dg/minute
and a
density from 0.855 g/cc to 0.975 g/cc; the first ethylene interpolymer may
comprise for
5 to 100 wt% of the ethylene interpolymer product. The second ethylene
interpolymer
may comprise from 0 to 95 wt% of the ethylene interpolymer product, has melt
index
from 0.3 to 1000 dg/minute and a density from 0.855 g/cc to 0.975 g/cc. The
third
ethylene interpolymer may comprise from 0 to 30 wt% of the ethylene
interpolymer
product, has a melt index from 0.4 to 2000 dg/minute and a density from 0.855
g/cc to
0.975 g/cc. Weight percent, 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, melt index is measured according to ASTM D1238 (2.16 kg
load
and 190 C) and density is measured according to ASTM D792.
In further embodiments, the upper limit on the CDBI50 of the first and second
ethylene
interpolymers may be 98%, in other cases 95% and in still other cases 90%; and
the
lower limit on the CDBI50 of the first and second ethylene interpolymers may
be 70%,
in other cases 75% and in still other cases 80%. The upper limit on the CDB150
of the
third ethylene interpolymer may be 98%, in other cases 95% and in still other
cases
90%; and the lower limit on the CDBI5D of the third ethylene interpolymer may
be 35%,
in other cases 40% and in still other cases 45%.
In other embodiments, the upper limit on the Mw/IVIn of the first and second
ethylene
interpolymers may be 2.4, in other cases 2.3 and in still other cases 2.2; and
the lower
limit on the Mw/Mn the first and second ethylene interpolymers may be 1.7, in
other
6
'CA 2984838 2019-06-25 017066Canada revised disclosure and claims pages docx
cases 1.8 and in still other cases 1.9. The upper limit on the Mw/Mn of the
third
ethylene interpolymer may be 5.0, in other cases 4.8 and in still other cases
4.5; and
the lower limit on the Mw/Mn of the optional third ethylene interpolymer may
be 1.7, in
other cases 1.8 and in still other cases 1.9.
In this disclosure the amount of long chain branching in ethylene
interpolymers was
characterized by the dimensionless long chain branching factor `LCBF'. In some
embodiments the upper limit on the LCBF of the first and second ethylene
interpolymers may be 0.5, in other cases 0.4 and in still other cases 0.3
(dimensionless); and the lower limit on the LCBF of the first and second
ethylene
interpolymers may be 0.001, in other cases 0.0015 and in still other cases
0.002
(dimensionless). The upper limit on the LCBF of the third ethylene
interpolymer may
be 0.5, in other cases 0.4 and in still other cases 0.3 (dimensionless); and
the lower
limit on the LCBF of the third ethylene interpolymer may be less than 0.001,
i.e. an
undetectable level of long chain branching.
In this disclosure, the Unsaturation Ratio 'UR' was used to characterize the
degree of
unsaturation in ethylene interpolymers. In some embodiments the upper limit on
the
UR of the first and second ethylene interpolymers may be 0.06, in other cases
0.04
and in still other cases 0.02 (dimensionless), and the lower limit on the UR
of the first
and second ethylene interpolymers may be -0.40, in other cases -0.30 and in
still
other cases -0.20 (dimensionless). The upper limit on the UR of the third
ethylene
interpolymer may be 0.06, in other cases 0.04 and in still other cases 0.02
(dimensionless); and the lower limit on UR of the third ethylene interpolymer
may be -
1.0, in other cases -0.95 and in still other cases -0.9.
In this disclosure the amount of residual catalytic metal in ethylene
interpolymers was
characterized by Neutron Activation Analysis %IAA'. The upper limit on the ppm
of
metal AR1 in the first ethylene interpolymer may be 5.0 ppm, in other cases
4.0 ppm
and in still other cases 3.0 ppm, and the lower limit on the ppm of metal AR1
in the first
ethylene interpolymer may be 0.03 ppm, in other cases 0.09 ppm and in still
other
cases 0.15 ppm. The upper limit on the ppm of metal AR2 in the second ethylene
interpolymer may be 5.0 ppm, in other cases 4.0 ppm and in still other cases
3.0 ppm;
while the lower limit on the ppm of metal AR2 in the second ethylene
interpolymer may
7
\CA 2984838 2019-06-25017066Canada revised disclosure and claims pages docx
be 0.03 ppm, in other cases 0.09 ppm and in still other cases 0.15 ppm. The
catalyst
residue in the third ethylene interpolymer reflected the catalyst employed in
its
manufacture. If a bridged metallocene catalyst formulation was used, the upper
limit
on the ppm of metal AR3 in the third ethylene interpolymer may be 5.0 ppm, in
other
cases 4.0 ppm and in still other cases 3.0 ppm; and the lower limit on the ppm
of
metal AR3 in the third ethylene interpolymer may be 0.03 ppm, in other cases
0.09
ppm and in still other cases 0.15 ppm. If an unbridged single site catalyst
formulation
was used, the upper limit on the ppm of metal CR3 in the third ethylene
interpolymer
may be 3.0 ppm, in other cases 2.0 ppm and in still other cases 1.5 ppm and
the lower
limit on the ppm of metal 0R3 in the third ethylene interpolymer may be 0.03
ppm, in
other cases 0.09 ppm and in still other cases 0.15 ppm. In the case of a
homogeneous catalyst formulation containing a bulky ligand-metal complex that
is not
a member of the genera defined by Formula (I) or (II), the upper limit on the
ppm of
metal BR3 in the third ethylene interpolymer may be 5.0 ppm, in other cases
4.0 ppm
and in still other cases 3.0 ppm; and the lower limit on the ppm of metal BR3
in the
third ethylene interpolymer may be 0.03 ppm, in other cases 0.09 ppm and in
still
other cases 0.15 ppm. If a heterogeneous catalyst formulation was used, the
upper
limit on the ppm of metal ZR3 in the third ethylene interpolymer may be 12
ppm, in
other cases 10 ppm and in still other cases 8 ppm; and the lower limit on the
ppm of
metal ZR3 in the third ethylene interpolymer may be 0.5 ppm, in other cases 1
ppm and
in still other cases 3 ppm.
Non-limiting embodiments of manufactured articles include a film comprising at
least
one layer, where the layer comprises at least one of the ethylene interpolymer
products disclosed herein; where the ethylene interpolymer product has 1) a
dimensionless Long Chain Branching Factor, LCBF, greater than or equal to
0.001, 2)
a residual catalytic metal of from 0.03 to 5 5 ppm of hafnium and 3) a
dimensionless
unsaturation ratio, UR, of from -0.40 to 5- 0.06. In other embodiments the
film has a
film gloss at 45 that is from 10% to 30% higher relative to a comparative
film and/or
the film has a film haze that is from 30% to 50% lower compared to a
comparative
film; where the comparative film has the same composition except the ethylene
interpolymer product synthesized with a bridged metallocene catalyst
formulation is
replaced with a comparative ethylene interpolymer product synthesized with an
unbridged single site catalyst formulation.
8
'CA 2984838 2019-06-25017066Canada revised disclosure and claims pages.docx
Additional film embodiments include films where the at least one layer further
comprises at least one second polymer; where the second polymer may be one or
more ethylene polymers, one or more propylene polymers or a mixture of
ethylene
polymers and propylene polymers. Further embodiments include films having a
total
thickness from 0.5 mil to 10 mil. Other embodiments include multilayer films
that have
from 2 to 11 layers, where at least one layer comprises at least one ethylene
interpolymer product.
Brief Description of Figures
.. The following Figures are presented for the purpose of illustrating
selected
embodiments of this disclosure. It being understood, that embodiments in this
disclosure are not limited by these figures; for example, the precise number
of vessels
shown in Figures 3 and 4, or the arrangement of vessels is not limiting.
Figure 1 compares the Unsaturation Ratio 'UR' for Examples 1-6, relative to
Comparatives Q through V and 1 through 5.
Figure 2 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
ordinate plotted was the log of the corrected Intrinsic Viscosity (log(IVc)).
Ethylene
polymers that do not have LCB, or undetectable LCB, fall on the reference
line.
Ethylene polymers having LCB deviate from the reference line and were
characterized
by the dimensionless Long Chain Branching Factor (LCBF). LCBF = (Sh x S)/2;
where Sh and Sv are horizontal and vertical shift factors, respectively.
Figure 3 illustrates embodiments of a continuous solution polymerization
process
employing one CSTR reactor (vessel 11a) and one tubular reactor (vessel 17).
Figure 4 illustrates embodiments of a continuous solution polymerization
process
employing two CSTR reactors (vessels 111a and 112a) and one tubular reactor
(vessel 117). The two CSTR may be operated in series or parallel modes.
Figure 5 SEC determined molecular weight distribution and GPCFTIR determined
branch content (BrF, C6/10000) in Example 14 and Comparative 14.
9
CA 2984838 2019-06-25 017066Canada revised disclosure and claims pages docx
Figure 6 deconvolution of ethylene interpolymer product Example 15 into a
first,
second and third ethylene interpolymer.
Figure 7 multilayer film cold seal force (Newtons, N) as a function of sealing
temperature.
Figure 8 multilayer film hot tack force (Newtons, N) as a function of sealing
temperature.
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.
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.
\cA 2984838 2019-06-25017066Canada revised disclosure and claims pages docx
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 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 frequently 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
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
11
'CA 2984838 2019-06-25017066Canada revised disclosure and claims pages clocx
comonomers. The term ethylene polymer also includes combinations of, or blends
of,
the ethylene polymers described above.
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
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
CDB150 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 GDBI50 less than 70%; in this disclosure such a blend may be
referred to
as a homogeneous blend or homogeneous composition. Similarly, a blend of two
or
more homogeneous ethylene interpolymers (that differ in weight average
molecular
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pages.docx
weight (Mw)) may have a Mw/Mn 2.8; in this disclosure such a blend may be
referred
to 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 defined by the
characteristics of
the polymer produced by the homogeneous catalyst. More 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 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 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
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- 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 (-
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
14
\CA 2984838 2019-06_25)17066Canada revised disclosure and claims pages.docx
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-
and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,
arylamino
radicals and combinations thereof.
Herein the term "R1" and its superscript form "Ri" refers to a first reactor
in a
continuous solution polymerization process; it being understood that R1 is
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.
\\'CA 2984838 2019-06_25 17066Canada revised disclosure and claims pages.doex
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
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. In addition, in solution polymerization there is a
need for
catalyst formulations that are very efficient at incorporating one or more a-
olefins into
the propagating macromolecular chain. Expressed in different manner, 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. In
addition,
there is a need for ethylene interpolymer products that upon conversion into
manufactured articles have improved properties.
In the embodiments disclosed herein, 'a bridged metallocene catalyst
formulation' was
employed in at least one solution polymerization reactor. This catalyst
formulation
included a bulky ligand-metal complex, 'Component A', defined by Formula (I).
R1
X (R6)
R4 \M/ __ X(R6)
/G
(I)
R5 R3
R2
16
\\CA 2984838 2019-06 _2517066Canada revised disclosure and claims pages.doex
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 01-20 hydrocarbyl radical, a C1-20 alkoxy radical or a 06-10
aryl oxide
radical (these radicals may be linear, branched or cyclic or further
substituted with
halogen atoms, Ci_10 alkyl radicals, Ci_io alkoxy radicals, 06-10 aryl or
aryloxy radicals);
Ri represents a hydrogen atom, a 01-20 hydrocarbyl radical, a C1-20 alkoxy
radical, a
06-10 aryl oxide radical or alkylsilyl radicals containing at least one
silicon atom and 03-
30 carbon atoms; R2 and R3 are independently selected from a hydrogen atom, a
01-20
hydrocarbyl radical, a C1-20 alkoxy radical, a C6-10 aryl oxide radical or
alkylsilyl
radicals containing at least one silicon atom and C3-30 carbon atoms, and; R4
and R5
are independently selected from a hydrogen atom, a C1-20 hydrocarbyl radical,
a 01-20
alkoxy radical a C6-10 aryl oxide radical, or alkylsilyl radicals containing
at least one
silicon atom and C3-30 carbon atoms.
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(R6) group is an 'activatable ligand'. Further non-limiting examples of the
X(R6)
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). While not to be construed as limiting, two species of component A
include: diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium
dichloride
having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfC12], and;
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dimethyl
having
the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].
In the embodiments disclosed herein, 'a bridged metallocene catalyst
formulation' was
employed in: (i) a first reactor to produce a first ethylene interpolymer, or
(ii) a first and
17
VCA 2984838 2019-0 6-2517066Canada revised disclosure and claims pages.docx
third reactor, to produce a first and third ethylene interpolymer, or (iii) a
first and
second reactor, to produce a first and second ethylene interpolymer, or (iv) a
first,
second and third solution polymerization reactor, to produce a first, second
and third
ethylene interpolymer. The first and second reactors may be operated in series
or
parallel mode. In series mode the effluent from the first reactor flows
directly into the
second reactor. In contrast, in parallel mode the effluent from the first
reactor by-
passes the second reactor and the effluent from the first and second reactor
are
combined downstream of the second reactor.
A wide variety of catalyst formulations may be employed in the optional third
reactor.
Non-limiting examples of the catalyst formulation employed in the third
reactor include
the bridged metallocene catalyst formulation described above, the unbridged
single
site catalyst formulation described below, a homogeneous catalyst formulation
comprising a bulky ligand-metal complex that is not a member of the genera
defined
by Formula (I) (above), or Formula (II) (below), or a heterogeneous catalyst
formulation. Non-limiting examples of heterogeneous catalyst formulations
include
Ziegler-Natta or chromium catalyst formulations.
In Comparative 1 samples disclosed herein, e.g. Comparative la and lb, 'an
unbridged single site catalyst formulation' was employed in at least one
solution
polymerization reactor. This catalyst formulation included a bulky ligand-
metal
complex, hereinafter 'Component C', defined 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
18
vcA 2984838 2019-06-25 17066Canada revised disclosure and claims pages doex
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 n-bonding to the metal M, such embodiments include
both
n3-bonding and n5-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)
wherein the RP groups are independently selected from: a hydrogen atom; a
halogen
atom; Ci_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 C6-10
aryloxy radical;
an amido radical; a sily1 radical of formula -Si(Rs)3, wherein the Rs groups
are
independently selected from, a hydrogen atom, a C1-8 alkyl or alkoxy radical,
a C6-10
aryl radical, a C6-10 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, C1-20 hydrocarbyl radicals, C1-20 alkoxy
radicals,
19
\\ICA 2984838 2019-06-2517066Canada revised disclosure and claims pages docx
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 any 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 Formula (II).
While not to be construed as limiting, two species of component C include:
cyclopentadienyl tri(tertiary butyl) phosphinimine titanium dichloride having
the
molecular formula [Cp[(t-Bu)3PN]TiC12], and; cyclopentadienyl
tri(isopropyl)phosphinimine titanium dichloride having the molecular formula
[Cp[(isopropy1)3PNI]TiC12].
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 interpolymer products were prepared by
employing an unbridged single site catalyst formulation. In these Comparative
samples, the unbridged single site catalyst formulation replaced the bridged
metallocene catalyst formulation in the first polymerization reactor, or the
first and
second polymerization reactor(s), or the first, second and third
polymerization
reactors. The unbridged single site 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.
11(CA 2984838 2019-06-2517066Canada revised disclosure and claims pages docx
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 aluminoxane (or MMAO-7)
wherein
each R group in Formula (IV) is a methyl radical.
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
21
\'CA 2984838 2019-06-25)l7066Canada revised disclosure and claims pages.docx
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)tZH][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
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(pentaf)uorophenyl)boron,
tri(n-
butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron,
N,N-
22
\\cA 298 4 838 2019-06-25 17066Canada revised disclosure and claims pagesvlocx
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, dicyclohexylammoniuni 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
tetrafluorophenyOborate. 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.
As fully described below, a highly active bridged metallocene catalyst
formulation was
produced by optimizing the quantity and mole ratios of the four components in
the
formulation; i.e., component A, component MA, component BA and optionally
component PA. Where highly active means a very large amount of ethylene
interpolymer is produced from a very small amount of catalyst formulation.
Similarly, a
23
cA 2984838 2019-06-25 I 7066Canada revised disclosure and claims pages.docx
highly active unbridged single site catalyst formulation (comparative catalyst
formulation) was produced by optimizing the quantity and mole ratios of the
four
components in the formulation; i.e., component C, component Mc, component BC
and
optionally component P.
In this disclosures, heterogeneous catalyst formulations may be employed in
the
optional third reactor to synthesize the third ethylene interpolymer. Non-
limiting
examples of heterogeneous catalyst formulations include: Ziegler-Natta and
chromium
catalyst formulations. Non-limiting examples of Ziegler-Natta catalyst
formulations
include 'an in-line Ziegler-Natta catalyst formulation' or 'a batch Ziegler-
Natta catalyst
formulation'. The term 'in-line' refers 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' refers 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
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
24
\\(cA 2984838 2019-06-2517066Canada revised disclosure and claims pages.docx
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 equivalent 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
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)i-i; 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):
\\(cA 2984838 2019-06-2517066Canada raked disclosure and claims pages does<
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 C5 to C12 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.
Additional embodiments of heterogeneous catalyst formulations include
formulations
where the "metal compound" is a chromium compound; non-limiting examples
include
silyl 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 examples of co-catalysts include trialkylaluminum,
alkylaluminoxane and dialkoxyalkylaluminum compounds and the like.
In this disclosure, the bridged metallocene catalyst formulation produced
solution
process ethylene interpolymer products having a unique unsaturation ratio, UR.
Table 1 discloses the amount of Internal, Side Chain and Terminal
unsaturations per
100 carbons (100C) in the Examples of this disclosure, relative to
Comparatives, i.e.
the amount of trans-vinylene, vinylidene and terminal vinyl groups as measured
26
\<;CA 2 98 48 38 2 019 ¨0 6-251 7066C anada revised disclosure and claims
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according to ASTM D3124-98 and ASTM D6248-98. Table 1 also discloses the
dimensionless Unsaturation Ratio', 'UR', as defined by the following equation
UR = (SCu-Tu)/Tu Eq.(UR)
where SCu are the side chain unsaturations and Tu are the terminal
unsaturations.
Graphically, Figure 1 compares the average UR values for Examples and
Comparatives. Statistically, the Examples (Examples 1 through 6) have a
significantly
different average UR value, relative to all Comparatives. For example, the
average
UR value for Examples 1 through 6 was -0.116 0.087 and the average UR value
for
Comparative Q1 through 04 was 0.085 0.014; these average UR values were
significantly different based on a t-test assuming equal variances, i.e. the t-
stat of 4.51
exceeded the two tail t-critical of 2.31 and the two tail P-value of 0.00197
was less
than 0.05. Comparative Q were commercial products called Queo available from
Borealis, Vienna, Austria; specifically Comparative Q1 was Queo 0201,
Comparative
Q2 was Queo 8201, Comparative Q3 was Queo 0203 and Comparative 04 was Queo
1001. Queo products are ethylene/1-octene copolymers, believed to be produced
in a
solution polymerization process employing one reactor and a metallocene
catalyst
formulation.
Statistically, the average UR value of Examples 1 through 6 was also
significantly
different from Comparative R, Comparative S, Comparative T, Comparative U,
Comparative V, Comparative 1, Comparative 2, Comparative 3, Comparative 4 and
Comparative 5. As shown in Table 1 and Figure 1, the average UR of Comparative
R
was 1.349 +0_907, this was the average of 7-samples of commercial products
called
AffinityTM available from The Dow Chemical Company, Midland, Michigan;
specifically,
AffinityTM PL1880 (3-samples), Affinity TM PF1140, Affinity TM PF1142 and
AffinityTM
PL1881. The Affinity TM samples were ethylene/1-octene copolymers believed to
be
produced in a solution polymerization process employing one reactor and a
single site
catalyst formulation. The average UR of Comparative S was 0.1833 0.0550, i.e.
an
average of 5-samples of commercial products called Enable TM available from
ExxonMobil Chemical Company, Spring, Texas; specifically, EnableTM 27-03CH (3-
samples) and Enable TM 20-05 (2-samples). Enable TM products were ethylene/1-
hexene copolymers, believed to be produced in a gas phase process employing
one
27
CA 2984838 2019-06-25 \2017066Canada revised disclosure and claims pages.docx
reactor and a metallocene catalyst formulation. The average UR of Comparative
T
was -0.6600 0.1306, i.e. an average of 48-samples of commercial products
called
Exceed TM available from ExxonMobil Chemical Company, Spring, Texas;
specifically,
ExceedTM 1018 (26-samples), ExceedTM 1023 (4-samples), ExceedTM 1015 (3-
samples), Exceedm 4518 (3-samples), ExceedTm 3518(4-samples), Exceed TM 1012
(3-samples), Exceed TM 1318CA (2-samples), Exceed TM 3812, Exceed TM 1023DA
and
ExceedTM 2718CB. Exceed TM products were ethylene/1-hexene copolymers believed
to be produced in a gas phase process employing one reactor and a metallocene
catalyst formulation. Comparative U, having a UR value of -0.667, was a
commercial
product called Elite TM AT 6202 available from The Dow Chemical Company,
Midland,
Michigan. Elite TM AT 6202 was an ethylene/1-hexene copolymer, believed to be
produced in a dual reactor solution process employing at least one homogeneous
catalyst formulation. The average UR of Comparative V was -0.8737 0.0663,
i.e. an
average of 25-samples of commercial products called Elite TM available from
The Dow
Chemical Company, Midland, Michigan; specifically, Elite TM 5400 (12-samples),
Elite TM 5100 (4-samples), EliteTm 5110 (2-samples), EliteTM 5230 (2-samples),
Elite TM
5101 and Elite TM 5500. Elite TM products were ethylene/1-octene copolymers
believed
to be produced in a solution polymerization process employing a single site
catalyst
formulation in a first reactor and a batch Ziegler-Natta catalyst formulation
in a second
reactor. The average UR of Comparative 1 was -0.4374 0.1698, i.e. an average
of
61-samples of a commercial product called SURPASSTM FPs117 available from
NOVA Chemicals Corporation, Calgary, Alberta. SURPASSTM FF's117 was an
ethylene/1-octene copolymer produced in a solution polymerization process
employing a single site catalyst formulation. The average UR of Comparative 2
was -
0.5000 0.1000, i.e. an average of 3-samples of an experimental product
manufactured by NOVA Chemicals Corporation, Calgary, Alberta. Comparative 2a,
2b and 2c were ethylene/1-octene copolymers (about 0.917 g/cc and about 1.012)
produced in a solution polymerization process employing a bridged metallocene
catalyst formulation in a first reactor and an unbridged single site catalyst
formulation
in a second reactor. The average UR of Comparative 3 was -0.8548 0.0427, i.e.
an
average of 4-samples of an experimental product manufactured by NOVA Chemicals
Corporation, Calgary, Alberta. Comparative 3a, 3b, 3c and 3d were ethylene/1-
octene
copolymers (about 0.917 g/cc and about 1.0 12) produced in a solution
polymerization
process employing a bridged metallocene catalyst formulation in a first
reactor and an
28
\lcCA 2984838 2019-06-2517066Canada revised disclosure and claims pages.docx
in-line Ziegler-Natta catalyst formulation in a second reactor. The average UR
of
Comparative 4 was -0.8633 0.0470, i.e. an average of 21-samples of commercial
products called SURPASSTM available from NOVA Chemicals Corporation, Calgary,
Alberta; specifically, SURPASS TM SPs116 (6-samples), SURPASSTM SPsK919 (5-
samples), SURPASSTM VPsK114 (3-samples) and SURPASSTM VPsK914 (7-
samples) were ethylene/l-octene copolymers produced in a solution
polymerization
process employing a single site catalyst formulation in a first reactor and an
in-line
Ziegler-Natta catalyst formulation in a second reactor. The average UR of
Comparative 5 was -0.8687 0.0296, i.e. an average of 137-samples of a
commercial
product called SCLAIRTM FP120 available from NOVA Chemicals Corporation,
Calgary, Alberta. FP120 was an ethylene/1-octene copolymer produced in a
solution
polymerization process employing an in-line Ziegler-Natta catalyst
formulation.
As evidenced by Figure 1 and Table 1, the UR values of Comparatives 3 to 5 and
Comparative V are not significantly different (the UR values ranged from -
0.8548 to -
0.8737) this is believed to reflect the fact that a Ziegler-Natta catalyst was
employed to
manufacture at least a portion of these copolymers.
In this disclosure, the bridged metallocene catalyst formulation produced
ethylene
interpolymer products having long chain branches, hereinafter `LCB'.
