Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02957706 2017-02-13
CAPS AND CLOSURES
FIELD OF THE INVENTION
This disclosure relates to caps and closures comprising at least one ethylene
interpolymer product manufactured in a continuous solution polymerization
process
utilizing at least two reactors employing at least one single-site catalyst
formulation and
at least one heterogeneous catalyst formulation to produce manufactured caps
and
closures having improved properties.
Ethylene interpolymer products are used in caps and closure applications to
produce a wide variety of manufactured articles, e.g. caps for carbonated or
non-
carbonated fluids, as well as dispensing closures including closures with a
living-hinge
functionality. Such caps and closures are typically produced using
conventional
injection or compression molding processes.
In some embodiments, the ethylene interpolymers disclosed herein, having melt
index 0.3 dg/min to 5 5.0 dg/min, have a GI@G"=500 Pa] that is advantageous in
compression molding processes, i.e. a GI@G"=500 Pa] from ?. 40 Pa to 5 70 Pa.
In
some embodiments, ethylene interpolymers disclosed herein, having melt index >
5.0
dg/min to 5 20 dg/min, have a GI@G"=500 Pa] that is advantageous in injection
molding processes, i.e. a GI@G"=500 Pa] from 2. 1 Pa to 5. 35 Pa. Further,
ethylene
interpolymers disclosed herein, having melt index > 0.3 dg/min to 8 dg/min,
have a
GI@G"=500 Pa] that is advantageous in continuous compression molding, i.e. a
G'[@G"=500 Pa] from 80 Pa to 5 120 Pa.
In caps and closure markets there are constant needs to develop new ethylene
interpolymers having improved properties. Non limiting examples of needs
include:
stiffer caps and closures (higher modulus) that allow the manufacture of
thinner and
lighter weight caps and closures, i.e. improved sustainability (source
reduction); higher
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heat deflection temperatures (HDT) which expands the upper use temperature of
caps
and closures and is advantageous in hot fill applications; faster
crystallization rates
which allows caps and closures to be manufactured at higher production rates,
e.g.
more parts per hour; and improved Environmental Stress Crack Resistance
(ESCR),
particularly for caps and closures used in chemically aggressive environments.
In some embodiments, the ethylene interpolymer products disclosed are
produced in a solution polymerization process, where catalyst components,
solvent,
monomers and hydrogen are fed under pressure to more than one reactor. For
ethylene homo polymerization, or ethylene copolymerization, solution reactor
.. temperatures can range from about 80 C to about 300 C while pressures
generally
range from about 3MPag to about 45MPag and the ethylene interpolymer produced
remains dissolved in the solvent. The residence time of the solvent in the
reactor is
relatively short, for example, from about 1 second to about 20 minutes. The
solution
process can be operated under a wide range of process conditions that allow
the
production of a wide variety of ethylene interpolymers. Post reactor, the
polymerization
reaction is quenched to prevent further polymerization, by adding a catalyst
deactivator,
and passivated, by adding an acid scavenger. Once passivated, the polymer
solution is
forwarded to a polymer recovery operation where the ethylene interpolymer is
separated from process solvent, unreacted residual ethylene and unreacted
optional a-
olefin(s). Further, the ethylene interpolymer products disclosed herein are
synthesized
using at least two reactors employing at least one single-site catalyst
formulation and at
least one heterogeneous catalyst formulation.
SUMMARY OF THE INVENTION
This disclosure relates to caps and closures comprising at least one ethylene
interpolymer product manufactured in a continuous solution polymerization
process
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utilizing at least two reactors employing at least one single-site catalyst
formulation and
at least one heterogeneous catalyst formulation to produce manufactured caps
and
closures having improved properties.
Embodiment of this disclosure include caps and closures having at least one
layer containing an ethylene interpolymer product comprising: (i) a first
ethylene
interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a
third ethylene
interpolymer; where the ethylene interpolymer product has a Dilution Index,
Yd, greater
than 0.
Other embodiment of this disclosure include caps and closures having at least
one layer containing an ethylene interpolymer product comprising: (i) a first
ethylene
interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a
third ethylene
interpolymer; where the ethylene interpolymer product has a Dilution Index,
Yd, less
than 0.