LCB is a structural feature in polyethylenes that is well known to those of
ordinary skill
in the art. Traditionally, there are three methods to quantify the amount of
LCB,
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, Roc. Chem.
Res. 1977, 10, 332-339. 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
29
\\ccA 2984838 2019-06-2517066Canada revised disclosure and claims pages docx
characterize LCB in ethylene/1-octene copolymers, which have hexyl groups as
side
branches).
The triple detection SEC method measures the intrinsic viscosity (RID (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, 0.D. Redwine, Macromolecules 2000; 33: 7489). By
referencing the intrinsic viscosity of a branched polymer (Ho to that of a
linear one
(ND at the same molecular weight, the viscosity branching index factor g'
(g'=[n]b/[n]i)
was used for branching characterization. However, both short chain branching
(SCB)
and long chain branching (LCB) make contribution to the intrinsic viscosity
(ND, effort
was made to isolate the SCB contribution for ethylene/l-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
SCB 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
140 C for the sample divided by the SCB corrected Mark-Houwink constant (Kc0)
for
linear ethylene/1-olefin copolymer, Eq.(1).
K N/A40.725
Viscosity LCB Index = ¨m = ____________________________________ Eq.(1)
Kc, (391.98¨A xscB)/i000000
Where [ri] was the intrinsic viscosity (dL/g) determined by 3D-SEC, An, was
the
viscosity average molar mass (g/mole) determined using 30-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.
\\ccA 2984838 2019-06-2517066Canada revised disclosure and claims pages.docx
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 (no) and weight average molar mass (Mw) data. The 3.41 power
dependence
(no = KxMw341) 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.
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
SCB and molar mass distribution (polydispersity), a 'Long Chain Branching
Factor',
hereinafter LCBF' was introduced to characterize the amount of LCB in
ethylene/a-
olefin copolymers, as fully described below.
In this disclosure the Long Chain Branching Factor (LCBF) was used to
characterize
the amount of LCB in ethylene interpolymer products. The disclosed ethylene
interpolymer products were produced employing the bridged metallocene catalyst
formulation in: (i) a first reactor; (ii) a first and second reactor; (iii) a
first, second and
third reactor; or (iv) optionally the bridged metallocene catalyst formulation
employed
in the third reactor may be replaced with an alternative homogeneous catalyst
formulation or a heterogeneous catalyst formulation.
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\\ecA 2 98 48 38 2 019 ¨0 6 ¨2517066Canacia revised disclosure and claims
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Figure 2 illustrates the calculation of the LCBF. The solid 'Reference Line'
shown in
Figure 2 characterizes ethylene polymers that do not contain LCB (or contain
undetectable levels of LCB).
Ethylene interpolymers containing LCB deviated from the Reference Line. For
example, ethylene interpolymer products Examples 1 through 3 (open circles in
Figure
2) deviated horizontally and vertically from the Reference Line.
The LCBF calculation requires the polydispersity corrected Zero Shear
Viscosity
(ZSVn) and the SCB corrected Intrinsic Viscosity (IV) as described by Eq.(2).
The correction to the Zero Shear Viscosity, ZSVn, having dimensions of poise,
was
performed as shown in equation Eq.(2):
1.8389 X tio
ZSV = _______________________________ Eq.(2)
c 2.4110Ln(Pc1)
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 dimensionless constants.
The correction to the Intrinsic Viscosity, IVn, having dimensions of dL/g, was
performed as shown in equation Eq.(3):
A X SCB X 11117725
117c -= [TA + Eq.(3)
l000000
where the intrinsic viscosity [n] (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.
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\\cCA 2984838 2019-06 ¨2517066Canada revised disclosure and claims pages.docx
In the case of an ethylene homopolymer no correction is required for the Mark-
Houwink constant, i.e. SCB is zero.
Linear ethylene/a-olefin interpolymers (which do not contain LCB or contain
.. undetectable levels of LCB) fall on the Reference Line defined by Eq.(4).
Log(IV) = 0.2100 x Log(ZSV,) ¨ 0.7879 Eq.(4)
As shown in Figure 2, the calculation of the LCBF was based on the Horizontal-
Shift
(Sh) and Vertical-Shift (Sv) from the linear reference line, as defined by the
following
equations:
Sh = Log (ZSV,) ¨ 4.7619 x Log (N) ¨ 3.7519 Eq.(5)
S, = 0.2100 x Log (ZSV,) ¨ Log(J17)¨ 0.7879 Eq.(6).
In Eq. (5) and (6), it is required that ZSVc and Ric have dimensions of poise
and dL/g,
respectively. The Horizontal-Shift (Sh) 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 ZSVe of the sample under test
relative to the
ZSVc of a linear ethylene polymer having the same IVc. The Horizontal-Shift
(Sh) was
dimensionless. The Vertical-Shift (Sv) was a shift in IVe 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 IV c 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
Linear ethylene/a-olefin interpolymers (which do not contain LCB or contain
undetectable levels of LCB) fall on the Reference Line defined by Eq.(4).
Table 2A
and 2B list 37 Reference Resins having no LCB (or undetectable LCB). Reference
33
cCA 2984838 2019-06-2517066Canada revised disclosure and claims pages.docx
Resins had Mw/Mn values that ranged from 1.68 to 9.23 and the "A" value in
Table 2A
indicates whether the reference resin contained 1-octene, 1-hexene or 1-butene
a-
olefin. Reference Resins included ethylene copolymers produced in solution,
gas
phase or slurry processes with Ziegler-Natta, homogeneous and mixed (Ziegler-
Natta
+ homogeneous) catalyst formulations. 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 2B where the reference resins had LCBF values ranging
from
0.000426 to 1.47x10-9.
Table 3A discloses the LCBF values of Examples and Comparatives. For example,
the Sh and Sv of long chain branched Example 1 were 0.646 and 0.136,
respectively,
and the LCBF was 0.044 ((0.646 x 0.136)/2). In contrast, the Sh and Sv of
Comparative la, which did not contain LCB, were -0.022 and -0.0047,
respectively,
and the LCBF was 0.0001 ((-0.022 x -0.047)/2).
In this disclosure, resins having LCB were characterized as having a LCBF ?_
0.001
(dimensionless); in contrast, resins having no LCB (or undetectable LCB) were
characterized by a LCBF of less than 0.001 (dimensionless).
The ethylene interpolymer products, disclosed herein, i.e. Examples 1-3
contained
LCB as evidenced by Table 3A and Figure 2. More specifically, as shown in
Table 3A
the LCBF of Examples 1 through 3 were 0.044, 0.054 and 0.056, respectively,
and do
not fall on the linear Reference Line shown in Figure 2. In contrast,
Comparative la
had a LCBF of 0.0001 (Table 3A) and falls on the Reference Line (Figure 2,
filled
triangle), i.e. did not contain LCB or had an undetectable level of LCB.
Examples 1-2
were ethylene interpolymer products produced using a bridged metallocene
catalyst
formulation in a first and a second solution polymerization reactor, Example 3
was
produced using a bridged metallocene catalyst formulation in a first solution
polymerization reactor. Comparative la was produced using an unbridged single
site
catalyst formulation in a first and a second solution polymerization reactor.
Comparative 1a was a commercially available product coded FPs117-C available
from
NOVA Chemical, Calgary, Alberta. Given Table 3A, it was evident that
Comparative
Q1, Q3 and 04 (open squares in Figure 2) contained long chain branching, i.e.
LCBF
values of 0.049, 0.018 and 0.067, respectively. Comparative Q were commercial
34
\\eCA 2984838 2019-06_25 7066Canada revised disclosure and claims pages.docx
products called Queo TM available from Borealis, Vienna, Austria; specifically
Comparative Q1 was Queo TM 0201, Comparative Q3 was Queo TM 0203 and
Comparative Q4 was Queo TM 1001.
Table 3B summarized Comparative R1 (open diamond in Figure 2) contained LCB,
having a LCBF value of 0.040. Comparative R1 was a commercial product called
Affinity PL1880G available from The Dow Chemical Company, Midland Michigan. As
shown in Table 3B Comparatives S1 and S2 (filled circles in Figure 2)
contained LCB,
having LCBF values of 0.141 and 0.333, respectively. Comparative Si and S2
were
commercial products called Enable available from ExxonMobil Chemical Company,
Spring Texas; specifically Enable 20-05HH and Enable 27-03. Table 3B disclosed
that Comparative U (crossed-x symbol in Figure 2) contained LCB, i.e. the LCBF
value was 0.036. Comparative U was a commercial product coded Elite AT 6202
available from The Dow Chemical Company, Midland, Michigan. The two samples of
Comparative V2 (dash-like symbol in Figure 2) summarized in Table 3B (V2a and
V2b), having LCBF values of 0.0080 and 0.0088 were a commercial product called
Elite 5100G available from The Dow Chemical Company, Midland, Michigan.
Comparative T was Exceed 1018 available from ExxonMobil Chemical Company,
Spring, Texas.
Although Comparative 4 and Comparative 5 do not appear in Tables 3A-3B or
Figure
2, these resins did not have LCB, or had an undetectable level of LCB, i.e.
LCBF <
0.001. Also not shown in Tables 3A-3B or Figure 2 were Comparatives 2 and 3.
Comparative 2 contained LCB, i.e. the average LCBF of three samples of
Comparative 2 (i.e. Comparative 2a through 2c) was 0.037. Comparative 3
contained
LCB, i.e. the average LCBF of four samples of Comparative 3 (i.e. Comparative
3a-
3d) was 0.016.
Solution Polymerization Process
Embodiments of the continuous solution polymerization process are shown in
Figures
3 and 4. Figures 3 and 4 are not to be construed as limiting, it being
understood, that
embodiments are not limited to the precise arrangement of, or number of,
vessels
shown. In brief, Figure 3 illustrates one continuously stirred tank reactor
(CSTR)
\\c CA 2984838 2019-06-25 7066Canada revised disclosure and claims pages.docx
followed by an optional tubular reactor and Figure 4 illustrates two CSTRs
followed by
an optional tubular reactor. The dotted lines in Figures 3 and 4 illustrate
optional
features of the continuous polymerization process. In this disclosure,
equivalent terms
for tubular reactor 117 shown in Figure 4, were the 'third reactor' or `R3';
optionally a
third ethylene interpolymer was produced in this reactor. Turning to Figure 3
that has
one CSTR, the terms third reactor or R3 were also used to describe tubular
reactor
17; wherein a third ethylene interpolymer was optionally produced.
In Figure 3 process solvent 1, ethylene 2 and optional a-olefin 3 are combined
to
produce reactor feed stream RF1 which flows into reactor 11a. 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 is generally added
to
control 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.
A bridged metallocene catalyst formulation is injected into reactor 11a via
stream 5e.
Catalyst component streams 5d, 5c, 5b and optional 5a refer to the ionic
activator
(Component B), the bulky ligand-metal complex (Component A), the alumoxane co-
catalyst (Component M) and optional hindered phenol (Component P),
respectively.
The catalyst component streams can be arranged in all possible configurations,
including an embodiment where streams 5a through 5d are independently injected
into reactor 11a. Each catalyst component is dissolved in a catalyst component
solvent. Catalyst component solvents, for Components A, B, M and P 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 component in stream 5e. In
this
disclosure, the term 'first homogeneous catalyst assembly' refers the
combination of
streams 5a through 5e, flow controllers and tanks (not shown in Figure 3) that
functions to deliver the bridged metallocene catalyst formulation to the first
reactor
11a. The optimization of the bridged metallocene catalyst formulation is
described
below.
36
\\cici. 2'984838 20-19-067066Canada revised disclosure and claims pages.docx
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 catalyst,
deactivated
catalyst, residual catalyst components and other impurities (if present).
Optionally the first exit stream, stream 11c, is deactivated by adding a
catalyst
deactivator A from catalyst deactivator tank 18A forming a deactivated
solution A,
stream 12e; in this case, Figure 3 defaults to a single reactor solution
process. If a
catalyst deactivator is not added, stream 11c enters tubular reactor
reactor 17. Catalyst deactivator A is discussed below.
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 3, 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, a homogeneous or a
heterogeneous catalyst formulations may be injected into reactor 17. Non-
limiting
examples of a homogeneous catalyst formulation includes a bridged metallocene
catalyst formulation, an unbridged single site catalyst formulation, or a
homogeneous
catalyst formulation where the bulky ligand-metal complex is not a member of
the
genera defined by Formula (I) or Formula (II). Stream 40 in Figure 3
represents the
output from a 'second homogeneous catalyst assembly'. One embodiment of the
second homogeneous catalyst assembly is similar to the first homogeneous
catalyst
assembly described above, i.e. having similar streams, flow controllers and
vessels.
__ In Figure 3, streams 34a through 34h represent a 'heterogeneous catalyst
assembly'.
In one embodiment an in-line Ziegler-Natta catalyst formulation is produced in
the
heterogeneous catalyst assembly. The components that comprise the in-line
Ziegler-
Natta catalyst formulation are introduced through streams 34a, 34b, 34c and
34d.
Stream 34a contains a blend of an aluminum alkyl and a magnesium compound,
37
\\cicA 2984838 2019-06 ¨257066Canada revised disclosure and claims pages.docx
stream 34b contains a chloride compound, stream 34c contains a metal compound
and stream 34d contains an alkyl aluminum co-catalyst. An efficient in-line
Ziegler-
Natta catalyst formulation if formed by optimizing the following molar ratios:
(aluminum
alkyl)/(magnesium compound) or (ix)/(v); (chloride compound)/(magnesium
compound) or (vi)/(v); (alkyl aluminum co-catalyst)/(metal compound) or
(viii)/(vii), and;
(aluminum alkyl)/(metal compound) or (ix)! (vii); as well as the time these
compounds
have to react and equilibrate.
Stream 34a contains a binary blend of a magnesium compound, component (v) and
an aluminum alkyl, component (ix), in process solvent. The upper limit on the
(aluminum alkyl)/(magnesium compound) molar ratio in stream 10a may be 70, in
some cases 50 and is other cases 30. The lower limit on the (aluminum
alkyl)/(magnesium compound) molar ratio may be 3.0, in some cases 5.0 and in
other cases 10. Stream 34b contains a solution of a chloride compound,
component
(vi), in process solvent. Stream 34b is combined with stream 34a and the
intermixing
of streams 34a and 34b produces a magnesium chloride catalyst support. To
produce
an efficient in-line Ziegler-Natta catalyst (efficient 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 4, in some
cases 3.5 and is other cases 3Ø The lower limit on the (chloride
compound)/(magnesium compound) molar ratio may be 1.0, in some cases 1.5 and
in other cases 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;
hereafter 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 70 seconds, in some cases 60 seconds and is other cases 50 seconds. The
lower limit on HUT-1 may be 5 seconds, in some cases 10 seconds and in other
cases 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; hereafter 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 50 seconds, in some cases 35 seconds and is other cases
38
cICA 2984838 2019-06-257066Canada revised disclosure and claims pages docx
25 seconds. The lower limit on HUT-2 may be 2 seconds, in some cases 6 seconds
and in other cases 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 10, in some cases 7.5 and is
other
cases 6Ø The lower limit on the (alkyl aluminum co-catalyst)/(metal
compound)
molar ratio may be 0, in some cases 1.0 and in other cases 2Ø In addition,
the time
between the addition of the alkyl aluminum co-catalyst and the injection of
the in-line
Ziegler-Natta catalyst formulation into reactor 17 is controlled; hereafter
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
15 seconds, in some cases 10 seconds and is other cases 8 seconds. The lower
limit on HUT-3 may be 0.5 seconds, in some cases 1 seconds and in other cases
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 3, 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 34e.
The quantity of in-line heterogeneous catalyst formulation added to reactor 17
is
expressed as the parts-per-million (ppm) of metal compound (component (vii))
in the
reactor solution, hereafter "R3 (vii) (ppm)". The upper limit on R3 (vii)
(ppm) may be
10 ppm, in some cases 8 ppm and in other cases 6 ppm. The lower limit on R3
(vii)
(ppm) in some cases may be 0.5 ppm, in other cases 1 ppm and in still other
cases
.. 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 2, in some cases 1.5 and is other
cases
1Ø The lower limit on the (aluminum alkyl)/(metal compound) molar ratio may
be
0.05, in some cases 0.075 and in other cases 0,1.
39
CA 2984838 2019-06-25017066Canada revised disclosure and claims pages docx
Any combination of the streams employed to prepare and deliver the in-line
Ziegler-
Natta catalyst formulation to reactor 17 may be heated or cooled, i.e. streams
34a
through 34h; in some cases the upper temperature limit of streams 34a through
34h
.. may be 90 C, in other cases 80 C and in still other cases 70 C and; in some
cases
the lower temperature limit may be 20 C; in other cases 35 C and in still
other cases
50 C.
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. A third ethylene interpolymer will be formed if
catalyst
deactivator B is added downstream of reactor 17 via catalyst deactivator tank
18B
forming a deactivated solution, i.e. stream 19.
.. 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 optional 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 fresh catalyst formulation is added to reactor 17 to
polymerize
residual ethylene and residual optional a-olefin to form the optional third
ethylene
interpolymer, or; (d) fresh process solvent 13, ethylene 14, optional a-olefin
15 and a
fresh catalyst formulation are added to reactor 17 to form the optional third
ethylene
interpolymer.
In Figure 3, deactivated solution A (stream 12e) or B (stream 19) passes
through
pressure let down device 20 and heat exchanger 21. If the optional
heterogeneous
.. catalyst formulation has been added, a passivator may be added via tank 22
forming a
passivated solution 23. The passivated solution, deactivated solution A or
deactivated
solution B passes through pressure let down device 24 and enters a first
vapor/liquid
separator 25; hereinafter, "V/L" is equivalent to vapor/liquid. Two streams
are formed
in the first V/L separator: a first bottom stream 27 comprising a solution
that is
clCA 2984838 2019-06-257066Canada revised disclosure and claims pages. docx
ethylene interpolymer rich 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 enters a second V/L separator 28. In the second V/L
separator two streams are formed: a second bottom stream 30 comprising a
solution
that is richer in ethylene interpolymer product 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 flows into a third V/L separator 31. In the third
V/L
separator two streams are 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.
Embodiments also include the use of one or more V/L separators operating at
reduced pressure, i.e. the operating pressure is lower than atmospheric
pressure
and/or embodiments where heat is added during the devolitization process, i.e.
one or
more heat exchangers are employed upstream of, or within, one or more of the
V/L
separators. Such embodiments facilitate the removal of residual process
solvent and
comonomer such that the residual volatiles in ethylene interpolymer products
are less
than 500 ppm.
Product stream 33 proceeds 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. Other embodiments include the use of a devolatilizing extruder,
where
residual process solvent and optional a-olefin may be removed such that the
volatiles
in the ethylene interpolymer product is less than 500 ppm. Once pelletized the
solidified ethylene interpolymer product is typically transported to a product
silo.
41
AcCA 2984838 2019-06-25 7066Canada revised disclosure and claims pages.docx
The first, second and third gaseous overhead streams shown in Figure 3
(streams 26,
29 and 32, respectively) are sent to a distillation column where solvent,
ethylene and
optional ot-olefin are separated for recycling, or; the first, second and
third gaseous
overhead streams are recycled to the reactors, or; a portion of the first,
second and
third gaseous overhead streams are recycled to the reactors and the remaining
portion is sent to a distillation column.
Figure 4 illustrates an embodiment of the continuous solution polymerization
process
employing two CSTR reactors and an optional tubular reactor. Process solvent
101,
ethylene 102 and optional a-olefin 103 are combined to produce reactor feed
stream
RF101 which flows into reactor 111a. Optionally hydrogen may be injected into
reactor 111a through stream 104. Reactor 111a is continuously stirred by
stirring
assembly 111b.
A first bridged metallocene catalyst formulation is injected into reactor 111a
via stream
105e. Catalyst component streams 105d, 105c, 105b and optional 105a contain
the
ionic activator (Component B1, where the superscript '1' denotes the first
reactor), the
bulky ligand-metal complex (Component A1), the alumoxane co-catalyst
(Component
IV11) and optional hindered phenol (Component P1), respectively. Each catalyst
component is dissolved in a catalyst component solvent. Catalyst component
solvents, for Components A1, B1, M1 and P1 may be the same or different. In
Figure 4,
the first homogeneous catalyst assembly refers the combination of streams 105a
through 105e, flow controllers and tanks that functions to deliver the active
bridged
metallocene catalyst formulation to reactor 111a.
Reactor 111a produces a first exit stream, stream 111c, containing the first
ethylene
interpolymer dissolved in process solvent. Figure 4 includes two embodiments
where
reactors 111a and 112a can be operated in series or parallel modes. In series
mode
100% of stream 111c (the first exit stream) passes through flow controller
111d
forming stream 111e which enters reactor 112a. In contrast, in parallel mode
100% of
stream 111c passes through flow controller 111f forming stream 111g. Stream
111g
by-passes reactor 112a and is combined with stream 112c (the second exit
stream)
forming stream 112d (the third exit stream).
42
CA 2984838 2019-06-252017066Canada revised disclosure and claims pages.docx
Fresh reactor feed streams are injected into reactor 112a; process solvent
106,
ethylene 107 and optional a-olefin 108 are combined to produce reactor feed
stream
RF102. It is not important that stream RF102 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 112a
through stream 109 to control the molecular weight of the second ethylene
interpolymer. Reactor 112a is continuously stirred by stirring assembly 112b
which
includes a motor external to the reactor and an agitator within the reactor.
As shown in Figure 4, a second bridged metallocene catalyst formulation is
injected
into reactor 112a through stream 110e and a second ethylene interpolymer is
formed
in reactor 112a. Catalyst component streams 110d, 110c, 110b and 110a contain
the
ionic activator Component B2 (where the superscript '2' denotes the second
reactor),
the bulky ligand-metal complex (Component A2), the alumoxane co-catalyst
(Component M2) and optional hindered phenol (Component P2), respectively. The
catalyst component streams can be arranged in all possible configurations,
including
an embodiment where streams 110a through 110d are independently injected into
reactor 111a. Each catalyst component is dissolved in a catalyst component
solvent.
Formula (I) defines the genus of catalyst Component A; however, Component A2
employed in reactor 112a may be the same, or different, relative to catalyst
Component A1 employed in reactor 111a. Similarly, the chemical composition of
catalyst Components B2 and B1, catalyst Components M2 and M1 and catalysts
Component P2 and P1 may be the same, or different. In this disclosure, the
term
'second homogeneous catalyst assembly' refers the combination of streams 110a
through 110e, flow controllers and tanks that functions to deliver the second
bridged
metallocene catalyst formulation to the second reactor, reactor 112a in Figure
4. The
optimization of the first and second bridged metallocene catalyst formulation
is
described below.
Although not shown in Figure 4, an additional embodiment includes the
splitting of
stream 105a into two streams, such that a portion of steam 105a is injected
into
reactor 111a and the remaining portion of stream 105a is injected into reactor
112a.
43
AchcA 2984838 2019-06-257066Canada revised disclosure and claims pages .docx
In other words, the first bridged metallocene catalyst formulation is injected
into both
reactors.
If reactors 111a and 112a are operated in a series mode, the second exit
stream 112c
.. 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 112c is deactivated by adding a catalyst deactivator A from catalyst
deactivator tank 118A forming a deactivated solution A, stream 112e; in this
case,
Figure 4 defaults to a dual reactor solution process. If the second exit
stream 112c is
not deactivated the second exit stream enters tubular reactor 117.
If reactors 111a and 112a are operated in parallel mode, the second exit
stream 112c
contains the second ethylene interpolymer dissolved in process solvent. The
second
exit stream 112c is combined with stream 111g forming a third exit stream
112d, the
latter contains the second ethylene interpolymer and the first ethylene
interpolymer
dissolved in process solvent. Optionally the third exit stream 112d is
deactivated by
adding catalyst deactivator A from catalyst deactivator tank 118A forming
deactivated
solution A, stream 112e. If the third exit stream 112d is not deactivated the
third exit
stream 112d enters tubular reactor 117.
Optionally, one or more of the following reactor feed streams may be injected
into
tubular reactor 117; process solvent 113, ethylene 114 and a-olefin 115. As
shown in
Figure 4, streams 113, 114 and 115 may be combined forming reactor feed stream
RF103 and injected into reactor 117. It is not particularly important that
stream RF103
be formed; i.e. reactor feed streams can be combined in all possible
combinations.
Optionally hydrogen may be injected into reactor 117 through stream 116.
Optionally, a homogeneous or a heterogeneous catalyst formulations may be
injected
into reactor 117. Non-limiting examples of a homogeneous catalyst formulation
includes a bridged metallocene catalyst formulation, an unbridged single site
catalyst
formulation, or a homogeneous catalyst formulation where the bulky ligand-
metal
complex is not a member of the genera defined by Formula (I) or Formula (II).
Stream
44
\\crcA 2984838 2019-06 ¨257066Canada revised disclosure and claims pages.docx
140 in Figure 4 represents the output from a 'third homogeneous catalyst
assembly'.
One embodiment of the third homogeneous catalyst assembly is similar to the
first
homogeneous catalyst assembly described above, i.e. having similar streams,
flow
controllers and vessels.
In Figure 4, streams 134a through 134h represent a 'heterogeneous catalyst
assembly'. In one embodiment an in-line Ziegler-Natta catalyst formulation is
produced in the heterogeneous catalyst assembly. The components that comprise
the in-line Ziegler-Natta catalyst formulation are introduced through streams
134a,
134b, 134c and 134d. Stream 134a contains a blend of an aluminum alkyl and a
magnesium compound, stream 134b contains a chloride compound, stream 134c
contains a metal compound and stream 134d contains an alkyl aluminum co-
catalyst.
The optimization of an in-line Ziegler-Natta catalyst formulation is described
above.
Once prepared, the in-line Ziegler-Natta catalyst is injected into reactor 117
through
stream 134e; optionally, additional alkyl aluminum co-catalyst is injected
into reactor
117 through stream 134h. As shown in Figure 4, optionally, 100% of stream
134d, the
alkyl aluminum co-catalyst, may be injected directly into reactor 117 via
stream 134h.
Optionally, a portion of the alkyl aluminum co-catalyst may be injected
directly into
reactor 117 via stream 134h and the remaining portion injected into reactor
117 via
stream 134e. Any combination of the streams that comprise the heterogeneous
catalyst assembly may be heated or cooled, i.e. streams 134a-134e and 134h.
A third ethylene interpolymer may, or may not, form in reactor 117. A third
ethylene
interpolymer will not form if catalyst deactivator A is added upstream of
reactor 117 via
catalyst deactivator tank 118A. A third ethylene interpolymer will be formed
if catalyst
deactivator B is added downstream of reactor 117 via catalyst deactivator tank
118B.
The optional third ethylene interpolymer produced in reactor 117 may be formed
using
a variety operational modes, as described above; with the proviso that
catalyst
deactivator A is not added upstream of reactor 17.
In series mode, Reactor 117 produces a third exit stream 117b containing the
first
ethylene interpolymer, the second ethylene interpolymer and optionally a third
ethylene interpolymer. As shown in Figure 4, catalyst deactivator B may be
added to
1\chCA 2 98 48 38 2 019 ¨0 6 ¨257066Canada revised disclosure and claims pages
docx
the third exit stream 117b via catalyst deactivator tank 118B producing a
deactivated
solution B, stream 119; with the proviso that catalyst deactivator B is not
added if
catalyst deactivator A was added upstream of reactor 117. As discussed above,
if
catalyst deactivator A was added, deactivated solution A (stream 112e) is
equivalent
to stream 117b that exits tubular reactor 117.
In parallel mode, reactor 117 produces a fourth exit stream 117b containing
the first
ethylene interpolymer, the second ethylene interpolymer and optionally a third
ethylene interpolymer (as discussed above, in parallel mode, stream 112d is
the third
exit stream). As shown in Figure 4, in parallel mode, catalyst deactivator B
is added
to the fourth exit stream 117b via catalyst deactivator tank 118B producing a
deactivated solution B, stream 119; with the proviso that catalyst deactivator
B is not
added if catalyst deactivator A was added upstream of reactor 117.
In Figure 4, deactivated solution A (stream 112e) or B (stream 119) passes
through
pressure let down device 120 and heat exchanger 121. Optionally, if a
heterogeneous
catalyst formulation has been added, a passivator may be added via tank 122
forming
a passivated solution 123.
Deactivated solution A, deactivated solution B or passivated solution 123 pass
through pressure let down device 124 and enter a first V/L separator 125. Two
streams are formed in the first V/L separator: a first bottom stream 127
comprising a
solution that is rich in ethylene interpolymers, and; a first gaseous overhead
stream
126 rich in ethylene, solvent, optional a-olefins and optional hydrogen.
The first bottom stream enters a second V/L separator 128. In the second V/L
separator two streams are formed: a second bottom stream 130 comprising a
solution
that is richer in ethylene interpolymer and leaner in process solvent relative
to the first
bottom stream 127, and; a second gaseous overhead stream 129.
The second bottom stream 130 flows into a third V/L separator 131. In the
third V/L
separator two streams are formed: a product stream 133 comprising an ethylene
interpolymer product, deactivated catalyst residues and less than 5 weight %
of
46
\\cilcA 2984838 2019-06 ¨25066Canada revised disclosure and drums pages.docx
residual process solvent, and; a third gaseous overhead stream 132. Product
stream
133 proceeds to polymer recovery operations.
Other embodiments include the use of one or more V/L separators operating at
reduced pressure, i.e. the operating pressure is lower than atmospheric
pressure
and/or embodiments where heat is added during the devolitization process, i.e.
one or
more heat exchangers are employed upstream of, or within, one or more of the
V/L
separators. Such embodiments facilitate the removal of residual process
solvent and
comonomer such that the residual volatiles in ethylene interpolymer products
are less
than 500 ppm,
Product stream 133 proceeds 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. Other embodiments include the use of a devolatilizing extruder,
where
residual process solvent and optional a-olefin may be removed such that the
volatiles
in the ethylene interpolymer product is less than 500 ppm. Once pelletized the
solidified ethylene interpolymer product is typically transported to a product
silo.
A highly active bridged metallocene catalyst 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) per (pounds of catalyst consumed). In the case
of a
single CSTR, the quantity of the bulky ligand-metal complex, Component A,
added to
reactor 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 5A.
The upper
limit on the ppm of Component A may be 5, in some cases 3 and is other cases
2.
The lower limit on the ppm of Component A may be 0.02, in some cases 0.05 and
in
other cases 0.1. In the case of two CSTRs, the quantity of Component A added
to R1
and R2 was controlled and expressed as the parts per million (ppm) of
Component A
in R1 and R2, optionally the quantity of Component A added to R3 was
controlled and
expressed as the parts per million (ppm) of Component A in R3.
47
\\chCA 2984838 2019-06-25'066Canada revised disclosure and claims pages.docx
The proportion of Catalyst component B, the ionic activator, added to R1 was
optimized by controlling the (ionic activator)/(Component A) molar ratio,
([8]/[All, in the
R1 solution. The upper limit on the R1 ([13101) may be 10, in some cases 5 and
in
other cases 2. The lower limit on R1 ([B]/[A]) may be 0.3, in some cases 0.5
and in
other cases 1Ø The proportion of catalyst Component M was optimized by
controlling the (alumoxane)/(Component A) molar ratio, ([MHAD, 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 300, in some cases 200
and is
other cases 100. The lower limit on R1 DAMN), may be 1, in some cases 10 and
in
other cases 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]/(M]), molar ratio in R1. The upper limit
on R1
([13]/[M]) may be 1, in some cases 0.75 and in other cases 0.5. The lower
limit on R1
([13]/[M]) may be 0.0, in some cases 0.1 and in other cases 0.2.
In embodiments employing two CSTR's and two homogeneous catalyst assemblies a
second bridged metallocene catalyst formulation may be prepared independently
of
the first bridged metallocene catalyst formulation and optimized as described
above.
Optionally, a bridged metallocene catalyst formulation may be employed in the
tubular
reactor and optimized as described above.
In the continuous solution processes embodiments shown in Figures 3 and 4 a
variety
of solvents may be used as the process solvent; non-limiting examples include
linear,
branched or cyclic C5 to C12 alkanes. Non-limiting examples of a-olefins
include 1-
propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene and 1-decene.
Suitable
catalyst component solvents include aliphatic and aromatic hydrocarbons. Non-
limiting examples of aliphatic catalyst component solvents include linear,
branched or
cyclic CS-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-
48
chCA 2984838 2019-06-257066Canada revised disclosure and claims pages docx
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 are 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 reactor shown in Figure 3, or the first and second
reactors shown
in Figure 4, any combination of the feed streams may be heated or cooled: more
specifically, streams 1 ¨4 in Figure 3 and streams 101-104 and 106-109 in
Figure 4.
The upper limit on reactor feed stream temperatures may be 90 C; in other
cases
80 C and in still other cases 70 C. The lower limit on reactor feed stream
temperatures may be 20 C; in other cases 35 C and in still other cases 50 C.
Any combination of the streams feeding the tubular reactor may be heated or
cooled;
for example, streams 13 ¨ 16 in Figures 3 and 4. 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 200 C, in other cases 170 C and in still other cases
140 C; the lower temperature limit on the tubular reactor feed streams in some
cases
are 60 C, in other cases 90 C and in still other cases 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.
The operating temperature of the solution polymerization reactors, e.g.
vessels 111a
(R1) and 112a (R2)) in Figure 4 can vary over a wide range. For example, the
upper
limit on reactor temperatures in some cases may be 300 C, in other cases 280 C
and
in still other cases 260 C; and the lower limit in some cases may be 80 C, in
other
49
\\chcA 2984838 2019-06 ¨25'066Canada revised disclosure and claims pages docx
cases 100 C and in still other cases 125 C. The second reactor, reactor 112a
(R2), is
operated at a higher temperature than the first reactor 111a (R1). The maximum
temperature difference between these two reactors (1R2- TRI) in some cases is
120 C, in other cases 100 C and in still other cases 80 C; the minimum (TR2 -
TRI) in
some cases is 1 C, in other cases 5 C and in still other cases 10 C. The
optional
tubular reactor, reactor 117 (R3), may be operated in some cases 100 C higher
than
R2; in other cases 60 C higher than R2, in still other cases 10 C higher than
R2 and
in alternative cases0 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 100 C, in other
cases
60 C and in still other cases 40 C. The minimum temperature difference between
the
inlet and outlet of R3 is in some cases may be 0 C, in other cases 3 C and in
still
other cases 10 C. In some cases R3 is operated an adiabatic fashion and in
other
cases R3 is heated.
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
Figures 3
and 4, 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
45 MPag, in other cases 30 MPag and in still other cases 20 MPag; and the
lower limit
in some cases may be 3 MPag, in other some cases 5 MPag and in still other
cases 7
MPag.
Referring to the embodiments shown in Figures 3 and 4, prior to entering the
first V/L
separator, deactivated solution A, deactivated solution B or the passivated
solution
may have a maximum temperature in some cases of 300 C, in other cases 290 C
and
in still other cases 280 C; the minimum temperature may be in some cases 150
C, in
other cases 200 C and in still other cases 220 C. Immediately prior to
entering the
first V/L separator, deactivated solution A, deactivated solution B or the
passivated
solution in some cases may have a maximum pressure of 40 MPag, in other cases
25
MPag and in still cases 15 MPag; the minimum pressure in some cases may be 1.5
MPag, in other cases 5 MPag and in still other cases 6 MPag.
\\ohcA 2984838 2019-06-257066Canada revised disclosure and claims pages.docx
The first V/L separator (vessels 25 and 125 in Figures 3 and 4, respectively)
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
300 C, in other cases 285 C and in still other cases 270 C; the minimum
operating
temperature in some cases may be 100 C, in other cases 140 C and in still
other
cases 170 C. The maximum operating pressure of the first V/L separator in some
cases may be 20 MPag, in other cases 10 MPag and in still other cases 5 MPag;
the
minimum operating pressure in some cases may be 1 MPag, in other cases 2 MPag
and in still other cases 3 MPag.
The second V/L separator 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 300 C, in other cases 250 C and
in
still other cases 200 C; the minimum operating temperature in some cases may
be
100 C, in other cases 125 C and in still other cases 150 C. The maximum
operating
pressure of the second V/L separator in some cases may be 1000 kPag, in other
cases 900 kPag and in still other cases 800kPag; the minimum operating
pressure in
some cases may be 10 kPag, in other cases 20 kPag and in still other cases 30
kPag_
The third V/L separator (vessels 31 and 131 in Figures 3 and 4, respectively)
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
300 C, in other cases 250 C, and in still other cases 200 C; the minimum
operating
temperature in some cases may be 100 C, in other cases 125 C and in still
other
cases 150 C. The maximum operating pressure of the third V/L separator in some
cases may be 500 kPag, in other cases 150 kPag and in still other cases 100
kPag;
the minimum operating pressure in some cases may be 1 kPag, in other cases 10
kPag and in still other cases 25 kPag.
Embodiments of the continuous solution polymerization process shown in Figures
3
and 4 show three V/L separators. However, continuous solution polymerization
embodiments may include configurations comprising at least one V/L separator.
51
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CA 2984838 2 0 19-06-25-017066Canada revised disclosure and claims pages.docx
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 111a (R1) and reactor 112a
(R2)
in Figure 4; 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
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 is
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, is 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
52
uh(cA 2984838 2019-06-25066Canada revised disclosure and claims pages.docx
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 600 seconds, in other cases
360
seconds and in still other cases 180 seconds. The lower limit on the average
reactor
residence time of the solution in R1 in some cases may be 10 seconds, in other
cases
20 seconds and in still other cases 40 seconds. The upper limit on the average
reactor residence time of the solution in R2 in some cases may be 720 seconds,
in
other cases 480 seconds and in still other cases 240 seconds. The lower limit
on the
average reactor residence time of the solution in R2 in some cases may be 10
seconds, in other cases 30 seconds and in still other cases 60 seconds. The
upper
limit on the average reactor residence time of the solution in R3 in some
cases may
be 600 seconds, in other cases 360 seconds and in still other cases 180
seconds.
The lower limit on the average reactor residence time of the solution in R3 in
some
cases may be 1 second, in other cases 5 seconds and in still other cases 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 4. In
this
disclosure, the number of reactors is not particularly important; with the
proviso that
the continuous solution polymerization process comprises at least one reactor
that
employs at least one bridged metallocene catalyst formulation.
In operating the continuous solution polymerization process embodiments shown
in
Figure 4 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 is
referred to as
the Ethylene Split (ES), i.e. "Esrm", "ESR2" and "ESR3" refer to the weight
percent of
ethylene injected in R1, R2 and R3, respectively; with the proviso that ES R1+
ESR2+
ESR3 = 100%. This is accomplished by adjusting the ethylene flow rates in the
following streams: stream 102 (R1), stream 107 (R2) and stream 114 (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 10%, in other
cases
about 15% and in still other cases about 20%. The upper limit on ESR2 in some
cases
is about 90%, in other cases about 80% and in still other cases about 70%; the
lower
limit on ESR2 in some cases is about 20%, in other cases about 30% and in
still other
53
\\chicA 2984838 2019-06-25066Canada revised disclosure and claims pages.docx
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 4 the ethylene concentration in each reactor is also controlled. The
ethylene
concentration in reactor 1, hereafter ECRI, is defined as the weight of
ethylene in
reactor 1 divided by the total weight of everything added to reactor 1; ECR2
and ECR3
are defined similarly. Ethylene concentrations in the reactors (ECRI 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 A 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 4 the total amount of ethylene converted in each reactor is monitored.
The
term "QR1" refers to the percent of the ethylene added to R1 that is converted
into an
ethylene interpolymer by the catalyst formulation. Similarly QR2 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 QRI and QR2 in
some
cases is about 99%, in other cases about 95% and in still other cases about
90%; the
lower limit on both QRI and QR2 in some cases is about 65%, in other cases
about
70% and in still other cases about 75%. The upper limit on 0R3 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%.
54
9 8 4 8 3-8 2-01:9 -o 6 L-'7066Canada revised disclosure and claims pages.docx
Referring to Figure 4, optionally, a-olefin may be added to the continuous
solution
polymerization process. If added, a-olefin may be proportioned or split
between R1,
R2 and R3. This operational variable is referred to as the Comonomer (a-
olefin) 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 CSR1+
csR2
CSR3 = 100%. This is accomplished by adjusting a-olefin flow rates in the
following
streams: stream 103 (R1), stream 108 (R2) and stream 115 (R3). The upper limit
on
CSRI 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 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%.
In the continuous polymerization processes described in this disclosure,
polymerization is terminated by adding a catalyst deactivator. Embodiments in
Figure
3 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 C12 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
\\ca 29848313 261:9-0617066Canada revised disclosure and claims pages.docK
(e.g. U.S. Pat. No. 4,379,882 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 5
(catalyst
deactivator)/((total catalytic metal)+(alkyl aluminum co-catalyst)+(aluminurn
alkyl)) 5_
2.0; where the total catalytic metal is the total moles of catalytic metal
added to the
solution process. The upper limit on the catalyst deactivator molar ratio may
be 2, in
some cases 1.5 and in other cases 0.75. The lower limit on the catalyst
deactivator
molar ratio may be 0.3, in some cases 0.35 and in still other cases 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.
If the optional heterogeneous catalyst formulation was employed in the third
reactor,
prior to entering the first V/L separator, a passivator or acid scavenger was
added to
deactivated solution A or B to form a passivated solution, i.e. passivated
solution
stream 23 as shown in Figure 3. Optional 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
C12 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.
In this disclosure, an unbridged single site catalyst formulation was employed
in the
comparative solution process and comparative ethylene interpolymer products
were
produced. A highly active unbridged single site catalyst formulation was
produced by
optimizing the proportion of each of the four catalyst components: Component
C,
56
11ch 6-25'" '066Canada revised disclosure and claims pages.docx
CA 2984838 2019-0
Component Mc (where the superscript 'c' denotes the unbridged single site
catalyst
formulation), Component Bc and Component Pc.
In the case of one CSTR, the quantity of the bulky ligand metal complex,
Component
C, added to the first reactor (R1) was expressed as the parts per million
(ppm) of
Component C in the total mass of the solution in R1, i.e. "R1 catalyst (ppm)".
In the
case of two CSTRs, the quantity of Component C added to R1 and R2 was
controlled
and expressed as the parts per million (ppm) of Component C in R1 and R2;
optionally the quantity of Component C added to R3 was controlled and
expressed as
the parts per million (ppm) of Component C in R3. The upper limit on the ppm
of
Component C in any reactor may be 5, in some cases 3 and is other cases 2. The
lower limit on the ppm of Component C in any reactor may be 0.02, in some
cases
0.05 and in other cases 0.1.
The proportion of catalyst Component BC was optimized by controlling the
(ionic
activator)/(bulky ligand-metal complex) molar ratio, aBcMCD, in a reactor. The
upper
limit on reactor ([Bc]/[C]) may be 10, in some cases 5 and in other cases 2.
The lower
limit on reactor ([139/[C]) may be 0.3, in some cases 0.5 and in other cases
1Ø The
proportion of catalyst Component Mc was optimized by controlling the
(alumoxane)/(bulky ligand-metal complex) molar ratio, ([Mc]/[C]), in a
reactor. The
alumoxane co-catalyst was generally added in a molar excess relative to the
bulky
ligand-metal complex. The upper limit on reactor ([Mc]/[C]) molar ratio may be
1000,
in some cases 500 and is other cases 200. The lower limit on reactor ([Mc/Ed)
molar
ratio may be 1, in some cases 10 and in other cases 30. The addition of
catalyst
Component Pc is optional. If added, the proportion of Component Pc was
optimized
by controlling the (hindered phenol)/(alumoxane) molar ratio, ([Pc]I[Mc]), in
any
reactor. The upper limit on reactor ([Pc]/[Mc]) molar ratio may be 1.0, in
some cases
0.75 and in other cases 0.5. The lower limit on reactor ([Pc]/[Mc]) molar
ratio may be
0.0, in some cases 0.1 and in other cases 0.2.
Interpolymers
The first ethylene interpolymer was synthesized by a bridged metallocene
catalyst
formulation. Referring to the embodiment shown in Figure 3, if the optional a-
olefin is
57
\\eh 2984838 9-06-25
-066Canada revised disclosure and claims pages.docx
CA 201
not added to reactor lie (R1), then the first ethylene interpolymer is an
ethylene
homopolymer. If an a-olefin is added, the following weight ratio is 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. Hereafter, the symbol
"al" refers
to the density of the first ethylene interpolymer produced in R1, i.e. reactor
11a in
Figure 3 or reactor 111a in Figure 4. The upper limit on al may be 0.975 g/cc;
in
some cases 0.965 Wm and; in other cases 0.955 g/cc. The lower limit on al may
be
0.855 g/cc, in some cases 0.865 g/cc, and; in other cases 0.875 g/cc. Density
decreases as the content of one or more a-olefins in the first ethylene
interpolymer
increases. The cc-olefin content was expressed as the mole percent of a-olefin
in the
first ethylene interpolymer. The upper limit on the mole percent of a-
olefin(s) in the
first ethylene interpolymer may be 25%; in some cases 23% and in other cases
20%.
The lower limit on the mole percent of a-olefin in the first ethylene
interpolymer was
0%, i.e. no a-olefin was added to the solution polymerization process and the
first
ethylene interpolymer was an ethylene homopolymer.
Methods to determine the CDBI50 (Composition Distribution Branching Index) of
an
ethylene interpolymer are well known to those skilled in the art. The CDBI5o,
expressed as a percent, was defined as the percent of the ethylene
interpolymer
whose comonomer (a-olefin) 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 98%, in other cases 95% and in still other cases
90%.
The lower limit on the CDB150 of the first ethylene interpolymer may be 70%,
in other
cases 75% and in still other cases 80%.
The upper limit on the Mw/Mn of the first ethylene interpolymer may be 2.4, in
other
cases 2.3 and in still other cases 2.2. The lower limit on the Mw/Mn the first
ethylene
interpolymer may be 1.7, in other cases 1.8 and in still other cases 1.9.
58
Vr-'= "- --'e -`"17066Canada revised disclosure and claims pages.docx
CA 2984838 2019-06-25
The first ethylene interpolymer contains long chain branching as characterized
by the
dimensionless LCBF parameter discussed above. The upper limit on the LCBF of
the
first ethylene interpolymer may be 0.5, in other cases 0.4 and in still other
cases 0.3
(dimensionless). The lower limit on the LCBF of the first ethylene
interpolymer may
be 0.001, in other cases 0.0015 and in still other cases 0.002
(dimensionless).
The first ethylene interpolymer has an Unsaturation Ratio, UR, defined by
Eq.(UR)
discussed above. The upper limit on the UR of the first ethylene interpolymer
may be
0.06, in other cases 0.04 and in still other cases 0.02 (dimensionless). The
lower limit
on the UR of the first ethylene interpolymer may be -0.40, in other cases -
0.30 and in
still other cases -0.20 (dimensionless).
The first ethylene interpolymer contained 'a residual catalytic metal' that
reflected the
chemical composition of the bridged metallocene catalyst formulation injected
into the
first reactor. Residual catalytic metal was quantified by Neutron Activation
Analysis
(NAA), i.e. the parts per million (ppm) of catalytic metal in the first
ethylene
interpolymer, where the catalytic metal originated from the metal in Component
A
(Formula (I)); this metal will be referred to as "metal AR1". Non-limiting
examples of
metal AR1 include Group 4 metals, titanium, zirconium and hafnium. In the case
of an
ethylene interpolymer product that contains one interpolymer, i.e. the first
ethylene
interpolymer, the residual catalytic metal is equal to the ppm metal AR1 in
the ethylene
interpolymer product. The upper limit on the ppm of metal AR1 in the first
ethylene
interpolymer may be 5.0 ppm, in other cases 4.0 ppm and in still other cases
3.0 ppm.
The lower limit on the ppm of metal AR1 in the first ethylene interpolymer may
be 0.03
ppm, in other cases 0.09 ppm and in still other cases 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 in melt
index, hereafter 121 (melt index is measured at 190 C using a 2.16 kg load
following
the procedures outlined in ASTM D1238). This is accomplished by adjusting the
hydrogen flow rate in stream 4 (Figure 3). The quantity of hydrogen added to
reactor
11a (R1) is expressed as the parts-per-million (ppm) of hydrogen in R1
relative to the
total mass in reactor RI; hereinafter H2R1 (ppm). In some cases H2R1 (ppm)
ranges
from 100 ppm to 0 ppm, in other cases from 50 ppm to 0 ppm, in alternative
cases
59
\\cCA 2984838 2019-06-25 7066Canada revised disclosure and claims pages.docx
from 20 to 0 and in still other cases from 2 ppm to 0 ppm. The upper limit on
121 may
be 200 dg/min, in some cases 100 dg/min; in other cases 50 dg/min, and; in
still other
cases 1 dg/min. The lower limit on 121 may be 0.01 dg/min, in some cases 0.05
dg/min; in other cases 0.1 dg/min, and; in still other cases 0.5 dg/min.
The upper limit on the weight percent (wt%) of the first ethylene interpolymer
in the
ethylene interpolymer product may be 100 wt%, in some cases 60 wt%, in other
cases
55 wt% and in still other cases 50 wt%. The lower limit on the wt % of the
first
ethylene interpolymer in the ethylene interpolymer product may be 5 wt%; in
other
cases 8 wt% and in still other cases 10 wt%.
The second ethylene interpolymer, may, or may not, be present. Figure 3
illustrates
an embodiment where the second ethylene interpolymer is not present, i.e.
where one
CSTR was used and stream 11 c was deactivated (via deactivator tank 18A).
Turning
to Figure 4, a second ethylene interpolymer was synthesized by injecting a
bridged
metallocene catalyst formulation into the second solution polymerization
reactor 112a
(or R2). If optional a-olefin is not added to reactor 112a (R2) either through
fresh a-
olefin stream 108 or carried over from reactor 111a (R1) in stream 111e
(series
mode), then the second ethylene interpolymer was an ethylene homopolymer. If
of, -
olefin was present in R2, the following weight ratio was one parameter to
control the
density of the second ethylene interpolymer: ((a-olefin)/(ethylene))R2. The
upper limit
on ((a-olefin)/(ethylene))R2 may be 3; in other cases 2 and in still other
cases 1. The
lower limit on ((a-olefin)/(ethylene))R2 may be 0; in other cases 0.25 and in
still other
cases 0.5. Hereafter, the symbol "o-2" refers to the density of the second
ethylene
interpolymer. The upper limit on cr2 may be 0.975 g/cc; in some cases 0.965
g/cc and;
in other cases 0.955 g/cc. The lower limit on cr2 may be 0.855 g/cc, in some
cases
0.865 g/cc, and; in other cases 0.875 g/cc. The upper limit on the mole
percent of one
or more a-olefins in the second ethylene interpolymer may be 25%; in some
cases
23% and in other cases 20%. The lower limit on the mole percent of a-olefin in
the
second ethylene interpolymer was 0%, i.e. no a-olefin was added to the
solution
polymerization process and the second ethylene interpolymer was an ethylene
homopolymer.
\cb.ik. 2984838 2019-06-2517066Canada revised disclosure and claims pages docx
The upper limit on the C0B150 of the second ethylene interpolymer may be 98%,
in
other cases 95% and in still other cases 90%. The lower limit on the CDBI50 of
the
second ethylene interpolymer may be 70%, in other cases 75% and in still other
cases
80%.
The upper limit on the Mw/Mn of the second ethylene interpolymer may be 2.4,
in other
cases 2.3 and in still other cases 2.2. The lower limit on the Mw/Mn the
second
ethylene interpolymer may be 1.7, in other cases 1.8 and in still other cases
1.9.
The second ethylene interpolymer contains long chain branching as
characterized by
the dimensionless LCBF parameter. The upper limit on the LCBF of the second
ethylene interpolymer may be 0.5, in other cases 0.4 and in still other cases
0.3
(dimensionless). The lower limit on the LCBF of the second ethylene
interpolymer
may be 0.001, in other cases 0.0015 and in still other cases 0.002
(dimensionless).
The second ethylene interpolymer has an Unsaturation Ratio, UR, defined by Eq.
(UR). The upper limit on the UR of the second ethylene interpolymer may be
0.06, in
other cases 0.04 and in still other cases 0.02 (dimensionless). The lower
limit on the
UR of the second ethylene interpolymer may be -0.40, in other cases -0.30 and
in still
other cases -0.20 (dimensionless).
The catalyst residue in the second ethylene interpolymer reflects the amount
of the
bridged metallocene catalyst formulation employed in R2 or the amount of
Component
A employed in R2. The species of Component A (Formula (I)) containing 'metal
AR2'
employed in second reactor may differ from the species of Component A employed
in
the first reactor. In the case of a pure sample of the second ethylene
interpolymer, the
upper limit on the ppm of metal AR2 in the second ethylene interpolymer may be
5.0
ppm, in other cases 4.0 ppm and in still other cases 3.0 ppm; while the lower
limit on
the ppm of metal AR2 in the second ethylene interpolymer may be 0.03 ppm, in
other
cases 0.09 ppm and in still other cases 0.15 ppm.
Referring to the embodiments shown in Figure 4, the amount of hydrogen added
to R2
can vary over a wide range which allows the continuous solution polymerization
process to produce second ethylene interpolymers that differ in melt index,
hereinafter
61
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122. This is accomplished by adjusting the hydrogen flow rate in stream 109.
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 100 ppm to 0 ppm, in some cases from 50 ppm to 0 ppm,
in
other cases from 20 to 0 and in still other cases from 2 ppm to 0 ppm. The
upper limit
on 122 may be 1000 dg/min; in some cases 750 dg/min; in other cases 500
dg/min,
and; in still other cases 200 dg/min. The lower limit on 122 may be 0.3
dg/min, in some
cases 0.4 dg/min, in other cases 0.5 dg/min, and; in still other cases 0.6
dg/min.
The upper limit on the weight percent (wt%) of the second ethylene
interpolymer in the
ethylene interpolymer product may be 95 wt%, in other cases 92 wt% and in
still other
cases 90 wt%. The lower limit on the wt % of the second ethylene interpolymer
in the
ethylene interpolymer product may be 0 wt%, in some cases 20 wt%, in other
cases
30 wt% and in still other cases 40 wt%.
Optionally, embodiments of ethylene interpolymer products contained a third
ethylene
interpolymer. Referring to Figure 3, a third ethylene interpolymer was
produced in
reactor 17 (R3) if catalyst deactivator A was not added upstream of reactor
17.
Referring to Figure 4, a third ethylene interpolymer was produced in reactor
117 if
catalyst deactivator was not added upstream of reactor 117. If a-olefin was
not
added, the third ethylene interpolymer was an ethylene homopolymer. If 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 3; in other cases 2 and in still other cases
1. The
lower limit on ((a-olefin)/(ethylene))R3 may be 0; in other cases 0.25 and in
still other
cases 0.5. Hereinafter, the symbol "cs3" refers to the density of the third
ethylene
interpolymer. The upper limit on cy3 may be 0.975 g/cc; in some cases 0.965
g/cc and;
in other cases 0.955 g/cc. The lower limit on cr3 may be 0.855 g/cc, in some
cases
0.865 g/cc, and; in other cases 0.875 g/cc. The upper limit on the mole
percent of one
or more a-olefins in the third ethylene interpolymer may be 25%; in some cases
23%
and in other cases 20%. The lower limit on the mole percent of a-olefin in the
third
ethylene interpolymer was 0%, i.e. no a-olefin was added to the solution
polymerization process and the third ethylene interpolymer was an ethylene
homopolymer.
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One or more of the following homogeneous catalyst formulations may be injected
into
R3: the bridged metallocene catalyst formulation, the unbridged single site
catalyst
formulation or a homogeneous catalyst formulation that contains a bulky ligand-
metal
complex that is not a member of the genera defined by Formula (I) or Formula
(II).
Figures 3 and 4 illustrates the injection of a homogeneous catalyst
formulation into
reactor 17 or 117, respectively, through stream 40 or 140, respectively. This
disclosure includes embodiments where a heterogeneous catalyst formulation was
injected into the third reactor (R3). Figure 3 illustrates a non-limiting
example were a
heterogeneous catalyst assembly (streams 34a ¨ 34e and 34h) was employed to
produce and inject an on-line Ziegler-Natta catalyst formulation into reactor
17.
Similarly, Figure 4 illustrates a non-limiting example were a heterogeneous
catalyst
assembly (streams 134a ¨ 134e and 134h) was employed to produce and inject an
on-line Ziegler-Natta catalyst formulation into reactor 117.
The upper limit on the CDBI50 of the third ethylene interpolymer may be 98%,
in other
cases 95% and in still other cases 90%. The lower limit on the CDB150 of the
optional
third ethylene interpolymer may be 35%, in other cases 40% and in still other
cases
45%.
The upper limit on the Mw/Mn of the third ethylene interpolymer may be 5.0, in
other
cases 4.8 and in still other cases 4.5. The lower limit on the Mw/Mn of the
optional
third ethylene interpolymer may be 1.7, in other cases 1.8 and in still other
cases 1.9.
If the bridged metallocene catalyst formulation was employed in the third
reactor the
third ethylene interpolymer contained long chain branching as characterized by
the
dimensionless LCBF parameter discussed above. The upper limit on the LCBF of
the
third ethylene interpolymer may be 0.5, in other cases 0.4 and in still other
cases 0.3
(dimensionless). The lower limit on the LOBE of the third ethylene
interpolymer may
be 0.001, in other cases 0.0015 and in still other cases 0.002
(dimensionless). If the
unbridged single site catalyst formulation was employed in the third reactor
the third
ethylene interpolymer contained an undetectable amount of long chain
branching, i.e.
the third ethylene interpolymer had a dimensionless LCBF value of less than
0.001. If
a heterogeneous catalyst formulation was employed in the third reactor the
third
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CA 2984838 2019-06-25
ethylene interpolymer contained an undetectable amount of long chain
branching. If a
homogeneous catalyst formulation containing a bulky ligand-metal complex that
is not
a member of the genera defined by Formula (I) or Formula (II) was employed in
R3,
the third ethylene interpolymer may, or may not, contain LOB.
If the third ethylene interpolymer was synthesized by the bridged metallocene
catalyst
formulation, the third ethylene interpolymer was characterized by an
Unsaturation
Ratio, UR; where the upper limit on UR was 0.06, in other cases 0.04 and in
still other
cases 0.02 (dimensionless) and the lower limit on UR was -0.40, in other cases
-0.30
and in still other cases -0.20 (dimensionless). If the third ethylene
interpolymer was
synthesized by the unbridged single site catalyst formulation, the third
ethylene
interpolymer was characterized by an Unsaturation Ratio, UR; where the upper
limit
on UR was -0.1, in other cases -0.2 and in still other cases -0.3 and the
lower limit on
UR was -0.8, in other cases -0.65 and in still other cases -0.5. If the third
ethylene
interpolymer was synthesized by a Ziegler-Natta catalyst formulation, the
third
ethylene interpolymer was characterized by the an Unsaturation Ratio, UR;
where the
upper limit on UR was -0.7, in other cases -0.75 and in still other cases -0.8
and the
lower limit on UR was -1.0, in other cases -0.95 and in still other cases -
0.9.
The catalyst residue in the third ethylene interpolymer reflected the catalyst
employed
in its manufacture. If the bridged metallocene catalyst formulation was used,
the
species of Component A (Formula (I)) containing 'metal AR3' employed in the
third
reactor may differ from the species employed in R1, or R1 and R2. In other
words,
the catalytic metal employed in R3 may differ from the catalytic metal
employed in R1
and/or R2. In the case of a pure sample of the third ethylene interpolymer,
the upper
limit on the ppm of metal AR3 in the third ethylene interpolymer may be 5.0
ppm, in
other cases 4.0 ppm and in still other cases 3.0 ppm; while the lower limit on
the ppm
of metal AR3 in the third ethylene interpolymer may be 0.03 ppm, in other
cases 0.09
ppm and in still other cases 0.15 ppm.
The third ethylene interpolymer may be synthesized using an unbridged single
site
catalyst formulation comprising Component C and a catalytic 'metal 0R3". Non-
limiting
examples of metal 0R3 include the Group 4 metals titanium, zirconium and
hafnium.
In the case of a pure sample of the third ethylene interpolymer, the upper
limit on the
64
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C
ppm of metal CR3 in the third ethylene interpolymer may be 3.0 ppm, in other
cases
2.0 ppm and in still other cases 1.5 ppm. The lower limit on the ppm of metal
CR3 in
the third ethylene interpolymer may be 0.03 ppm, in other cases 0.09 ppm and
in still
other cases 0.15 ppm.
The third ethylene interpolymer may be synthesized using a homogeneous
catalyst
formulation that contains a bulky ligand-metal complex, containing metal
'BR3', that is
not a member of the genera defined by Formula (I) or Formula (II). Non-
limiting
examples of metal BR3 include the Group 4 metals titanium, zirconium and
hafnium. In
the case of a pure sample of the third ethylene interpolymer, the upper limit
on the
ppm of metal BR3 in the third ethylene interpolymer may be 5.0 ppm, in other
cases
4.0 ppm and in still other cases 3.0 ppm. The lower limit on the ppm of metal
BR3 in
the third ethylene interpolymer may be 0.03 ppm, in other cases 0.09 ppm and
in still
other cases 0.15 ppm.
The third ethylene interpolymer may be synthesized using a heterogeneous
catalyst
formulation. A non-limiting example of a heterogeneous catalyst formulation is
an in-
line Ziegler-Natta catalyst formulation; Figures 3 and 4 illustrate the
injection of in-line
Ziegler-Natta catalyst formulations into tubular reactor 17 or 117,
respectively, through
streams 34e or 134e, respectively. The in-line Ziegler-Natta catalyst
formulation
comprises a metal compound (component (vii)) and the term 'metal ZR3' refers
to the
metal in this compound. Non-limiting examples of metal ZR3 include metals
selected
from Group 4 through Group 8 of the Periodic Table. In the case of a pure
sample of
the third ethylene interpolymer, the upper limit on the ppm of metal ZR3 in
the third
ethylene interpolymer may be 12 ppm, in other cases 10 ppm and in still other
cases
8 ppm; while the lower limit on the ppm of metal ZR3 in the third ethylene
interpolymer
may be 0.5 ppm, in other cases 1 ppm and in still other cases 3 ppm.
Referring to the embodiments shown in Figures 3 and 4, optional hydrogen may
be
injected into the tubular reactor 17 or 117, respectively, through stream 16
or stream
116, respectively. 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 third ethylene interpolymers that differ widely in
melt
index, hereinafter 123. The amount of optional hydrogen added to R3 ranges
from 100
\\clicA 2984838 2019-06 ¨257066Canada revised disclosure and claims pages.docx
ppm to 0 ppm, in some cases from 50 ppm to 0 ppm, in other cases from 20 to 0
and
in still other cases from 2 ppm to 0 ppm. The upper limit on l23 may be 2000
dg/min;
in some cases 1500 dg/min; in other cases 1000 dg/min, and; in still other
cases 500
dg/min. The lower limit on l23 may be 0.4 dg/min, in some cases 0.6 dg/min, in
other
cases 0.8 dg/min, and; in still other cases 1.0 dg/min.
The upper limit on the weight percent (wt%) of the optional third ethylene
interpolymer
in the ethylene interpolymer product may be 30 wt%, in other cases 25 wt% and
in still
other cases 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
5 wt%
and in still other cases 10 wt%.
Embodiments of the ethylene interpolymer product may comprise: (i) the first
ethylene
interpolymer; (ii) the first ethylene interpolymer and the third ethylene
interpolymer; (iii)
the first ethylene interpolymer and the second ethylene interpolymer, or; (iv)
the first
ethylene interpolymer, the second ethylene interpolymer and the third ethylene
interpolymer.
The upper limit on the density of the ethylene interpolymer product (pf) may
be 0.975
g/cc; in some cases 0.965 g/cc and; in other cases 0.955 g/cc. The lower limit
on the
density of the ethylene interpolymer product may be 0.855 g/cc, in some cases
0.865
g/cc, and; in other cases 0.875 g/cc. The upper limit on the mole percent of
one or
more a-olefins in the ethylene interpolymer product may be 25%; in some cases
23%
and in other cases 20%. The lower limit on the mole percent of a-olefin in the
ethylene interpolymer product was 0%, i.e. no a-olefin was added to the
solution
polymerization process and the ethylene interpolymer product was an ethylene
homopolymer.
The upper limit on the CDB150 of the ethylene interpolymer product may be 98%,
in
other cases 90% and in still other cases 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 1%, in other cases 2% and in still other cases 3%.
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The upper limit on the Mw/Mn of the ethylene interpolymer product depends on
the
number of reactors employed and polymerizations conditions. For example,
referring
to Figure 3, if stream 11c is deactivated upstream of tubular reactor 17 the
upper limit
on the Mw/Mn of the ethylene interpolymer product may be 2.4, in other cases
2.3 and
in still other cases 2.2; while the lower limit on the Mw/Mn of this ethylene
interpolymer
product may be1.7, in other cases 1.8 and in still other cases 1.9. Referring
to multi-
reactor Figure 4, the upper limit on the Mw/Mn of an ethylene interpolymer
product
(comprising a first, second and optionally a third ethylene interpolymer) may
be 25, in
other cases 20 and in still other cases 15; while the lower limit on the Mw/Mn
of this
ethylene interpolymer product may be 1.8, in other cases 1.9 and in still
other cases
2Ø
The ethylene interpolymer product contains long chain branching (LCB) and LCB
was
characterized by the dimensionless LCBF parameter discussed above. The upper
limit on the LCBF of the third ethylene interpolymer may be 0.5, in other
cases 0.4 and
in still other cases 0.3 (dimensionless). The lower limit on the LCBF of the
third
ethylene interpolymer may be 0.001, in other cases 0.0015 and in still other
cases
0.002 (dimensionless).
If the ethylene interpolymer product was synthesized using one or more bridged
metallocene catalyst formulations, the ethylene interpolymer product was
characterized by an Unsaturation Ratio, UR; where the upper limit on UR was
0.06, in
other cases 0.04 and in still other cases 0.02 (dimensionless) and the lower
limit on
UR was -0.40, in other cases -0.30 and in still other cases -0.20
(dimensionless). If
the ethylene interpolymer product contained a portion of a third ethylene
interpolymer
synthesized using an unbridged single site catalyst formulation, the ethylene
interpolymer product was characterized by an Unsaturation Ratio, UR; where the
upper limit on UR was 0.06, in other cases 0.04 and in still other cases 0.02
and the
lower limit on UR was -0.8, in other cases -0.65 and in still other cases -
0.5. If the
ethylene interpolymer product contained a portion of a third ethylene
interpolymer
synthesized using a Ziegler-Natta catalyst formulation, the ethylene
interpolymer
product was characterized by the an Unsaturation Ratio, UR; where the upper
limit on
UR was 0.06, in other cases 0.04 and in still other cases 0.02 and the lower
limit on
UR was -1.0, in other cases -0.95 and in still other cases -0.9.
67
etcA 2984838 2019-06-257066Canada revised disclosure and claims pages docx
Table 4 discloses the 'residual catalytic metal' in ethylene interpolymer
product
Examples 1-6 as determined by Neutron Activation Analysis (NAA). In Examples
1, 2
and 4-6 the same bridged metallocene catalyst formulation was injected into
reactors
111a and 112a (Figure 4) and the residual catalytic metals in these samples
varied
from 1.38 to 1.98 ppm Hf. In Example 3 one CSTR was employed and the bridged
metallocene catalyst formulation was injected into reactor 11a (Figure 3),
Example 3
had a residual catalytic metal of 2.20 ppm Hf. In Examples 1-6 the quantity of
titanium
was below the N.A.A. detection limit. Comparatives Q1-Q4 were manufactured
using
a Hf-based catalyst formulation and contained from 0.24-0.34 ppm Hf and
undetectable Ti. Comparative 2 and Comparative 3 were manufactured using a Hf-
based and a Ti-based catalyst formulation. The remaining comparatives in Table
4
were produced with various Ti-based catalyst formulations, i.e. Comparatives
R, S, U,
V, 1,4 and 5 where the Ti content ranged from 0.14 to 7.14 ppm Ti.
In embodiments where the same species of Component A was employed in one or
more reactors, the upper limit on the residual catalytic metal in the ethylene
interpolymer product may be 5.0 ppm, in other cases 4.0 ppm and in still other
cases
3.0 ppm, and; the lower limit on the residual 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.
In embodiments where two or more reactors were operating and different species
of
Component A (having different metals) were employed in each reactor, the upper
limit
on the ppm of metal AR1 in the ethylene interpolymer product may be 3.0 ppm,
in other
cases 2.5 ppm and in still other cases 2.0 ppm; while the lower limit on the
ppm of
metal AR1 in the ethylene interpolymer product may be 0.0015 ppm, in other
cases
0.005 ppm and in still other cases 0.01 ppm.
In embodiments where the ethylene interpolymer product contained two
interpolymers
and different species of Component A (having different metals) were employed
in R1
(vessel 111a Figure 4) and R2 (vessel 112a Figure 4), the upper limit on the
ppm of
metal AR2 in the ethylene interpolymer product may be 5.0 ppm, in other cases
4.0
ppm and in still other cases 3.0 ppm; while the lower limit on the ppm of
metal AR2 in
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CA 2984838 2019-06-25
the ethylene interpolymer product may be 0.0012 ppm, in other cases 0.04 ppm
and in
still other cases 0.06 ppm.
In embodiments where the ethylene interpolymer product contains a third
ethylene
interpolymer and different species of Component A (having different metals)
were
employed in R1, R2 and R3 (vessel 117 Figure 4) the upper limit on the ppm of
metal
AR2 in the ethylene interpolymer product may be 3.5 ppm, in other cases 2.5
ppm and
in still other cases 2.0 ppm, and; the lower limit on the ppm of metal AR2 in
the
ethylene interpolymer product may be 0.003 ppm, in other cases 0.01 ppm and in
still
other cases 0.015 ppm.
In embodiments where the ethylene interpolymer product contained a third
ethylene
interpolymer and different species of Component A (having different metals)
were
employed in R1, R2 and R3 the upper limit on the ppm of metal AR3 in the
ethylene
interpolymer product may be 1.5 ppm, in other cases 1.25 ppm and in still
other cases
1.0 ppm. In embodiments where an unbridged single site catalyst formulation,
comprising metal CR3, was injected into the tubular reactor the upper limit on
the ppm
of metal 0R3 in the ethylene interpolymer product may be 1.0 ppm, in other
cases 0.8
ppm and in still other cases 0.5 ppm. In embodiments were a homogeneous
catalyst
formulation, comprising metal BR3, was injected into the tubular reactor the
upper limit
on the ppm of metal BR3 in the ethylene interpolymer product may be 1.5 ppm,
in other
cases 1.25 ppm and in still other cases 1.0 ppm. In embodiments were a
heterogeneous catalyst formulation, comprising metal ZR3, was injected into
the
tubular reactor the upper limit on the ppm of metal ZR3 in the ethylene
interpolymer
product may be 3.5 ppm, in other cases 3 ppm and in still other cases 2.5 ppm.
The
lower limit on the ppm of metal AR3, CR3, BR3 or ZR3 in the ethylene
interpolymer
product was 0.0, i.e. a catalyst deactivator was added upstream of the tubular
reactor
(R3).
The upper limit on melt index of the ethylene interpolymer product may be 500
dg/min,
in some cases 400 dg/min; in other cases 300 dg/min, and; in still other cases
200
dg/min. The lower limit on the melt index of the ethylene interpolymer product
may be
0.3 dg/min, in some cases 0.4 dg/min; in other cases 0.5 dg/min, and; in still
other
cases 0.6 dg/min.
69
CA 2984838 2019-06-25ns62017066Canada revised disclosure and claims pages docx
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 (M DO) 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
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
\\cleA 2984838 2019-06 ¨257066Canada revised disclosure and claims pages docx
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 thermoplastic 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
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 0.5
mil (13
pm) to 4 mil (102 pm), and; in heavy duty sack applications film thickness may
range
from 2 mil (51pm) to 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
3
wt%, in other cases 10 wt% and in still other cases 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 90 wt% and in still other cases 70 wt%.
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CA 2984838 2019-06-25
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 5%, in other cases 15% and in still other cases 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
95%, in
other cases 80% and in still other cases 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
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,
72
7066Canada revised disclosure and claims pages docx
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, overwrap
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,
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:
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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 ethylene interpolymer products disclosed herein have improved bubble
stability,
e.g. relative to the Comparative 1 products disclosed herein. Improved bubble
stability allows one to produce mono or multilayer films at higher production
rates.
Melt strength, measured in centi-Newtons (cN), is frequently used as a measure
of
bubble stability; i.e. the higher the melt strength the higher the bubble
stability. As
shown in Table the Example 1 (4.56 cN) and Example 2 (3.2 cN) have higher melt
strengths relative to Comparative 15 (2.78 cN) and Comparative 16 (3.03). In
other
words, the ethylene interpolymer products disclosed herein have an improved
melt
strength of from 65% to 25%, relative to comparatives.
The films used in the 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, 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.
The processes disclosed herein are also capable of making ethylene
interpolymer
products that have a useful combination of desirable physical properties for
use in
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CA 2984838 2019-06-25
rigid applications or rigid 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 vessels, 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
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
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CA 2984838 2019-06-25
absorbers, lubricants, pigments, plasticizers, nucleating agents and
combinations
thereof.
Additional Embodiments
The following paragraphs disclose additional embodiments of this invention.
An ethylene interpolymer product comprising: (i) a first ethylene
interpolymer; (ii) a
second ethylene interpolymer, and; (iii) optionally a third ethylene
interpolymer;
wherein said ethylene interpolymer product has: a) a dimensionless Long Chain
Branching Factor, LCBF, greater than or equal to 0.001; b) a residual
catalytic metal
of from ?_ 0.03 to 5 ppm of hafnium; c) a dimensionless unsaturation ratio,
UR, of
from ?_ -0.40 to 5. 0.06, wherein UR is defined by the relationship; UR = (SCu-
Tu)/Tu;
wherein, SCu is the amount of a side chain unsaturation per 100 carbons and Tu
is
amount of a terminal unsaturation per 100 carbons, in said ethylene
interpolymer
product. Other embodiments of the ethylene interpolymer products described in
this
paragraph may have a melt index from about 0.3 to about 500 dg/minute, a
density
from about 0.855 to about 0.975 g/cc, a Mw/Mn from about 1.7 to about 25 and a
CDBI50 from about 1% to about 98%. Other embodiments of the ethylene
interpolymer products described in this paragraph may contain: from 5 to 60
weight
percent of the first ethylene interpolymer having a melt index from 0.01 to
200 dg/min
and a density of 0.855 g/cc to 0.975 g/cc; from 20 to 95 weight percent of the
second
ethylene interpolymer having a melt index from 0.3 to 1000 dg/min and a
density of
0.855 g/cc to 0.975 g/cc, and; optionally from 0 to 30 weight percent of the
third
ethylene interpolymer having a melt index from 0.5 to 2000 dg/min and a
density of
0.855 g/cc to 0.975 g/cc; where weight percent is the weight of said first,
said second
or said optional third ethylene interpolymer, individually, divided by the
weight of said
ethylene interpolymer product. Other embodiments of the ethylene interpolymer
products described in this paragraph may contain from 0 to about 25 mole
percent of
one or more a-olefin; non-limiting examples of a-olefins include C3 to Cio a-
olefins.
Other embodiments of the ethylene interpolymer products may be manufactured in
a
solution polymerization process. The first and second ethylene interpolymers,
in the
ethylene interpolymer products of this paragraph, may be synthesized using a
bridged
metallocene catalyst formulation that comprises a Component A defined by
Formula
(I)
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R1
1O(2 X (R6)
R4
M¨X(R6)
,G
R57 R3
(I)
R2
wherein M is a metal selected from titanium, hafnium and zirconium; G is the
element
carbon, silicon, germanium, tin or lead; X represents a halogen atom, 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, C1-10 alkyl radicals,
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 C1-20 hydrocarbyl radical, a C1-
20
alkoxy radical or a C6-10 aryl oxide radical, and; R4 and R5 are independently
selected
from a hydrogen atom, a C1-20 hydrocarbyl radial, a C1-20 alkoxy radical or a
C6-10 aryl
oxide radical. The bridged metallocene catalyst formulation may further
comprise: a
component M, comprising an alumoxane co-catalyst; a component B, comprising a
boron ionic activator, and; optionally, a component P, comprising a hindered
phenol.
The optional third ethylene interpolymer may be synthesized using a
homogeneous
catalyst formulation or a heterogeneous catalyst formulation; non-limiting
examples of
homogeneous catalyst formulations include bridged metallocene catalyst
formulations
or unbridged single site catalyst formulations; non-limiting examples of
heterogeneous
catalyst formulations include in-line Ziegler-Natta catalyst formulations or
batch
Ziegler-Natta catalyst formulations. Optionally a heterogeneous catalyst
formulation
comprising metal ZR3 may be injected into the tubular reactor, in this case
embodiments of ethylene interpolymer products may contain from 0.1 to 3.5 ppm
of
metal ZR3.
Other embodiments include: a continuous solution polymerization process
comprising:
i) injecting ethylene, a process solvent, a bridged metallocene catalyst
formulation,
optionally one or more a-olefins and optionally hydrogen into a first reactor
to produce
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a first exit stream containing a first ethylene interpolymer in said process
solvent; ii)
passing said first exit stream into a second reactor and injecting into said
second
reactor, ethylene, said process solvent, said bridged metallocene catalyst
formulation,
optionally one or more a-olefins and optionally hydrogen to produce a second
exit
stream containing a second ethylene interpolymer and said first ethylene
interpolymer
in said process solvent; iii) passing said second exit stream into a third
reactor and
optionally injecting into said third reactor, ethylene, process solvent, one
or more a-
olefins, hydrogen and a homogeneous catalyst formulation or a heterogeneous
catalyst formulation to produce a third exit stream containing an third
ethylene
interpolymer, said second ethylene interpolymer and said first ethylene
interpolymer in
said process solvent; iv) phase separating said third exit stream to recover
an
ethylene interpolymer product comprising said first ethylene interpolymer,
said second
ethylene interpolymer and said optional third ethylene interpolymer; where
said
continuous solution polymerization process is improved by having (a) and/or
(b):
(a) at least a 70% reduced [a-olefin/ethylene] weight ratio as defined by the
following
formula
(a ¨ olefin)11 (a ¨ olefin\c
% Reduced ________________
[a¨ ole f in] = ethylene) __ ethylene)
100 x < ¨70%
I. ethylene (a ¨ olefin )C
ethylene
wherein (a-olefin/ethylene)' is calculated by dividing the weight of said a-
olefin added
to said first reactor by the weight of said ethylene added to said first
reactor, wherein
said first ethylene interpolymer having a target density is produced by said
bridged
metallocene catalyst formulation, and; (a-olefin/ethylene)c is calculated by
dividing the
weight of said a-olefin added to said first reactor by the weight of said
ethylene added
to said first reactor, wherein a control ethylene interpolymer having said
target density
is produced by replacing said bridged metallocene catalyst formulation with an
unbridged single site catalyst formulation;
(b) at least a 5% improved weight average molecular weight as defined by the
following formula
% Improved Mw = 100% x (MwA-Mwc)/Mwc 10%
wherein MwA is a weight average molecular weight of said first ethylene
interpolymer
and MAP is a weight average molecular weight of a comparative ethylene
interpolymer;
wherein said comparative ethylene interpolymer is produced in said first
reactor by
replacing said bridged metallocene catalyst formulation with said unbridged
single site
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CA 2984838 2019-06-25
catalyst formulation. Additional steps of this process may comprise: a)
optionally
adding a catalyst deactivator A to said second exit stream, downstream of said
second reactor, forming a deactivated solution A; b) adding a catalyst
deactivator B to
said third exit stream, downstream of said third reactor, forming a
deactivated solution
B; with the proviso that step b) is skipped if said catalyst deactivator A is
added in step
a); c) phase separating said deactivated solution A or B to recover said
ethylene
interpolymer product. If a heterogeneous catalyst formulation was added to the
third
reactor, additional process steps may comprise: d) adding a passivator to said
deactivated solution A or B forming a passivated solution, with the proviso
that step d)
is skipped if said heterogeneous catalyst formulation is not added to said
third reactor,
and; e) phase separating said deactivated solution A or B, or said passivated
solution,
to recover said ethylene interpolymer product. The bridged metallocene
catalyst
formulation may comprise: a bulky ligand-metal complex 'Component A'; a
component
M, comprising an alumoxane co-catalyst; a component B, comprising a boron
ionic
activator, and; optionally, a component P, comprising a hindered phenol;
wherein the
following mole ratios may be employed: a molar ratio of said component B to
said
component A from about 0.3 : 1 to about 10 : 1; a molar ratio of said
component M to
said component A from about 1 : 1 to about 300 : 1, and; a molar ratio of said
optional
component P to said component MA from 0.0: 1 to about 1 : 1. Non-limiting
examples
of components M, B and P include: methylalumoxane (MMAO-7); trityl tetrakis
(pentafluoro-phenyl) borate; and 2,6-di-tert-butyl-4-ethylphenol,
respectively. The
process may further comprise the injection of said bridged metallocene
catalyst
formulation into said first reactor and optionally said second reactor at a
catalyst inlet
temperature from about 20 C to about 70 C; optionally, said component M and
said
component P may be deleted from said bridged metallocene catalyst formulation
and
replaced with a component J defined by the formula Al(R1)n(0R2)0, wherein the
(R1)
groups may be the same or different hydrocarbyl groups having from 1 to 10
carbon
atoms; the (OR2) groups may be the same or different, alkoxy or aryloxy
groups,
wherein R2 is a hydrocarbyl group having from 1 to 10 carbon atoms bonded to
oxygen, and; (n+o) = 3, with the proviso that n is greater than 0. Optionally,
said
bridged metallocene catalyst formulation may be injected into said reactors at
a
catalyst inlet temperature from 80 C to 180 C. Optionally said homogeneous
catalyst
formulation injected into said third reactor is said bridged metallocene
formulation,
said single site catalyst formulation, or a homogeneous catalyst formulation
wherein
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the bulky metal-ligand complex is not a member of the genera defined by
Formula (I)
or (II). Optionally, said heterogeneous catalyst formulation injected into
said third
reactor is an in-line Ziegler-Natta catalyst formulation or a batch Ziegler-
Natta catalyst
formulation. The in-line Ziegler-Natta catalyst formulation is formed in an in-
line
process comprising: i) forming a first product mixture in an in-line
heterogeneous
catalyst assembly by combining a stream Si and a stream S2 and allowing said
first
product mixture to equilibrate for a HUT-1 seconds; wherein said stream S1
comprises a magnesium compound and an aluminum alkyl in said process solvent
and said stream S2 comprises a chloride compound in said process solvent; ii)
forming a second product mixture in said in-line heterogeneous catalyst
assembly by
combining said first product mixture with a stream S3 and allowing said second
product mixture to equilibrate for a HUT-2 seconds; wherein said stream S3
comprises a metal compound in said process solvent; iii) forming said in-line
Ziegler-
Natta catalyst formulation in said in-line heterogeneous catalyst assembly by
combining said second product mixture with a stream S4 and allowing said in-
line
Ziegler-Natta catalyst formulation to equilibrate for a HUT-3 seconds prior to
injection
into said third reactor, wherein said stream S4 comprises an alkyl aluminum co-
catalyst in said process solvent; iv) optionally, step iii) is skipped and
said in-line
Ziegler-Natta catalyst formulation is formed inside said third reactor;
wherein, said
second product mixture is equilibrated for an additional HUT-3 seconds and
injected
into said third reactor and said stream S4 is independently injected into said
third
reactor. Typical Hold-Up-Times include: said HUT-1 is from about 5 seconds to
about
70 seconds, said HUT-2 is from about 2 seconds to about 50 seconds and said
HUT-3
is from about 0.5 to about 15 seconds; and said in-line Ziegler-Natta catalyst
formulation and optionally said second product mixture are injected at a
catalyst inlet
temperature from about 20 C to about 70 C. The in-line Ziegler-Natta catalyst
formulation may comprise: i) said magnesium compound is defined by the formula
Mg(R1)2, wherein the R1 groups may be the same or different; ii) said aluminum
alkyl
is defined by the formula Al(R3)3, wherein the R3 groups may be the same or
different;
iii) said chloride compound is defined by the formula R2CI; iv) said metal
compound is
defined by the formulas M(X)n or MO(X)n, wherein M represents titanium,
zirconium,
hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten,
manganese, technetium, rhenium, iron, ruthenium, osmium or mixtures thereof, 0
represents oxygen, X represents chloride or bromide and n is an integer that
satisfies
CA 2984838 2019-06-25?017066Canada revised disclosure and claims pages.docx
the oxidation state of the metal M, and; v) said alkyl aluminum co-catalyst is
defined
by the formula Al(R4)p(0R5)q(X)r, wherein the R4 groups may be the same or
different,
the OR5 groups may be the same or different and (p+q+r) = 3, with the proviso
that p
is greater than 0; wherein R1, R2, R3, R4 and R5 represent hydrocarbyl groups
having
from Ito 10 carbon atoms; optionally R2 may be a hydrogen atom. The in-line
Ziegler-Natta catalyst formulation may comprise: a molar ratio of said
aluminum alkyl
to said magnesium compound in said third reactor from 3.0 : 1 to 70: 1; a
molar ratio
of said chloride compound to said magnesium compound in said third reactor
from 1.0
: 1 to 4.0: 1; a molar ratio of said alkyl aluminum co-catalyst to said metal
compound
in said third reactor from 0: 1 to 10: 1, and; a molar ratio of said aluminum
alkyl to
said metal compound in said third reactor from 0.05 : 1 to 2 : 1. In the
process
embodiment described in this paragraph: the process solvent may be one or more
C5
to C12 alkanes; said first, second and third reactors may operate at
temperatures from
80 C to 300 C, and; pressures from 3 MPag to 45 MPag. The process solvent in
said
first reactor has an average reactor residence time from about 10 seconds to
about
600 seconds and said process solvent in said second reactor has an average
reactor
residence time from about 10 seconds to about 720 seconds. The process may
also
have a reactor temperature difference (1R2¨ TR1) ranging from 1 C to 120 C;
wherein
1R2 is the temperature of the solution in said second reactor and TR1 is the
temperature of the solution in said first reactor. Said optional a-olefins may
be one or
more of C3 to C10 a-olefins. Ethylene interpolymer products may be produced
employing embodiments of the solution polymerization process disclosed in this
paragraph.
.. Other embodiments include: a continuous solution polymerization process
comprising:
i) injecting ethylene, a process solvent, a bridged metallocene 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 said process
solvent; ii)
injecting ethylene, said process solvent, said bridged metallocene 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 said
process solvent; iii) combining said first and said second exit streams to
form a third
exit stream; iv) passing said third exit stream into a third reactor and
optionally
injecting into said third reactor, ethylene, process solvent, one or more a-
olefins,
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CA 2984838 2019-06-25
hydrogen and a homogeneous catalyst formulation or a heterogeneous catalyst
formulation to produce a fourth exit stream containing an optional third
ethylene
interpolymer, said second ethylene interpolymer and said first ethylene
interpolymer in
said process solvent; v) phase separating said fourth exit stream to recover
an
ethylene interpolymer product comprising said first ethylene interpolymer,
said second
ethylene interpolymer and said optional third ethylene interpolymer; wherein,
said
continuous solution polymerization process is improved by having one or more
of the
following, i.e. (a) and/or (b):
(a) at least an 70% reduced [a-olefin/ethylene] weight ratio as defined by the
following
formula
(a ¨ olefin)' (a ¨ olefin)c
[ a ¨ ole f in] ethylene) ethylene)
% Reduced __________________ = 100 x < ¨70%
ethylene (a ¨ olefin
ethylene
wherein (a-olefin/ethylene)' is calculated by dividing the weight of said a-
olefin added
to said first reactor by the weight of said ethylene added to said first
reactor, wherein
said first ethylene interpolymer having a target density is produced by said
bridged
metallocene catalyst formulation, and; (a-olefin/ethylene)c is calculated by
dividing the
weight of said a-olefin added to said first reactor by the weight of said
ethylene added
to said first reactor, wherein a control ethylene interpolymer having said
target density
is produced by replacing said bridged metallocene catalyst formulation with an
unbridged single site catalyst formulation;
(b) at least a 5% improved weight average molecular weight as defined by the
following formula
% Improved Mw = 100% x (MwA-Mwc)/Mwc 5%
wherein Mv,/ is a weight average molecular weight of said first ethylene
interpolymer
and Mwe is a weight average molecular weight of a comparative ethylene
interpolymer;
wherein said comparative ethylene interpolymer is produced in said first
reactor by
replacing said bridged metallocene catalyst formulation with said unbridged
single site
catalyst formulation.
Additional steps of this process may comprise: a) optionally adding a catalyst
deactivator A to said third exit stream, downstream of said second reactor,
forming a
deactivated solution A; b) adding a catalyst deactivator B to said fourth exit
stream,
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downstream of said third reactor, forming a deactivated solution B; with the
proviso
that step b) is skipped if said catalyst deactivator A is added in step a); c)
phase
separating said deactivated solution A or B to recover said ethylene
interpolymer
product. If a heterogeneous catalyst formulation was added to the third
reactor,
additional process steps may comprise: d) adding a passivator to said
deactivated
solution A or B forming a passivated solution, with the proviso that step d)
is skipped if
said heterogeneous catalyst formulation is not added to said third reactor,
and; e)
phase separating said deactivated solution A or B, or said passivated
solution, to
recover said ethylene interpolymer product. Ethylene interpolymer products may
be
produced employing embodiments of the solution polymerization process
disclosed in
this paragraph.
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.
83
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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 ShodexTM 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 (DR1) as the concentration detector. 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 200 pL. 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 D6474-12 (December 2012). The SEC
raw data were processed with the Cirrus TM GPC software, to produce molar mass
averages (Mr, Mw, Mz) and molar mass distribution (e.g. Polydispersity,
Mw/Mr). In the
polyethylene art, a commonly used term that is equivalent to SEC is GPC, i.e.
Gel
Permeation Chromatography.
Triple Detection Size Exclusion 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-buty1-4-
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 (H1803, 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 (H). 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 TM GPC 150C chromatography unit equipped with four Shodex TM
columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a
flow rate of 1.0 mUminute, 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 TM 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-Ho uwink 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).
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,
CA 2984838 2019-06-25, 85
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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 CRYSTAFTTREF 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
through the column at 0.75 mL/minute, while the column was slowly heated from
30 C
30 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 (a-olefin) composition; CDBI50 was calculated from
the composition distribution cure and the normalized cumulative integral of
the
86
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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. 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 (0.75 mUminute) through the column for 30
minutes. CTREF deconvolutions were performed to determine the amount of
branching (BrF (#C6/1000C)) and density of the first ethylene interpolymer
using the
following equations: BrF (#C6/1000C) = 74,29 ¨ 0.7598 (rcTREF), where TPCTREF
is the
peak elution temperature of the first ethylene interpolymer in the CTREF
chromatogram, and BrF (#C6/1000C) = 9341.8 (p1)2¨ 17766 (p1) + 8446.8, where
p1
was the density of the first ethylene interpolymer. The BrF (#C6/1000C) and
density of
the second ethylene interpolymer was determined using blending rules, given
the
overall BrF (#C6/1000C) and density of the ethylene interpolymer product. The
BrF
(#C6/1000C) 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
aged for 300 seconds or long half-life elements were aged for several days.
After
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aging, the gamma-ray spectrum of the sample was recorded using a germanium
semiconductor gamma-ray detector (Ortec TM model GEM55185, Advanced
Measurement Technology Inc., Oak Ridge, TN, USA) and a multichannel analyzer
(Ortec TM 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 TM 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).
Unsaturation
The quantity of unsaturated groups, i.e. double bonds, in an ethylene
interpolymer
product was determined according to ASTM D3124-98 (published March 2011) and
ASTM D6248-98 (published July 2012). An ethylene interpolymer product sample
was: a) first subjected to an overnight 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 to quantify the amount of terminal (vinyl) and internal unsaturation
(trans-
vinylene), and; d) the sample plaque was brominated and reanalyzed by FTIR to
quantify the amount of side chain unsaturation (vinylidene). The IR resonances
of
these groups appear at 908cm-1, 965cm-1 and 888cm-1, respectively. The
procedure
is based on Beer's Law: A=abdc, where a is the extinction coefficient for the
specific
unsaturation being measured, b is the plaque thickness, d the plaque density
and c
the selected unsaturation. Experimentally, the weight and area of the plaque
are
measured rather than the density and the thickness.
Comonomer (a-Olefin) 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
CH3#/1000C (number of methyl branches per 1000 carbon atoms). This test was
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2984838 2019-06-25
completed according to ASTM D6645-01 (2001), employing a compression molded
polymer plaque and a Thermo-Nicolet 750 Magna-IRTm Spectrophotometer. The
polymer plaque was prepared using a compression molding device (Wabash-Genesis
Series press) according to ASTM D4703-16 (April 2016).
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 DHR3
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 (no) 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-Interscience 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 no.
In this disclosure the onset of shear thinning, T (s-1), was determined by
fitting the
three parameter Ellis model (110, t and n) to the 190 C DMA data (complex
viscosity
(yr) versus frequency (61)): i.e. (ri* =
The Flow Activation Energy (FAE) having dimensions of J/mol was also
determined.
The RheometricsTM RDSII was used to generate the data from which the FAE was
calculated; specifically, the melt viscosity flow curves (from 0.05 to 100
rad/s at 7 data
points per decade) at four different temperatures (160, 175, 190 and 205 C)
were
measured. Using 190 C as the reference temperature, a time-temperature-
superposition shift was carried out to obtain the shift factors. The FAE of
each sample
was calculated using TTS (time-temperature superposition (see Markovitz, H.,
"Superposition in Rheology", J. Polym. Sci., Polymer Symposium Series 50, 431-
456
89
CA 2984838 2019-06-252017066Canada revised disclosure and claims pages docx
(1975)) shifting of the flow curves and Arrhenius equation fitting on zero
shear
viscosity of each temperature with RheoPlusTM and OrchestratorTM software.
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 (1(0) which has the units of
reciprocal
modulus. The inverse of Kt) 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
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 2, for linear
ethylene interpolymers was also valid if the creep determined 'no was used
rather than
the DMA determined no. In this disclosure, the LCBF (Long Chain Branching
Factor)
was determined using the DMA determined io. To be absolutely clear, the zero
shear
viscosity (ZSV [poise]) data reported in Tables 1A, 2 and 3 were measured
using
DMA.
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Melt Strength
The Accelerated-Haul-Off (AHO) Melt Strength (MS), having dimensions of centi-
Newtons (cN), was measured on a Rosand TM RH-7 capillary rheometer (available
from Malvern Instruments Ltd, Worcestershire, UK) having a barrel diameter of
15mm,
a flat die of 2-mm diameter and L/D ratio of 10:1 and equipped with a pressure
transducer of 10,000 psi (68.95 MPa). The polymer melt was extruded through a
capillary die under a constant rate (constant piston speed of 5.33 mm/min at
190 C)
which formed an extruded polymer filament. The polymer filament was then
passed
through a set of rollers and stretched at an ever increasing haul-off speed
until
rupture. More specifically, the initial polymer filament speed was increased
from 0
m/min at a constant acceleration rate from 50 to 80 m/min2 until the polymer
filament
ruptured. During this experiment, the force on the rollers was constantly
measured,
initially the force rises quickly and then plateaus prior to filament rupture.
The
maximum value of the force in the plateau region of the force versus time
curve was
defined as the melt strength for the polymer, measured in centi-Newtons (cN).
Vicat Softening Point (Temperature)
The Vicat softening point of an ethylene interpolymer product was determined
according to ASTM D1525-07 (published December 2009). This test determines the
temperature at which a specified needle penetration occurs when samples are
subjected to ASTM D1525-07 test conditions, i.e. heating Rate B (120 10 C/hr
and
938 gram load (10 0.2N load).
Heat Deflection Temperature
The heat deflection temperature of an ethylene interpolymer product was
determined
using ASTM D648-07 (approved March 1, 2007). The heat deflection temperature
is
the temperature at which a deflection tool applying 0.455 MPa (66 PSI) stress
on the
center of a molded ethylene interpolymer plaque (3.175 mm (0.125 in) thick)
causes it
to deflect 0.25 mm (0.010 in) as the plaque is heated in a medium at a
constant rate.
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Flexural Properties
The flexural properties, i.e. flexural secant and tangent modulus and flexural
strength
were determined using ASTM D790-10 (published in April 2010).
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 Lub-Tef Puncture
The 'Lub-Tef Puncture' test was performed using a specifically designed Teflon
TM
probe at a 20 in/min. puncture rate, the purpose of this test was to determine
the
puncture resistance of monolayer ethylene interpolymer product films. An MTS
Insight/Instron Model 5 SL Universal Testing Machine equipped with MTS
Testworks
4TM software was used: MTS 1000 N or 5000 N load cells were used. Film samples
were ASTM conditioned for at least 24 hours prior to testing. Given a roll of
blown
film, 4.25 inch sample were cut in the transverse direction, having a length
of the film
roll layflat dimension and the outside of the film is labelled (the probe
impacts the
outside of the film). Mount the Teflon coated puncture probe and set the
testing
speed to 20 inch/min. Mount the film sample into the clamp and deposit 1 cm3
of lube
onto the center of the film. When the crosshead is in the starting test
position, set the
limit switches on the Load Cell frame to 10 inch below and above the
crosshead.
Measure and record film sample thickness and begin (start) the puncture test.
Prior to
the next test thoroughly clean the probe head. Repeat until at least 5
consistent
puncture results are obtained, i.e. standard deviation less than 10%. The
lubricant
used was MukoTM Lubricating Jelly: a water-soluble personal lubricant
available from
92
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Cardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe
head was machined Teflon having a 1.4 inch cone shape with a flat tip.
Film Tensile Properties
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) and tensile elongation at yield (3/0). 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 Instron 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
name into the Instron 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 Instron
software.
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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 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 Opticals
Film optical properties were measured as follows: Haze, ASTM D1003-13
(November
15, 2013), and; Gloss ASTM D2457-13 (April 1, 2013).
Film Dynatup Impact
Instrumented impact testing was carried out on a machine called a Dynatup TM
Impact
Tester purchased from Illinois Test Works Inc., Santa Barbara, CA, USA; those
skilled
in the art frequently call this test the Dynatup TM impact test. Testing was
completed
according to the following procedure. Test samples are prepared by cutting 5
inch
(12.7 cm) wide and 6 inch (15.2 cm) long strips from a roll of blown film;
film was 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 TM 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 Ws. A weight was added
to the
crosshead such that: 1) the crosshead 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,
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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.
Cold Seal Strength
The cold seal strength of 3.5 mil (88.9 pm) 9-layer films were measured using
a
conventional Instron Tensile Tester. In this test, two multilayer films were
sealed
(layer 1 to layer 1) over a range of temperatures, the seals were then aged at
least 24
hours at 73 F (23 C) and prior to tensile testing. The following parameters
were used
in the Cold Seal Strength Test: the film specimen width was 1 inch (25.4 mm);
film
sealing time, 0.5 second; film sealing pressure, 0.27 N/mm2; temperature
range, 90 C
to 170 C with temperature increments of 5 or 10 C. After aging, seal strength
was
determined using the following tensile parameters: pull (crosshead) speed, 12
in/min
(30.48 cm/min); grip separation 0.39 in (0.99 cm); direction of pull, 90 to
seal; and 4
to 8 samples of each multilayer film were tested at each temperature increment
to
calculate an average value. In the cold seal test, the Seal Initiation
Temperature (SIT)
was recorded, in C; the SIT was the temperature at which the seal strength
reached
8.8 N/in.
Film Hot tack Strength
The hot tack strength of 3.5 mil (88.9 pm) 9-layer films were measured using a
J&B
Hot Tack Tester (commercially available from Jbi Hot Tack, Geloeslaan 30, B-
3630
Maamechelen, Belgium). In the hot tack test the strength of a polymer to
polymer seal
is measured immediately after heat sealing two films together, i.e., when the
polyolefin
is in a semi-molten state. This test simulates heat sealing on 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 N/mm2; seal
time, 0.5
CA 2984838 2019-0 6 ¨25onse\2017066Canada revised disclosure and claims
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s, cool time, 0.5 second; film peel speed, 7.9 in/second (200 mm/second);
temperature range, 90 C to 170 C; temperature increments of 5 or 10 C; and 4
to 8
samples of each multilayer film were tested at each temperature increment to
calculate an average value. In this disclosure, the Hot Tack Onset (HTO)
temperature, measured in C, was the temperature at which the hot tack force
reached 1N. In addition, the Maximum Hot Tack Force (Max. HTF) was recorded,
i.e.
the maximum hot tack force (N) recorded during the hot tack experiment; as was
the
temperature ( C) at which the Max. HTF was observed.
Film Hexane Extractables
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
ytm) monolayer film was placed in a stainless steel basket, the film and
basket were
weighed (w). 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 (we). The percent loss in weight is the percent hexane
extractables (WC6): WC6 = 100 x (w'-wf)/wl.
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. Examples of ethylene
interpolymer
products were prepared in a continuous solution process pilot plant as
described
below.
Solution process conditions for Examples 1-3 are summarized in Tables 5A and
5B.
Two CSTR reactors (R1 and R2), configured in series, were employed to
manufacture
Examples 1 and 2. One CSTR reactor was employed to manufacture Example 3
(R2). R1 pressure varied from 14 MPa to 18 MPa; R2 was operated at a lower
pressure to facilitate continuous flow from R1 to R2. CSTR's were agitated to
give
conditions in which the reactor contents were well mixed. The process was
operated
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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 bridged metallocene catalyst
formulation: component A, diphenylmethylene(cyclopentadienyl)(2,7-di-t-
butylfuorenyl)hafnium dimethyl, [(2,7-tBu2Flu)Ph2C(Cp)I-1fMe21 (abbreviated
CpF-2);
component M, methylaluminoxane (MMA0-07); component B, trityl
tetrakis(pentafluoro-phenyl)borate, and; component P, 2,6-di-tert-butyl-4-
ethylphenol.
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 manufactured using the
unbridged
single site catalyst formulation comprising: component C, cyclopentadienyl
tri(tertiary
butyl)phosphinimine titanium dichloride [Cp[(t-Bu)3PN]TiC12] (abbreviated PIC-
1);
component M, methylaluminoxane (MMA0-07); component B, trityl
tetrakis(pentafluoro-phenyl)borate, and; component P, 2,6-di-tert-butyl-4-
ethylphenol.
The following catalyst component solvents were used: methylpentane for
components
M and P, and; xylene for component A and B.
In the case of Example 1, Table 5A shows the quantity of CpF-2 in reactor 1
(R1) was
0.85 ppm, i.e. `R1 catalyst (ppm)'. The efficiency of the bridged metallocene
catalyst
formulation was optimized by adjusting the mole ratios of the catalyst
components and
the R1 catalyst inlet temperature. As shown in Table 5A, the mole ratios
optimized
were: ([M]/[A]), i.e. [(MMA0-07)/(CpF-2)]; ([P]/M1), i.e. [(2,6-di-tert-butyl-
4-
ethylphenol)/(MMA0-07)], and; ([B]/[A]), i.e. [(trityl tetrakis(pentafluoro-
phenyl)borate)/(CpF-2)]. To be more clear, in Example 1 (Table 5A), the mole
ratios
in R1 were: R1 ([M]/[A]) = 50; R1 ([P]/[M]) = 0.40, and; R1 ([B]/[A]) = 1.2.
As shown in
Table 5B, the R1 catalyst inlet temperature was 21 C in the case of Example I.
In
Examples 1 and 2 a second bridged metallocene catalyst formulation was
injected into
the second reactor (R2). Tables 5A and 5B disclose additional process
parameters,
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e.g. ethylene and 1-octene splits between the reactors, and reactor
temperatures and
ethylene conversions, etc.
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 shown in Tables 5A and 5B: average reactor residence times were: 61
seconds in R1, 73 seconds in R2, 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
catalytic metal and aluminum added to the polymerization process.
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 lrganox 1076TM (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.
Ethylene Interpolymer product Examples 1-3 were characterized and the results
are
disclosed in Table 6A. Table 6A also discloses Examples 4-6 prepared on the
same
solution pilot plant employing the bridged metallocene catalyst formulation
and reactor
configuration as described above for Examples 1-3. In Table 6A the term 'FAE
(J/mol)' was the Flow Activation Energy of Examples 1-6 determined as
described in
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the experimental section; 'MS (cN)' was the Melt Strength, and; 't (s-1)
discloses the
rheological onset of shear thinning.
Table 6B characterizes comparative ethylene interpolymer products. Comparative
la
was SURPASS FPs117-C, Comparative 2a was produced in the solution pilot plant
using a bridged metallocene catalyst formulation in the first reactor and an
unbridged
single site catalyst formulation in the second reactor, Comparative 3a was
produced in
the solution pilot plant using a bridged metallocene catalyst formulation in
the first
reactor and an in-line Ziegler-Natta catalyst formulation in the second
reactor,
Comparative 4a was SURPASS VPsK914, Comparative 5a was SCLAIR FP120 and
Comparatives 14-16 were was produced in the solution pilot plant employing an
unbridged single site catalyst formulation in reactors 1 and 2.
Table 6C characterizes additional comparative ethylene interpolymer products.
Comparatives Q1-Q4 were Queo products, specifically Queo 0201, Queo 8201, Queo
0203 and Queo 1001, respectively. The remaining comparative sampes were:
Comparative R1 was Affinity PL1880; Comparative Si was Enable 20-05HH;
Comparative T1 was Exceed 1018CA; Comparative U1 was Elite AT 6202, and;
Comparative V1 was Elite 5401G.
There is a need to improve the continuous solution polymerization process,
e.g. to
increase the production rate, where production rate is the kilograms of
ethylene
interpolymer product produced per hour. Tables 7A and 7B disclose series dual
reactor solution polymerization process conditions that produced products
having melt
-- indexes (12) of about 1.0 dg/min and densities of about 0.9175 g/cc. An
improved
continuous solution polymerization process is represented by Example 6 in
Table 7A.
Example 6 was an ethylene interpolymer product produced on the solution pilot
plant
(described above) by injecting the bridged metallocene catalyst formulation
(CpF-2)
into reactors 1 and 2.
A comparative continuous solution polymerization process is represented by
Comparative 8 in Table 7A. Comparative 8 was a comparative ethylene
interpolymer
product produced on the same solution pilot plant by injecting the unbridged
single
site catalyst formulation (P1C-1) into reactors 1 and 2. The improved process
had a
production rate, PRA, of 93.0 kg/hr; in contrast the comparative process had a
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comparative production rate, PRc, of 81.3 kg/hr. The improved process had an
increased production rate, PR', of 14.5%, i.e.
PR' = 100 x (PRA-PRc)/PRc = 100 x ((93.0-81.3)/81.3) = 14.5%.
Tables 8A and 8B disclose series dual reactor solution polymerization process
conditions that produced products having fractional melt indexes (12) of about
0.8
dg/min and densities of about 0.9145 g/cc. Example 5 was synthesized using the
bridged metallocene catalyst formulation; in contrast, Comparative 9 was
synthesized
using the unbridged single site catalyst formulation. In the case of Example
5, the
improved continuous solution polymerization process had a production rate,
PRA, of
93.9 kg/hr; in contrast the comparative process had a comparative production
rate,
PRc, of 79.4 kg/hr. The improved process had an increased production rate,
PR', of
18.3%.
There is a need to improve the continuous solution polymerization process,
e.g. to
increase the molecular weight of the ethylene interpolymer product produced at
a
specific reactor temperature. In addition, in solution polymerization there is
a need for
catalyst formulations that efficiently incorporate a-olefins into the
propagating
macromolecular chain. Expressed alternatively, there is a need for catalyst
formulations that produce an ethylene interpolymer product, having a specific
density,
at a lower (a-olefin/ethylene) ratio in the reactor.
Table 9 compares the solution polymerization conditions of Example 10
manufactured
using a bridged metallocene catalyst formulation (CpF-2) and Comparative 10s
simulated using an unbridged single site catalyst formulation (PIC-1). Example
10
was produced on the continuous solution process pilot plant (described above)
employing one CSTR reactor. Relative to Example 10, Comparative 10s was
computer simulated using the same reactor configuration, same reactor
temperature
(165 C), same hydrogen concentration (4 ppm), same ethylene conversion (90%
(QT))
and the [a-olefin/ethylene] ratio was adjusted to produce an ethylene
interpolymer
product having the same branch frequency as Example 10 (about 16 C6/1000C).
Given Table 9 it is evident that Example 10 characterizes an improved solution
polymerization process, relative to Comparative 10s, i.e. an improved 'A
Reduced [a-
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olefin/ethylene]' ratio results. Elaborating, the N.-olefin/ethylener weight
ratio of
Example 10 was 83.8% lower (improved) relative to the [a-olefin/ethylene]c
weight
ratio of Comparative 10s, i.e.:
( a ¨ olefin)A (cc ¨ olefin)'
% Reduced ____________________
[a ¨ ole f in] = 100 ethylene) ethylene)
x
ethylene (a ¨ olefin )C
V ethylene
[a ¨ olefin i= 100 x {0,17 ¨ 1.05} % Reduced
ethylene 1.05
where the superscript A represents catalyst Component A (Formula (I)) and the
superscript c represents catalyst Component C (Formula (II)). In addition, the
bridged
metallocene catalyst formulation produced a '"70 Improved Mw'. Elaborating,
the
weight average molecular weight of Example 10 (MwA) was 73.6% higher
(improved),
relative to the weight average molecular weight of Comparative lOs (Mc), i.e.:
% Improved Mw = 100 x (mw,a_mwc)/mwc
A Improved Mw = 100 x (82720 - 47655)/47655 = 73.6%.
Similarly, Table 9 also compares the solution polymerization conditions of
Example 11
manufactured using the bridged metallocene catalyst formulation (CpF-2) with
simulated Comparative 10s using the unbridged single site catalyst formulation
(PIC-
1). Example 11 and Comparative 11s were manufactured or simulated,
respectively,
using the same reactor configuration, same reactor temperature (165 C), same
hydrogen concentration (6 ppm), same ethylene conversion (85% (QT)) and the
respective [a-olefin/ethylene] ratio was adjusted to produce ethylene
interpolymer
products having about the same branch frequency (about 21.5 C6/10000). The [a-
olefin/ethylene]A weight ratio of Example 11 was 72.7% lower (improved)
relative to
the [a-olefin/ethylene]c of Comparative 11s. In addition, the weight average
molecular
weight of Example 11 (MwA) was 199% higher (improved), relative to the weight
average molecular weight of Comparative 11s (Mwc), as shown in Table 9.
Table 10 summarizes solution polymerization process data at higher and lower
reactor
temperatures, relative to Table 9. For example, at 190 C reactor temperature,
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Example 12 can be compared with simulated Comparative 12s. The [a-
olefin/ethylene]' weight ratio of Example 12 was 90.8% lower (improved)
relative to
the [a-olefin/ethylene]C weight ratio of Comparative 12s. In addition, the
weight
average molecular weight of Example 12 (MwA) was 70.4% higher (improved),
relative
to the weight average molecular weight of Comparative 12s (Mwc), as shown in
Table
10.
In Table 10, Example 13 can be compared with simulated Comparative 13s, both
at
reactor temperatures of 143 C. The [c-olefin/ethylene]' weight ratio of
Example 13
was 88.9% lower (improved) relative to the [a-olefin/ethylene]C of Comparative
13s
and the weight average molecular weight of Example 13 (MwA) was 182% higher
(improved) relative to the weight average molecular weight of Comparative 13s
(Mwc).
Tables 11A and 11B compare dual reactor solution polymerization conditions of
Example 14 and Comparative 14. Table 11A discloses reactor 1 process
conditions
and Table 11B discloses reactor 2 process conditions. Example 14 was a dual
reactor ethylene interpolymer product containing a first ethylene interpolymer
synthesized using a bridged metallocene catalyst formulation and a second
ethylene
interpolymer synthesized using an unbridged single site catalyst. Comparative
14 was
a comparative dual reactor ethylene interpolymer product where both the first
and
second ethylene interpolymers were synthesized using an unbridged single site
catalyst. Table 11A shows reactor temperatures (118.7 C 0.7%) and ethylene
conversions (80.0%) were the same for Example 14 and Comparative 14; however,
in
the case of the bridged metallocene catalyst formulation an 87.3% lower (a-
olefin/ethylene) weight fraction was employed in the first reactor, i.e. a
0.35 weight
fraction, relative to the unbridged single site catalyst formulation, i.e.
2.76 weight
fraction. In addition, the amount of hydrogen employed in reactor 1 was 3-fold
higher
when using the bridged metallocene catalyst formulation relative to the
unbridged
single site catalyst formulation. 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 and
reducing
the molecular weight of an ethylene interpolymer.
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Table 12 summarizes SEC deconvolution results, i.e. dual reactor Example 14
and
Comparative 14 were deconvoluted into first and second ethylene interpolymers.
Table 12 shows the weight average molecular weights (Mw) of the first ethylene
interpolymers were similar for Example 14 and Comparative 14, i.e. 249,902 Mw
Example 14 and 275,490 Mw Comparative 14; this similarity in Mw resulted even
though 3 ppm of hydrogen was used to produce the former and no hydrogen was
used to produce the latter. In other words, given Table 12 data it was evident
that the
bridged metallocene catalyst formulation produced higher molecular weight
ethylene
interpolymers, relative to the unbridged single site catalyst formulation, at
constant
polymerization temperature, ethylene conversion and hydrogen concentration.
Table 12 also shows the bridged metallocene catalyst formulation incorporated
more
a-olefin into the first ethylene interpolymer, i.e. 27.8 BrF (C6/1000C)
Example 14,
relative to the unbridged single site catalyst formulation, i.e. 22.9 BrF
(C6/1000C); note
that this difference in branch frequency occurred even though much less a-
olefin was
employed to produce the former relative to the latter, as shown in Table 11A.
In other
words, the bridged metallocene catalyst formulation is much more efficient at
incorporating a-olefin into the propagating macromolecule, relative to the
unbridged
single site catalyst formulation.
Figure 5 compares the SEC determined molecular weight distribution of Example
14
and Comparative 14, as well as the GPC-FTIR determined branching frequencies
as a
function of molecular weight. Example 14's branching distribution curve (BrF)
shows
a large difference in the a-olefin content of the first ethylene interpolymer,
i.e. 27.8
C6/1000C (a first ethylene interpolymer density of 0.8965 g/cc) and the second
ethylene interpolymer, i.e. 0.924 C6/1000C (0.9575 g/cc). This large
difference in
interpolymer density, i.e. Ap = 0.0610 g/cc = (p2 - p1), where p2 is the
density of the
second ethylene interpolymer and p1 is the density of the first ethylene
interpolymer,
reflects the fact that Example 14 was produced in parallel reactor mode as
well as the
different catalyst used in reactors 1 and 2. Higher Ap's are advantageous in
several
end-use applications, one non-limiting example includes higher film stiffness
while
maintaining or improving film toughness. In contrast, as shown in Table 12 the
Ap of
Comparative 14 was an order of magnitude lower, i.e. 0.0062 g/cc.
103
Date Recue/Date Received 2020-05-01
Figure 6 illustrates the deconvolution of Example 4's experimentally measured
SEC
chromatogram into three components, i.e. a first ethylene interpolymer, a
second
ethylene interpolymer and a third ethylene interpolymer. Example 4 is
characterized
in Table 13. Example 4 was produced in the solution pilot plant (described
above)
employing the bridged metallocene catalyst formulation (CpF-2) where the
volume of
the third reactor was 2.2 liters. To be more clear, as produced the ethylene
interpolymer product Example 4 had the following overall values: an 12 of 0.87
dg/min,
a density of 0.9112 9/cc and 105449 Mw (7.53 Mw/Mn) as measured by SEC. As
shown in Figure 6 and Table 13, Example 4 contained: 37 wt% of a first
ethylene
interpolymer having a Mw of 230042 and a branch content of 16.3 C6/1000C, 57
wt%
of a second ethylene interpolymer having a Mw of 22418 and a branch content of
21.3
C6/1000C, and; 6 wt% of a third ethylene interpolymer having a Mw of 22418 and
a
branch content of 21.3 C6/1000C (branch content was determined by
deconvoluting
GPC-FTIR data). The molecular weight distribution of the first, second and
third
.. ethylene interpolymers were characterized by Flory distributions, i.e.
Mw/Mn = 2Ø
Table 13 discloses two additional samples, Examples 5 and 6, also produced in
the
solution pilot plant employing the bridged metallocene catalyst formulation.
The SEC
and GPC-FTIR curves of Examples 5 and 6 were also deconvoluted into a 1st, 2"d
and
3rd ethylene interpolymer, as shown in Table 13.
Continuous Polymerization Unit (CPU)
Small scale continuous solution polymerizations were conducted on a Continuous
Polymerization Unit, hereinafter CPU. These experiments 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 160 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
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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)3PNI]fiC121). 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 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]f[A]) or ([M]/CD 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 cc-olefin
(comonomer, i.e. 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.
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2984838 2019-06-25
The ethylene conversion, QcF'u, 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
v-CPU = 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
CPU experiments, QCPLJ was held constant at about 90% and the HUTcPu was held
constant at about 2.5 minutes. Downstream of the reactor the pressure was
reduced
to atmospheric pressure. The ethylene interpolymer product was recovered as a
slurry in the process solvent and subsequently dried by evaporation in a
vacuum oven
prior to characterization.
CPU conditions were adjusted to synthesize ethylene interpolymer products at
approximately constant melt index and density; more specifically, an ethylene
interpolymer product was synthesized using the bridged metallocene catalyst
formulation and a comparative ethylene interpolymer product was synthesized
using
the unbridged single site catalyst formulation. As shown by each row in Table
14, the
µ% Improved Mw' was at least 10% when one compares the MwA of the ethylene
interpolymer product produced with the bridged metallocene catalyst
formulation and
the Mwc of the comparative ethylene interpolymer product produced with the
unbridged single site catalyst formulation.
As shown in Table 15, the reactor's (a-olefin/ethylene) weight ratio had to be
adjusted
such that ethylene interpolymer products were produced at target density. To
be
more clear, using the bridged metallocene catalyst formulation an (a-
olefin/ethylene)'
was required to synthesize an ethylene interpolymer product at target density;
and
using the unbridged single site catalyst formulation an (a-olefin/ethylene)c
was
required to synthesize a comparative ethylene interpolymer product at target
density.
As shown by each row in Table 15 the bridged metallocene catalyst formulation
allows
the operation of the continuous solution polymerization process at an improved
106
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.2 98 4838
(reduced) (a-olefin/ethylene) weight ratio relative to the control unbridged
single site
catalyst formulation, i.e. the % Reduced [a-olefin/ethylene] weight ratio was
at least -
70%.
Ethylene interpolymer product Example 20 was also produced on the CPU
described
above. Example 20 demonstrates the ability of the bridged metallocene catalyst
formulation containing CpF-2 ((2,7-tBu2Flu)Ph2C(Cp)HfMe2) to produce a low
density
product that was elastomeric in nature, i.e. Example 20 was characterized as
follows:
0.8567 g/cc, 72.9 BrF C6/1000C, 14.6 mole percent 1-octene and 40.6 weight
percent
1-octene.
Monolayer Films
Monolayer blown film samples of ethylene interpolymer product Examples 1 and 2
and
Comparatives 15 and 16 were prepared as disclosed in Table 16. Examples 1 and
2
have been described earlier; Comparatives 15 and 16 were pilot plant samples
produced by injecting the unbridged single site catalyst formulation (PIC-1)
into R1
and R2 (series mode). Monolayer blown film was produced on a Gloucester
extruder,
2.5 inch (6.45 cm) barrel diameter, 24/1 L/D (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. The extruder was equipped
with
the following screen pack: 20/40/60/80/20 mesh. Blown film, of about 1.0 mil
(25.4
urn) thick, was produced at a constant output rate of about 100 lb/hr (45.4
kg/hr) by
adjusting extruder screw speed, and; the frost line height (FLH) was
maintained from
16 to 18 inch (40.64 to 45.72 cm) by adjusting the cooling air. Additional
blown film
processing conditions are disclosed in Table 16.
Given Table 16, it is evident that the blown film extruder pressure of
Examples 1 and 2
were from -16% to -29% lower, relative to Comparatives 15 and 16. Lower blown
film
extruder pressure was an advantage because the output (lb/hr) of a blown film
line
may be limited by extruder pressure. In addition, the extruder amps of Example
1 and
2 were from -10% to -26% lower, relative to Comparative 15 and 16. Lower blown
film
extruder amps was an advantage because the electrical power consumption of a
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blown film line can be reduced if the ethylene interpolymer products disclosed
herein
are use.
Monolayer film physical properties are disclosed in Table 17 along with
selected
physical properties of the Examples 1 and 2 and Comparatives 15 and 16. An
ethylene interpolymer product having high melt strength was advantageous in
the
blown film conversion process, i.e. blown film output is frequently limited by
blown film
bubble instability and the bubble stability improves as resin melt strength
increases.
The melt strengths (measured in centi-Newtons (cN)) of Examples 1 and 2 were
from
25% to 65% higher, relative to Comparatives 15 and 16. Flow activation
energies
(kJ/mol) of Examples 1 and 2 were from 42% to 66% higher, relative to
Comparatives
and 16. Higher flow activation energies are desirable because such resins are
more responsive to changes in extrusion temperature, e.g. given a higher flow
activation energy resin viscosity decreases more rapidly (decreasing extruder
15 pressure and amps) with a given increase in extrusion temperature.
Desirable film physical properties include film optical properties, e.g. low
film haze and
high film Gloss 45 . Optical properties are important when a consumer
purchases an
item packaged in a polyethylene film. Elaborating, a package having better
contact
and/or see-through clarity will have lower internal film haze and higher film
gloss or
sparkle. A film's optical properties correlate with the consumer's perception
of product
quality. Given Table 17, it was evident that the haze of Examples 1 and 2 were
-40%
to -45% lower (improved), relative to Comparatives 15 and 16, and; film Gloss
45 of
Examples 1 and 2 were 16% to 21% higher (improved), relative to Comparatives
15
and 16. Additional blown film physical properties are summarized in Table 17.
Multilayer Films
Multilayer films were produced on a 9-layer line commercially available from
Brampton
Engineering (Brampton ON, Canada). The structure of the 9-layer films produced
is
shown in Table 18. Layer 1 contained the sealant resin under test. More
specifically,
layer 1 contained 91.5wt% of the sealant resin, 2.5 wt% of an antiblock
masterbatch, 3
wt% of a slip masterbatch and 3 wt% of a processing aid masterbatch, such that
layer
1 contained 6250 ppm of antiblock (silica (diatomaceous earth)), 1500 ppm of
slip
(eurcamide) and 1500 ppm of processing aid (fluoropolymer compound); additive
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masterbatch carrier resins were LLDPE, about 2 melt index (12) and about 0.918
g/cc.
Layer 1 was the insider layer, i.e. inside the bubble as the multilayer film
was ,
produced on the blown film line. The total thickness of the 9 layer film was
held
constant at 3.5-mil; the thickness of layer 1 was 0.385 mil (9.8 gm), i.e. 11%
of 3.5 mil
(Table 18). Layers 1-4 and 6-8 contained SURPASSTM FPs016-C an ethylene/1-
octene copolymer available from NOVA Chemicals Corporation having a density of
about 0.917 g/cc and a melt index (12) of about 0.60 dg/min. Layers 4, 6 and 8
also
contained 20 wt% BynelTM 41E710 a maleic anhydride grafted LLDPE available
from
DuPont Packaging & Industrial Polymers having a density of 0.912 Wm and a melt
F
index (12) of 2.7 dg/min. Layers 5 and 9 contained UltramidTM C40 La nylon
(polyamide 6/66) available from BASF Corporation having a melt index (12) of
1.1
dg/min. The multilayer die technology consisted of a pancake die, FLEX-STACKTm
Co-extrusion die (SCD), with flow paths machined onto both sides of a plate,
the die
tooling diameter was 6.3-inches, in this disclosure a die gap of 85-mil was
used
consistently, film was produced at a Blow-Up-Ratio (BUR) of 2.5 and the output
rate of
the line was held constant at 250 lb/hr. The specifications of the nine
extruders follow:
1
screws 1.5-in diameter, 30/1 length to diameter ratio, 7-polyethylene screws
with
single flights and Maddock mixers, 2-Nylon screws, extruders were air cooled,
equipped with 20-H.P. motors and all extruders were equipped with gravimetric
blenders. The nip and collapsing frame included a DecatexTM horizontal
oscillating
haul-off and pearl cooling slats just below the nips. The line was equipped
with a turret
winder and oscillating slitter knives. Table 19 summarizes the temperature
settings
used. All die temperatures were maintained at a constant 480 F, i.e. layer
sections,
mandrel bottom, mandrel, inner lip and outer lip.
f,
End users often desire improvements and/or a specific balance of several film
properties. Non-limiting examples include optical properties, melting point
for a given
density, heat seal and hot tack properties, and others. Elaborating, within
the
packaging industry there is a need to improve the heat seal and hot tack
properties of
films. For example, it is particularly desirable to lower the seal initiation
temperature
(SIT) and broaden the hot tack window while maintaining, or improving, other
film
physical properties such as stiffness, toughness and optical properties.
1
109
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CA 2984838 2020-03-12
1
Table 20 discloses cold seal data and seal initiation temperatures (SIT) of
four 9-layer
films coded (i) through (iv). Layer 1 of film (i), the sealant layer,
contained the
following binary blend: 70 wt% of Example 1 and 30 wt% of Comparative 5; the
latter
was SCLAIR FP120 (0.920 g/cc and 1.012); layer 1 also contained additives as
described above. Layer 1 of film (i) had a blended density of about 0.909
g/cc.
Surprisingly, as shown in Figure 7, the cold seal curves of film (i) and
Comparative
film (ii) were essentially equivalent; surprising because film (ii)'s layer 1
was 0.906
g/cc. Further, as shown in Table 20, the SIT's of films (i) and (ii) were
essentially
equivalent, i.e. 92.4 and 92.2 C, respectively; again surprising given the
difference in
layer 1 densities, i.e. 0.909 g/cc versus 0.906 g/cc, respectively. To be more
clear,
the polyethylene film art is replete with examples disclosing that seal
initiation
temperature (SIT) increases as film (i.e. the sealant layer) density
increases; Figure 7
evidences this trend, i.e. the cold seal curve of film (iv) having a layer 1
density of
0.914 g/cc was shifted to higher temperatures resulting in an SIT of 102.5 C
SIT
(Table 20).
Figure 7 and Table 20 demonstrate at least two advantages of the ethylene
interpolymer products disclosed herein, specifically: (a) at constant SIT, a
film (or
layer) having a higher density is desired (film (i)) because the film is
stiffer and more
easily processed through packaging equipment, relative to a lower density
comparative film, and; (b) the ethylene interpolymer products disclosed herein
can be
diluted with higher density LLDPE's, i.e. the overall cost of the sealant
resin
formulation can be reduced.
Specific hot tack properties are desired in high speed vertical and horizontal
form-fill-
seal processes where a product (liquid, solid, paste, part, etc.) is loaded
and sealed
inside a pouch-like package. For example, the packaging industry requires
sealant
resins that have broad hot tack windows, i.e. such resins consistently produce
leak-
proof packages as various parameters are changed on the packaging equipment.
Further, it is desirable that the Hot Tack Onset temperature (HTO ( C)) occurs
at the
lowest possible temperature. Also desirable is high temperature hot tack such
that the
seal strength remains sufficient at elevated temperatures. Poor hot tack
properties
frequently limit packaging line product rate.
110
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CA ¨25
Table 21 discloses hot tack data, the Hot Tack Onset (HTO) temperature as well
as
comments on the manner in which the 9-layer films failed. Surprisingly, the
HTO
temperatures of films (iii) and (ii) were similar, i.e. 86.3 and 86.8 C,
respectively;
surprising given the difference in layer 1 densities, i.e. 0.913 and 0.906
g/cc
respectively. This is surprising because the polyethylene film art discloses
that the
HTO temperature of a film (or layer) increases as film (or layer) density
increases.
Hot tack curves for film (iii) comprising Example 5 and film (ii) comprising
Comparative
are shown in Figure 8. Even though the density of Example 5 (film (iii)) was
higher,
the breadth of Example 5's hot tack window was similar to Comparative 15 (film
(ii)).
111
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Table 1: FTIR unsaturation in ethylene interpolymer products Examples 1-6,
relative to Comparatives and the Unsaturation Ratio UR.
UR =
Internal Side Chain Term Total
Sample (5Cu-
Unsat/100C Unsat/100C Unsat/100C Unsat/100C
Tu)/Tu
Example 1 0.011 0.006 0.008 0.025 -0.25
Example 2 0.011 0.006 0.007 0.024 -0.14
Example 3 0.014 0.009 0.009 0.032 0.00
'
Example 4 0.025 0.018 0.019 0.062 -0.05
Example 5 0.026 0.018 0.020 0.064 -0.10
Example 6 0.027 0.017 0.020 0.064 -0.15
Comp 01 0.014 0.012 0.011 0.037 0.091
_
Comp 02 0.017 0.016 0.015 0.048 0.067
Comp 03 0.015 0.013 - 0.012 0.040 0.083
Comp 04 0.013 0.011 0.010 0.034 0.100
0.0133 0.0140 0.0057 0.0330 1.349
Comp Ra
0.0055 +0.0077 0.0010 0.0046 0.907
0.0056 0.0034 0.0028 0.0118 ' 0.1833
Comp Sh
0.0024 +0.0023 0.0015 0.0026 0.0550
0.0209 0.0031 ' 0.0056 0.0296 -0.4374
Comp. lc
0.0037 0.0010 0.0006 0.0041 0.1698
0.0133 0.0027 - 0.0053 0.0213 -0.5000
Comp 2d
+0.0023 0.0006 0.006 0.0032 0.1000
0.0029 0.0031 0.0091 0.0152 -0.6600
Comp Te'
0.0024 0.0014 0.0037 0.0052 0.1306
Comp U 0.003 0.002 0.006 0.011 -0.667
_
0.0050 0.0045 0.0333 0.0428 -0.8548
Comp 3f
0.0008 0.0006 0.0107 0.0099 0.0427
0.0071 0.0043 0.0320 0.0434 -0.8633
Comp 4g
0.0008 0.0015 0.0068 0.0080 0.0470
_
0.0050 0.0065 0.0492 0.0607 -0.8687
Comp 5h
0.0016 0.0015 0.0025 0.0034 0.0296
112
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UR =
Internal Side Chain Term Total
Sample (SCu-
Unsat/100C Unsat/100C Unsat/100C Unsat/100C
TuvTu
0.0046 0.0032 0.0254 0.0332 -0.8737
Comp VI
0.0029 0.0015 0.0039 0.0044 0.0663
3 Average of 7 samples of Comparative R (Affinity)
h Average of 9 samples of Comparative S (Enable)
Average of 61 samples of Comparative 1
d Average of 3 samples of Comparative 2
e Average of 48 samples of Comparative T (Exceed)
f Average of 4 samples of Comparative 3
g Average of 21 samples of Comparative 4
h Average of 137 samples of Comparative 5
'Average of 25 samples of Comparative V (Elite)
113
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Table 2A: Reference resins (linear ethylene polymers) containing undetectable
levels of Long Chain Branching (LCB).
Reference Mv [Ili SCBD
Mw/Mn A ZSV (poise)
Resins (g/mole) (dL/g) CH3#/1000C
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 1.369 232 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
Resin 28 1.00E+05 1.547 3.33 2.1626 14.1 9.61E+04
Resin 30 1.04E+05 1.525 3.73 2.1626 13.4 ' 1.10E+05
114
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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
115
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Table 2B: Long Chain Branching Factor (LCBF) of reference resins (linear
ethylene polymers) containing undetectable levels of Long Chain Branching
(LCB).
Reference Log ZSV, Log IV, SF, 5, LCBF
Resins (log(poise)) log(dL/g) (dimensionless) (dimensionless)
(dimensionless)
Resin 1 4.87E+00 2.46E-01 -5.77E-02 -1.21E02 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
1 ___________________________________________________________________
Resin 26 4.97E+00 2.48E-01 3.94E-02 8.27E-03 1.63E-
04
Resin 28 4.79E+00 2.24E-01 -3.13E-02 -6.57E-03
1.03E-04
Resin 30 4.80E+00 2.18E-01 1.47E-02 3.08E-03 2.26E-
05
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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 .
117
\1ell(CA 2984838 2019-06-25066Canada revised disclosure and claims pages.docx
Table 3A: Long Chain Branching Factor (LCBF) of ethylene interpolymer
products Examples 1-3 and Comparatives 1a, Q1, Q3 and Q4.
Example Example Example Comp.
Comp. Comp
Sample Comp la
1 2 3 01 03 04
Mv
91070 86540 87980 99100 83916 65795 78793
(g/mole)
tnl
1.286 1.245 1.284 1.539 1.234 1.035 1.207
(dL/g)
Mw/Mn 3.320 2.510 1.870 3.09 2.00 2.13 2.16
A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626
2.1626
SCB
23.4 20.9 22.3 14.0 24.3 24.6 18.6
(CH3/1000C)
ZSV
257200 189500 179900 89432 148300 37310 158800
(poise)
Log ZSV,
5.22 5.19 5.28 4.78 5.17 4.55 5.17
(log(poise))
Log IVc
0.172 0.151 0.167 0.222 0.155 0.079 0.130
(log(dL/g))
Sh
0.646 0.718 0.732 -0.022 0.681 0.417 0.799
(dimensionless)
Sy
0.136 0.151 0.154 -0.0047 0.143 0.088 0.168
(dimensionless)
LC8F
0.044 0.054 0.056 0.0001 0.049 0.018 0.067
(dimensionless)
118
chel CA 2984838 2019-06 -2566Canada revised disclosure and claims pages.doex
Table 3B: Long Chain Branching Factor (LCBF) of Comparatives R1, S1, S2, U,
V2a, V2b and T
Comp Comp Comp
Sample Comp R1 Comp S2 Comp U Comp T
Si V2a V2b
Mv
89431 93207 103339 98451 101762 10425 107101
(g/mole)
1.314 1.464 1.588 1.405 1.488 1.507 1.681
(dL/g)
Mw/Mn 1.80 2.60 2.85 2.18 2.85 2.79 1.91
A 2.1626 1.9772 1.9772 1.9772 2.166 2.1626 1.9772
SCB
23.3 10.9 6.5 16.1 13.7 14.1 11.0
(CH3#/1000C)
ZSV
151100 825025 4948000 181700 142757 155400 82281
(poise)
Log ZSV,
5.22 5.82 6.559 5.226 5.019 5.065 4.932
(log(poise))
Log IVc
0.179 0.190 0.216 0.187 0.208 0.215 0.250
(log(dL/g))
Sh
0.614 1.158 1.780 0.584 0.276 0.290 -0.009
(dimensionless)
Sy
0.129 0.243 0.374 0.123 0.058 0.061 -0.002
(dimensionless)
LCBF
0.040 0.141 0.333 0.036 0.0080 0.0088
0.0000
(dimensionless)
119
eticA 2984838 2019-06-251066Canada revised disclosure and claims pages.docx
Table 4: Neutron Activation Analysis (NAA), catalyst residues in ethylene
interpolymer product Examples 1-3, relative to Comparatives.
Sample Hf (ppm) Ti (ppm)
Example 1 1.76 n.d.
Example 2 1.98 n.d.
Example 3 2.20 n.d.
Example 4 1.71 n.d.
Example 5 1.51 n.d.
Example 6 1.38 n.d.
Comparative Q1 0.28 n.d.
Comparative Q2 0.34 n.d.
Comparative Q3 0.24 n.d.
Comparative Q4 0.24 n.d.
0.33
Comparative R n.d.
+0.01
Comparative SID n.d. 0.14
Comparative Ue n.d. 0.73
Comparative VI n.d. 1.5 0.06
0.30
Comparative 1C n.d.
0.06
I 0.17
Comparative 2d 0.58 0.07
+0.06
6.34
Comparative 3f 0.52 +0.03 I
2.98
6.78
Comparative 4g n.d.
1.26
7.14
Comparative Sh n.d.
+1.22
a Comparative R, averages of Affinity
b Comparative S (Enable B120)
Comparative 1, Nova Chemicals database average
d Comparative 2, NOVA Chemicals database average
e Comparative U (Elite AT 6202)
f Comparative 3, NOVA Chemicals database average
120
Vkchcr ¨0 ¨66Canada revised disclosure and claims pages docx
CA 2984838 20196-25
g Comparative 4, NOVA Chemicals database average
Comparative 5, Nova Chemicals database average
' Comparative V. average (Elite)
Table 5A: Continuous solution process parameters for Examples 1-3.
Example Example Example
Sample
1 2 3
Reactor Mode Series Series Single
R1 Catalysta CpF-2 CpF-2 CpF-2
R2 Catalyst CpF-2 CpF-2
R1 catalyst (ppm) 0.85 1.02 1.47
R1 ([Mb]/[A]) mole ratio 50 50 31
R1 ([13c]/[M]) mole ratio 0.4 0.4 0.4
R1 ([131/[A]) mole ratio 1.2 1.2 1.2
R2 catalyst (ppm) 0.60 0.57 n/a
R2 ([M]/[A]) mole ratio 31 31 n/a
R2 ([11/[M]) mole ratio 0.4 0.4 n/a
R2 ([8]/1A1) mole ratio 1.2 1.2 n/a
R3 volume (L) 2.1 2.1 2.1
ES (%) 38 38 100
ESR2 (%) 62 62 0
ESR3 (%) 0 0 0
R1 ethylene concentration
9.9 10.8 14.3
(wt%)
R2 ethylene concentration
12.6 12.3 n/a
(wt%)
R3 ethylene concentration
12.6 12.3 n/a
(wt%)
((1-octene)/ (ethylene))Rl
0.30 0.37 0.410
(wt. fraction)
((1-octene)/ (ethylene))R2
0.46 0.37 n/a
(wt. fraction)
(1-octene/ethylene) 0.324 0.263 n/a
121
\\cheCA 2984838 2019 ¨06_25)66Canada revised disclosure and claims pages.docx
(wt. fraction, total)
Prod. Rate (kg/h) 72 70 56
a [(2,7-tBU2FIU)Ph2C(CP)HfMe2J
b methylaluminoxane (MMAO-7)
2,6-di-tert-butyl-4-ethylphenol
d trityl tetrakis(pentafluoro-phenyl)borate
10
20
30
122
chCA 2984838 2019-06-257066Canada revised disclosure and claims pages. ducx
Table 5B: Continuous solution process parameters for Examples 1-3.
Example Example Example
Sample
1 2 3
Reactor Mode Series Series Single
R1 total solution rate 1
266 238 400
(kg/h)
R2 total solution rate
284 312 250
(kg/h)
R3 solution rate (kg/h) 15 15 15
Total solution rate (kg/h)a 550 550 650
OS" (%) 74.8 71.3 100
05' (%) 25.2 28.7 n/a
OSR3(%) 0 0 n/a
H2R1 (ppm) 2.75 2.75 5.5
H2R2 (ppm) 16.0 12.0 n/a
H2R3(ppm) 0 0 n/a
R1 feed inlet temp ( C) 30 30 30
R2 feed inlet temp ( C) 30 30 n/a
R3 feed inlet temp( C) 130 130 130
R1 catalyst inlet temp ( C) 21 25 30
R2 catalyst inlet temp ( C) 36 39 n/a
R1 Mean temp ( C) 140 150 185
R2 Mean temp ( C) 180 180 n/a
R3 exit temp ( C) 182 183 201
cell (%) 80 80 80
QR2(%) 80 80 n/a
cli. (%) n/a n/a n/a
a Total solution rate (kg/h) = (R1 total solution rate (kg/h)) + (R2 total
solution rate (kg/h))
123
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Table 6A: Characterization of ethylene interpolymer product, Examples 1-6.
Sample Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 15
Density
0.9045 0.9069 0.9028 0.9112 0.9134 0.9174 0.9144
(g/cc)
12
0.93 1.1 0.91 0.87 0.89 0.86 0.86
(dg/min)
S.Ex. 1.58 1.52 1.44 1.73 1.75 1.74 1.54
12412 57 43.5 31.1 106 111 106 42.4
M,, 91509 90425 84299 105449 99451 105774 80547
MW/Mn 3.32 2.51 1.87 7.53 6.49 7.39 2.21
MIK, 2,69 2.44 1.63 4.12 3.44 4.74 1.90
BrF
23.4 20.9 22.3 18.1 15.5 14.1 16.0
C6/1000C
Mol%
4.7 4.2 4.5 4.4 4.1 3.7 3.2
a-olefin
CDBI50 89.3 92.4 92.5 75.2 74.7 74.1 89.9
FAE
48.34 54.38 59.03 44.30 44.51 45.98 n/a
(J/mol)
MS (cN) 4.56 3.82 n/a 4.63 4.63 4.76 4.33
T (s-1) 0.245 0.387 0.705 0.127 0.116 0.083 n/a
124
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Table 68: Characterization of comparative ethylene interpolymer products,
Comparative la-5a and 14-16.
Comp Comp Comp Comp Comp Comp Comp Comp
Sample
la 2a 3a 4a 5a 14 15 16
Density
0.9162 0.9172 0.917 0.9124 0.9188 0.9059 0.9064 0.9064
(g/cc)
lz (dg/min) 0.99 1.06 0.7 0.92 0.96 0.89 0.97 0.94
-
5.Ex. 1.27 1.45 1.4 1.24 1.34 1.66 1.24 1.42
1202 30.8 41.9 34.8 23.3 32.4 90.8 26 44.3
M, 102603 96238 106261 107517 110365 1 113541 107600 113161
MaMn 3.08 2.65 2.99 2.51 3.65 5.52 2.96 3.42
Mz/M, 2.32 2.14 2.05 2.14 3.16 3.55 2.30 2.93
BrF
14.6 15.8 16.7 18.1 12.9 23.4 21.2 21.2
C6/1000C
Mol%
19 32 3.3 3.6 2.6 4.7 4.2 4.2
a-olefin
CDB150 77,5 6.6 49.8 59.7 56.1 84.7 81.8 90.6
FAE (Vmol) 32.85 n/a n/a 32.46 30.46 n/a 32.85
33.93
MS (cN) 2.78 3.29 5.26 7.7 6.46 n/a 6.7 6.9
t (s-1) 12.9 n/a 0.467 8.37 3.09 n/a 12.9 3.27
,
125
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Table 6C: Characterization of comparative ethylene interpolymer products,
Comparative Ql-Q4, RI-VI.
Comp Comp Comp Comp Comp Comp Comp Comp Comp
Sample
01 02 Q3 04 R1 Si Ti U1 V1
Density 0.901 0.909 0.901 0.908
0.9006 0.8827 0.9205 0.9187 0.9179
(g/cc) 3 3 2 1
12 (dg/min) 1.12 1.13 3.04 1.14 1.03 0.52 0.94 0.86
1.02
S.Ex. 1.45 1.47 1.4 1.48 1.41 1.56 1.11 1.34
1.33
121/12 33.4 37.5 31.4 36.1 30 39.6 15.8 30 I 30.2
Mw 83303 93355 68628 82272 83474 93531 110641 94385 98469
Mw/Mn 2 1.93 2.13 2.16 1.79 2.74 2.18 2.18
2.74
Mz/Mw 1.71 1.7 1.77 1.82 1.63 1.91 1.71 1.86
2.17
BrF
24.3 38.5 24.6 18.6 23.3 10.9 13.4 16.1
14.2
C6/1000C
Mol%
4.9 7.7 4.9 3.7 4.7 2.2 2.7 3.2 2.8
a-olefin
CDBIso 92.1 97.6 89.4 86.7 89.2 88 70.8 86.5 57.1
FAE
57.12 54.68 50.67 60.64 56.60 56.82 29.59 n/a 39.50
(J/mol)
MS (cN) 3.64 3.69 1.75 3.71 n/a n/a 2.04 n/a 7.06
-c (s-i) 0.745 0.714 6.89 0.565 0.340 0.020 42.5
n/a 1.10
126
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Table 7A: Continuous solution process parameters for Example 6 and
Comparative 8, at about 112 and 0.9175 g/cc.
Sample Example 6 Comparative 8
Reactor Mode Series Series
I ____________________________________________________________
R1 Catalyst (i) CpF-2 PIC-1
R2 Catalyst (ii) CpF-2 PIC-1
Density (g/cc) 0.9180 0.9170
Melt Index, 12 (dg/min) 0.92 1.00
Stress Exponent, S.Ex. 1.75 1.29
MFR, 121/12 107 31.3
Branch Freq. (C6/1000C) 18.3 14.4
R1 Catalyst, (i) (ppm) 0.36 0.10
R1 ([M}/[(i))) (mole ratio) 31 100
R1 (MAW (mole ratio) 0.40 0.30
R1 ((B]/[W]) (mole ratio) 1.20 1.20
R2 Catalyst, (ii) (ppm) 0.76 0.22
R2 ([M]A(ii)]) (mole ratio) 31 25
R2 ([P]/[M]) (mole ratio) 0.4 0.30
R2 ([13]/[(ii)]) (mole ratio) 1.2 1.30
ESR1 (%) 45 50
ESR2 (%) 55 50
ES' (%) 0 0
R1 ethylene concentration (wt.fr.) 10.5 9.8
R2 ethylene concentration (wt.fr.) 13.8 12.6
R3 ethylene concentration (wt.fr.) 13.8 12.6
((1-octene)/(ethylene))Rl (wt.fr.) 0.19 1.40
((1-octene)/(ethylene))R2(wt.fr.) 0.30 0.0
((1-octene)/(ethylene)) Overall (wt.fr.) 0.25 0.71
OSR1 (%) 33.5 100
66.5 0
0SR3 (%) 0.0 0
H1R1 (PPrn) 2.75 0.4
127
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H2' (ppm) 10.0 0.8
H253(ppm) 0.0 0.0
Prod. Rate (kg/h) 93.0 81.3
Table 7B: Continuous solution process parameters for Example 6 and
Comparative 8, at about 112 and 0.9175 g/cc.
Sample Example 6 Comparative 8
Reactor Mode Series Series
R1 Catalyst (i) CpF-2 P1C-1
R2 Catalyst (ii) CpF-2 PIC-1
Density (g/cc) 0.9180 0.9170
Melt Index, 12 (dg/min) 0.92 1.00
Stress Exponent, S.Ex. 1.75 1.29
MFR, 121/12 107 31.3
Branch Freq. (C6/1000C) 18.3 14.4
R3 volume (L) 2.2 2.2
R1 total solution rate (kg/h) 354.0 387.2
R2 total solution rate (kg/h) 246.0 212.8
R3 solution rate (kg/h) 0.0 0
Total solution rate (kg/h) 600.0 600.0
R1 inlet temp ( C) 35 30
R1 catalyst inlet temp ( C) 27.7 30.3
R1 Mean temp ( C) 148.2 140.1
R2 inlet temp ( C) 45 30
R2 catalyst inlet temp ( C) 27.9 30.6
R2 Mean temp ( C) 209.0 189.1
R3 exit temp (CC) 210.2 191.6
(%) 80.3 81.6
ce2 (%) 85.0 83.9
Q53 (%) 70.3 53.6
QT (%) 97.1 95.6
Prod. Rate (kg/h) 93.0 81.3
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Table 8A: Continuous solution process parameters for Example 5 and
Comparative 9, at about 0.8 12 and 0.9145 g/cc.
Sample Example 5 Comparative 9
Reactor Mode Series Series
R1 Catalyst (i) CpF-2 PIC-1
R2 Catalyst (ii) CpF-2 PIC-1
Density (g/cc) 0.9153 0.9142
Melt Index, 12 (dg/min) 0.84 0.86
Stress Exponent, S.Ex. 1.76 1.32
MFR, 121/12 114 35.7
Branch Freq. (C6/1000C) 20.5 16.8
R1 Catalyst, (i) (ppm) 31 0.11
R1 ([M]/[(i)]) (mole ratio) 0.40 100
R1 ([131/[M]) (mole ratio) 1.20 0.30
R1 ([131/[(i)]) (mole ratio) 31.8 1.20
R2 Catalyst, (ii) (ppm) 0.78 0.14
R2 ([M]/[(i1)]) (mole ratio) 31 35
R2 ([13]/[M]) (mole ratio) 0.40 0.30
R2 ([6]/[(ii)]) (mole ratio) 1.20 1.50
ESR1 (%) 45 48
ESR2 (%) 55 37
ESR3(%) 0 15
R1 ethylene concentration (wt.fr.) 10.2 8.5
R2 ethylene concentration (wt.fr.) 13.7 10.8
R3 ethylene concentration (wt.fr.) 13.7 12.0
((1-octene)/(ethylene))R1 (wt.fr.) 0.2 1.72
((1-octene)j(ethylene))R2 (wt.fr.) 0.34 0.00
((1-octene)/(ethylene)) Overall (wt.fr.) 0.277 0.826
OS' (%) 32 100
OSR2 (%) 68 o
05R3 (%) 0 0
F12R1 (ppm) 2.75 0.4
129
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H2" (PPm) 10 0.8
FI2R3(ppm) 0 0
Prod. Rate (kg/h) 93.9 79.4
Table 8B: Continuous solution process parameters for Example 6 and
Comparative 9, at about 0.8 12 and 0.9145 g/cc.
Sample Example 5 Comparative 9
Reactor Mode Series Series
R1 Catalyst (1) CpF-2 PIC-1
R2 Catalyst (ii) CpF-2 PIC-1
Density (g/cc) 0.9153 0.9142
Melt Index, 12 (dg/min) 0.84 0.86
Stress Exponent, S.Ex. 1.76 1.32
MFR, 121/12 114 35.7
Branch Freq. (C6/1000C) 20.5 16.8
R3 volume (14 2.2 2.2
R1 total solution rate (kg/h) 364 410
R2 total solution rate (kg/h) 236 160
R3 solution rate (kg/h) 0 30
Total solution rate (kg/h) 600 600
RI. inlet temp (CC) 35 35
R1 catalyst inlet temp (cC) 27.7 30.3
R1 Mean temp (cC) 146 130
R2 inlet temp (cC) 45 55
R2 catalyst inlet temp ( C) 27.9 30.6
R2 Mean temp ( C) 209 177
R3 exit temp ( C) 210 198.5
QR2 (%) 80 81
0R2 (%) 85 87.9
0R3 (%) 70.2 78
(%) 97.1 _________ 95
Prod. Rate (kg/h) 93.9 79.4
130
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Table 9: Comparison of bridged metallocene and unbridged single site catalyst
formulations in a single reactor continuous solution polymerization process at
165 C, Examples 1041 and Comparatives 10s-11s, respectively.
Example Comparati Example Comparati
Sample
ve lOs 11 ve 11s
Reactor Mode Single Single Single Single
R1 Catalyst' CpF-2 PIC-1 CpF-2 PIC-1
a-olefin 1-octene 1-octene 1-octene 1-octene
R1 Mean temp ( C) 165.0 165.4 165.0 165.1 I
H2Ri. (ppm) ______ 4 4 6 6
((1-octene)/
(ethylene)) (wt. 0.17 b LOS 030b 1.10'
fraction)
QT (%) 90.0 90.1 85.0 85.2
SEC Mn 43,397 23,238 42,776 14,285
SEC Mw 82,720 d 47,655 e 86,239 d 28,838e
SEC M, 133,489 72,326 142,459 43,496
SEC Mw/Mõ 1.91 2.05 2.02 2.02
BrF (#C6/1000C) 15.9 16.1 21,6 21.4
% Reduced
- 83.8 - 72.7
fa-olefin/ethylene] f
% Improved Mw g 73.6 199
5 a CpF-2 = [(2,7-
tBu2Flu)Ph2C(Cp)HfMe2]; PIC-1 = (Cp((t-Bu)3PN]TiClz]
b (a-olefin/ethylene)A, bridged metallocene catalyst formulation
(a-olefin/ethylene), unbridged single site catalyst formulation
cl M.', bridged metallocene catalyst formulation
unbridged single site catalyst formulation
10 f% Reduced (a-olefin/ethylene) = 100 x (((a-olefin/ethylene)A-(a-
olefin/ethylene)c)/(a-olefin/ethylene)c)
g % Improved M. =100 x ((m.A - m.c)/mwc)
131
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Table 10: Comparison of bridged metallocene and unbridged single site
catalyst formulations in a single reactor continuous solution polymerization
process at 190 C and at 143 C, Examples 12-13 and Comparatives 12s-13s,
respectively.
Example Comparati Example Comparati
Sample
12 ye 12s 13 ye 13s
Reactor Mode Single Single Single Single
R1 Catalyst'
(component A, or CpF-2 PIC-1 CpF-2 PIC-1
component C)
a-olefin 1-octene 1-octene 1-octene 1-octene
R1 Mean temp ( C) 190.0 190.1 143.0 143.0
1-12R1 (PPm) 2 2 18 18
((1-octene)/
(ethylene))R1 (wt. 0.17 b 1.85 C 0.05 b 0.45 c
fraction)
(%) 85.0 85.2 80.0 80.2
SEC Mn 40618 23106 44718 13612
SEC Mw 79790d 46836 e 77190d 27341e
SEC M, 129396 70817 115557 41142
SEC Mw/Mn 1.96 2.03 1.73 2.01
BrF (4C6/1000C) 13.0 13.0 4.8 4.5
% Reduced
- 90.8 - 88.9
[a-olefin/ethylene] f
% Improved Mw g 70.4 182
CpF-2 = [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]; PIC-1 =- [Cp[(t-Bu)3PN]T1C121
(a-olefin/ethylene)A, bridged metallocene catalyst formulation
((x-olefin/ethylenef, unbridged single site catalyst formulation
MwA, bridged metallocene catalyst formulation
e M.c, unbridged single site catalyst formulation
f % Reduced (a-olefin/ethylene)= 100 x ffla-olefin/ethylener-(a-
olefin/ethylene)C)/(a-olefinfethylenen
g % Improved Mw = 100 x ((WI' - mwc)/mwc)
132
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Table 11A: Physical properties of dual reactor Example 14 and Comparative 14
and solution process conditions in reactor 1 (R1) using the bridged
metallocene
catalyst formulation (Example 14) or the unbridged single site catalyst
formulation (Comparative 14).
Comparative
Sample Example 14
14
Melt Index, 2, dg/min 1.11 0.89
Density, gicc 0.9327 0.9059
MFR, 121/12 127 90.6
BrF (C6/1000C) 13.5 23.4
Mw 93038 113541
Mw/Mn 8.73 5.25
Reactor Mode Parallel Series
R1 Catalyst CpF-2 PIC-1
R1 Catalyst (1) (ppm) 0.43 0.13
R1 ([M]/[(i)]) mole ratio 31 122
R1 aP]/[M]) mole ratio 0.40 0.40
R1 ([13])/[(i)]) mole ratio 1.20 1.47
ES R1 (%) 40 38
R1 ethylene concentration (wt.%) 7.8 7.3
((1-octene)/(ethylene))R1
0.35 2.76
(wt.fraction)
% Reduced [a-olefin/ethylene] a - 87.3
(1-octene)/(ethylene) (wt.fraction,
0.14 1.05
total)
OS' (%) 100 100
H2" (ppm) 3.0 0.0
R1 inlet temp (*C) 30 30
R1 Mean temp ( C) 118.1 119.3
Q.R1 (%) 80.0 80.0
% Reduced [a-olefin/ethylene] = 100 x ((0.35 - 2.76)/2.76)
133
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Table 11B: Dual reactor Example 14 and Comparative 14 solution process
conditions in reactor 2 (R2) using the unbridged single site catalyst
formulation.
Comparative
Sample Example 14
14
R2 Catalyst PIC-1 PIC-1
R2 Catalyst (i) (ppm) 9.0 0.45
R2 ([M]/[(i)]) mole ratio 65 25
R2 ([P]/[M]) mole ratio 0.3 0.30
R2 ([6])/[(1)]) mole ratio 1.5 1.50
R3 volume (L) 2.2 2.2
ESR2 (%) 60 62
ESR3 (%) 0 0
R2 ethylene concentration (wt%) 12.6 10.8
R3 ethylene concentration (wt%) 10.1 10.8
((1-octene)/ (ethylene)r2
0.0 0.0
(wt.fraction)
0SR2(%) 0 0
OS' (%) 0 0
H2R2 (ppm) 40.0 1.0
H2R3(ppm) 0.0 0.0
R1 total solution rate (kg/h) 249.0 309.2
R2 total solution rate (kg/h) 233.3 240.8
R3 solution rate (kg/h) 0 0
Total solution rate (kg/h) 450.0 550.0
R2 inlet temp (T) 50 30
R3 inlet temp( C) 131 130
R2 Mean temp (T) 199.9 175.5
R3 exit temp (actual) (T) 170.0 174.5
0R2(%) 92 89.7
QR3 (%) 4.7 12.4
93.7 93.7
134
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Table 12: Deconvolution of dual reactor ethylene interpolymer product Example
14 into a first and a second ethylene interpolymer and comparison with dual
reactor Comparative 14.
Below, Ethylene Interpolymer Product Properties (Overall)
Sample Example 14 Comparative 14
12 (CPA/Model) 1.11 0.89
Density (CPA/Model) 0.9327 0.9059
MFR, 121/12 127 90.6
BrF (C6/1000C) 13.5 23.4
Mw 93038 113541
Mw/Mn 8.73 5.25
LCBF 0.0104 <0.001
Below, SEC Deconvolution Into R1 and R2 Components
SEC Deco nvoluted SEC Deconvoluted
Ethylene Interpolymers Ethylene Interpolymers
15t 2nd 1st 2nd
Weight Percent (%) 40.7 59.3 30.9 69.1
Mn 126115 8678 137745 15352
Mw 249802 15238 275490 30704
Polydispersity
2.0 2.0 2.0 2.0
(Mw/Mn)
BrF (C6/1000C) 27.8 0.924 22.9 22.7
12 0.04 1445 0.016 81.70
Density (g/cc) 0.8965a 0.9575a 0.9016a 0.9078b
a = (- an ¨ (a12- 4*ao*(a2-(BrF(C6/1000C))) .5))/(2ao); where ao = 9341.81,
an = -17765.91 and an = 8446.849
b p2 (pf wtl*pl.)/f.--=2%
); where p1, p2 and pf are the densities of the 1 and 2nd interpolymer and the
overall
(blend) density, and wt' and wt2 represent the respective weight fractions
135
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Table 13: Deconvolution of ethylene interpolymer products Examples 4-6 into a
first, a second and a third ethylene interpolymer.
Sample Example 4 Example 5 Example 6
R3 vol. (L) 2.2 2.2 2.2
12 (dg/min) 0.87 0.89 0.86
Density
0.9112 0.9134 0.9174
(g/cc)
MFR, 121/12 105 110 106
105449 99451 105774
Mw/Mn 7.53 6.49 7.39
BrF C6/
18.1 15.49 14.05
1000C
CDBIso 75.2 74.7 74.1
UR -0.053 -0.100 -0.150
Below, SEC Deconvolution Into R1, R2 and R3 Components
SEC Deconvoluted SEC Deconvoluted SEC
Deconvoluted Ethylene
Ethylene Interpolymers Ethylene Interpolymers Interpolymers
1st rd 3rd 1st 2nd 3rd 1st 2nd 3rd
Wt.Frac. 0.37 0.57 0.06 0.38 0.58 0.04 0.37
0.57 0.06
M,
115000 11209 11209 119880 10332 8762 114689 10629 8852
Mw
230042 22418 22418 239761 20664 17524 229378 21259 17704
Mw/Mn) 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
BrF
16.3 21.3 21.3 14.2 19.8 20.0 11.6
18.2 18.2
(C6/1000C)
136
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Table 14: Percent (%) improved SEC weight average molecular weight (Mw)
when using the bridged metallocene catalyst formulation relative to the
unbridged single site catalyst formulation (CPU at 160 C reactor temperature
and about 900/o ethylene conversion).
Weight % 1-octene Bridged Metallocene Unbridged Single
Site % Improved
in Catalyst Formulation Catalyst
Formulation M,
ethylene (see3)
Component MA Component IVIõc
interpolymers
A (seel) 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 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 P1C-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 M.A = 164540 x (Octene) - 0.251; where (OctenewN is the weight % of octene
in the ethylene/1-octene
interpolymer
7 Mw` = 121267 x (Octene'f%) - 0.311
3 100% x (MW- Mwc)/M.c
137
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Table 15: Percent ( /0) improvement (reduction) in (a-olefin/ethylene) weight
ratio
in the reactor feed when using the bridged metallocene catalyst formulation
relative to the unbridged single site catalyst formulation (CPU at 160 C
reactor
temperature and about 90% ethylene conversion).
____________________________________________________________________
Weight % 1- Bridged Metallocene Unbridged Single
Site % Reduced
octene in Catalyst Formulation Catalyst
Formulation (a-olefin/
ethylene (a-olefin / (a-olefin /
ethylene)
Component Component
interpolymers ethylene)'' ethylene)c Ratio
A C
(see') (see') (see)
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 P IC-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%
1(a-olefin/ethylene)A= 0.0009 x (0ctenew)2+ 0.0027 x (Octenewt%) - 0.0046;
where (Octene%) is the weight %
of octene in the ethylene/1-octene interpolymer
2 (cc-olefiniethylene)1 = 0.0017 x (0ctenewt%)2+ 0.0771 x (Octenewt%) - 0.0208
3 100% x ((a.-olefiniethylene)1-(a-olefiniethylene)7(cc-olefiniethylene)c
138
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Table 16: Monolayer blown film conditions, Gloucester blown film line, 4 inch
die diameter and 35 mil die gap: Examples 1 and 2, relative to Comparatives 15
and 16.
,
Example Compartive Comparative
Sample Example 2
1 15 16
Thickness (mil) 1 1 1 1
BUR 2.5:1 2.5:1 2.5:1 2.5:1
Film Layflat (in) 15.7 15.7 15.7 15.7
Melt Temp ( F) 441 441 431 432
Output (lb/hr) 99.8 99.6 100 100
FLH (in) 18 18 18 18
Magnehelic (in-H20) 13.0 11.0 10.8 10.3
Nip Pressure (psi) 30 30 30 ¨ 30
Nip Speed: (ft/min) 129 129 132 88
Current: (Amps) 27.8 28.7 37.7 32.1
Voltage: (Volts) 192 183 188 195
Pressure (psi) 2882 2872 4040 3442
Screw Speed (rpm) 41 39 40 41
_ -
139
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Table 17: Monolayer film physical properties: Examples 1 and 2, relative to
Comparatives 15 and 16.
Example Example Comparative Comparative
Sample
1 2 15 16
Density (g/cc) 0.905 0.907 0.906 0.906
12 (dg/min) 0.93 1.12 0.97 0.94
Melt Flow Ratio (1202) 57.0 43,4 26 44.3
S.Ex. 1.58 1.52 1.24 1.42
Melt Strength (cN) 4.56 3.82 2.78 3.03
Flow Act. Energy (kJ/mol) 48.34 54.38 32.85 33.83
Onset shear thinning (1/s) 0.2454 0.3866 12.93 3.269
Film Haze (%) 3.8 4.0 6.7 6.9
Film Gloss at 45 75.2 74.5 64.0 62.0
Dart Impact (g/mil) ' 641 653 761 1100
Lub-Tef Puncture (J/mm2) 81 91 124 84
MD Tear (g/mil) 137 ' 161 201 214
TD Tear (g/mil) 270 292 330 304
MD 1% Sec Mod. (Mpa) 108.0 121.0 107.5 104.3
TD 1% Sec Mod. (Mpa) 107.0 121.0 107.9 106.4
MD 2% Sec Mod. (Mpa) 100 113 99.3 97.7
TD 2% Sec Mod. (Mpa) 99.0 111 99.1 99.3
MD Ten. Break Str.(MPa) 43.1 ' 40.6 50.0 43.1
TD Ten. Break Str.(MPa) 38.8 40.8 41.8 38.8
MD Elong. at Break (%) 481 493 516 481
TD Elong. at Break (%) 701 737 732 701
MD Ten. Yield Str (MPa) 7.6 7.1 7.8 7.6
TD Ten. Yield Str (MPa) 7.5 7.0 7.7 7.5
MD Elong at Yield (%) 10 10 10 10
TD Elong at Yield (%) 10 10 10 10
140
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Table 18: The multilayer film structure (9-layers) used to prepare 3.5 mil
blown
films, the material (sealant resin) under test was placed in layer 1.
% of 9- Materials and Weight% in Each Layer
Layer
layer Material A Material B
Number
structure Material wt. % Material wt. %
Layer 9 11 C40 L 100
Bynel TM
Layer 8 11 FPs016-C 80 20
41E710
Layer 7 11 FPs016-C 100
Bynel TM
Layer 6 11 FPs016-C 80 20
41E710
Layer 5 12 C40 L 100
ByneI
Layer 4 11 FPs016-C 80 20
Tm41E710
Layer 3 11 FPs016-C 100
Layer 2 11 FPs016-C 100
Additive
Layer 1 11 Test Material 91.5 8.5
Masterbatches
Table 19: Multilayer film fabrication conditions.
All temperatures in F
Barrel Barrel
Feed Barrel Barrel Scree
zone zone Adaptor
Throat zone 3 zone 4 n
Extruder/Layer 1 2
Layer 9
100 455 480 480 480 480 480
(outside of bubble)
Layer 8 75 360 420 410 410 410 410
Layer 7 75 360 420 410 410 410 410
Layer 6 75 360 420 410 410 410 410
Layer 5 100 455 480 480 480 480 480
Layer 4 75 360 420 410 410 410 410
Layer 3 75 360 420 410 410 410 410
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Layer 2 75 360 420 ' 410 410 410 410
Layer 1
75 360 420 410 410 410 410
(inside of Rubble)
Table 20: Cold seal data and SIT (Seal Initiation Temperature ( C)) for 9-
layer
films (i) though (iv).
9-Layer Film Code (i) (ii) (iii) (iv)
70wt% Example 1 +
30wt% Comparative
Example Example
Layer 1 Sealant Resin Comparative 5 15 5 15
Layer 1 Density (g/cc) 0.909' 0.906 0.913 0.914
Layer 112 (dgfrnin) 0.95' 0.97 0.89 0.86
_
_____________________________________ --
Seal Temp ( C) Force (N) Force (N) Force (N)
Force (N)
90 2.10 1.82 0.82 0.24
95 15.8 17.4 5.55 0.24
100 32.0 27.4 33.2 1.58
105 35.6 35.3 37.7 16.3
110 41.5 39.2 42.3 27.4
120 44.8 45.3 48.5 49.6
130 50.5 50.2 54.1 55.0
140 52.7 51.3 55.1 57.1
150 55.3 53.8 55.5 56.7
160 53.5 54.1 55.6 55.9
170 55.1 54.8 57.0 55.8
SIT @ 8.8 N ( C) 92.4 92.2 95.6 102.5
Max. Force (N) 55.3 54.8 57.0 57.1
Temp. @ Max Force 150 170 170 140
a density or melt index of the 70%/30% blend
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Table 21: Hot tack data and HTO (Hot Tack Onset temperature ( C)) for 9-layer
films (i) through liv).
9-Layer Film
(1) (ii) (iii) (iv)
Code
Layer 1 70wt% Example 1
Sealant + 30wt% Comparative 15 Example 5
Example 15
Resin Comparative 5
Layer 1
Density 0.909 0.906 0.913 0.914
(g/cc)
Layer 112
0.95 0.97 0.89 0.86
(dg/min)
Avg. Avg. Avg.
Hot Tack Avg. Force Failure Failure Failure
Failure
Force Force Force
Temp ( C) (N) Mode Mode Mode Mode
(N) (N) (N)
80 0.29 no seal 0.20 no seal 0.24 no seal 0.23 no
seal
85 0.31 no seal 0.69 no seal 0.52 no seal 0.24 no
seal
90 1.07 seal 1.54 seal 2.41 seal 0.20 no seal
95 1.95 seal 3.17 seal 3.89 seal 0.29 no seal
100 3.22 seal 4.81 seal 5.16 seal 1.40 seal
105 4.44 seal 5.37 seal 5.34 seal 3.91 seal
110 5.23 seal 7.52 seal 5.13 seal 6.40 seal
115 6.20 seal 7.92 seal 6.14 seal 9.47 stretch
120 6.79 stretch 8.26 seal 6.59 seal 9.21 stretch
125 10.05 stretch 11.85 s/pa 8.37 seal 12.86 stretch
130 9.50 stretch 11.62 sip 9.55 seal 12.47 stretch
135 9.51 stretch 10.81 s/p 9.42 seal 9.56 stretch
140 9.27 stretch 11.11 s/p 7.51 seal 9.12 stretch
145 6.65 stretch 9.20 s/p 7.74 seal 7.92 stretch
150 6.75 stretch 8.16 s/p 6.62 seal 6.58 stretch
155 5.39 stretch 7,12 s/p 5.28 seal 5.54 stretch -
160 5.19 stretch 6.33 s/p 4.49 seal 5.68 stretch
165 4.15 stretch 5.58 s/p 4.44 seal 5.49 stretch
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170 3.74 stretch 4.70 s/p 3.37 seal 3.50 stretch
175 2.86 stretch 4.05 s/p 2.93 seal 3.27 stretch
180 2.87 stretch 3.44 s/p 2.68 stretch 2.33 stretch
Hot Tack
89.5 86.8 86.3 98.2
Onset ( C)
Max. Force
10.1 11.9 9.6 12.9
(N)
Temp. @
Max Force 125 125 130 125
(N)
s/p = stretch/peel failure mode
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