Disclosed herein are caps or closures comprising at least one layer
comprising an ethylene interpolymer product comprising:
a first ethylene interpolymer;
a second ethylene interpolymer; and
optionally a third ethylene interpolymer;
wherein said first ethylene interpolymer is produced using a single site
catalyst
formulation comprising a component (i) defined by the formula
(LA)aM(PI)b(Q)n
wherein
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LA is selected from unsubstituted cyclopentadienyl, substituted
cyclopentadienyl,
unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and
substituted
fluorenyl;
M is a metal selected from titanium, hafnium and zirconium;
PI is a phosphinimine ligand;
Q is independently selected from a hydrogen atom, a halogen atom, a Ci_io
hydrocarbyl radical, a Ci_io alkoxy radical and a C5.10 aryl oxide radical;
wherein
each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted
or
further substituted by a halogen atom, a 01-18 alkyl radical, a C1-8 alkoxy
radical, a
C6-10 aryl or aryloxy radical, an amido radical which is unsubstituted or
substituted
by up to two 01-8 alkyl radicals or a phosphido radical which is unsubstituted
or
substituted by up to two C1-8 alkyl radicals;
wherein
a is 1; b is 1; n is 1 or 2; and (a+b+n) is equivalent to the valence of the
metal M;
wherein said second ethylene interpolymer is produced using a first in-line
Ziegler-Natta
catalyst formulation;
wherein said third ethylene interpolymer is produced using said first in-line
Ziegler-Natta
catalyst formulation or a second in-line Ziegler-Natta catalyst formulation;
wherein said
ethylene interpolymer product has a Dilution Index, Yd, less than 0;
wherein said ethylene interpolymer product has a melt index from about 0.3 to
about 7
dg/min, where the melt index is measured according to ASTM D1238 (2.16 kg load
and
190 C); and
wherein said ethylene interpolymer product has a GI@G"=500 Pa] from 80 Pa to
120
Pa.
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Embodiments of this include caps and closures having at least one layer
containing an
ethylene interpolymer product comprising: (i) a first ethylene interpolymer;
(ii) a second
ethylene interpolymer; and (iii) optionally a third ethylene interpolymer;
where the
ethylene interpolymer has 0.03 terminal vinyl unsaturations per 100 carbon
atoms.
Embodiments of this disclosure include caps and closures having at least one
layer containing an ethylene interpolymer product comprising: (i) a first
ethylene
interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a
third ethylene
interpolymer; where the ethylene interpolymer product has 3 parts per million
(ppm) of
a total catalytic metal.
Further embodiments include caps and closures having at least one layer
containing an ethylene interpolymer product comprising: (i) a first ethylene
interpolymer;
(i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and
(iii) optionally a
third ethylene interpolymer; where the ethylene interpolymer product has a
Dilution
Index, Yd, greater than 0 and 0.03 terminal vinyl unsaturations per 100 carbon
atoms
or 3 parts per million (ppm) of a total catalytic metal or a Dimensionless
Modulus, Xd,
> 0.
Further embodiments include caps and closures having at least one layer
containing an
ethylene interpolymer product comprising: (i) a first ethylene interpolymer;
(ii) a second
ethylene interpolymer; and (iii) optionally a third ethylene interpolymer;
where the
ethylene interpolymer product has a Dilution Index, Yd, less than 0 and 0.03
terminal
vinyl unsaturations per 100 carbon atoms or 3 parts per million (ppm) of a
total
catalytic metal or a Dimensionless Modulus, Xd, <0.
Additional embodiments include caps and closures having at least one layer
containing an ethylene interpolymer product comprising: (i) a first ethylene
interpolymer;
(ii) a second ethylene interpolymer; and (iii) optionally a third ethylene
interpolymer;
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where the ethylene interpolymer product has 0.03 terminal vinyl unsaturations
per
100 carbon atoms and 3 parts per million (ppm) of a total catalytic metal or a
Dimensionless Modulus, Xd, > 0.
Embodiments include caps and closures having at least one layer containing an
ethylene interpolymer product comprising: (i) a first ethylene interpolymer;
(ii) a second
ethylene interpolymer; and (iii) optionally a third ethylene interpolymer;
where the
ethylene interpolymer product has 3 parts per million (ppm) of a total
catalytic metal
and a Dimensionless Modulus, Xd, > 0.
Further embodiments include caps and closures having at least one layer
containing an ethylene interpolymer product comprising: (i) a first ethylene
interpolymer;
(ii) a second ethylene interpolymer; and (iii) optionally a third ethylene
interpolymer;
where the ethylene interpolymer product has a Dilution Index, Yd, greater than
0 and
0.03 terminal vinyl unsaturations per 100 carbon atoms and ?_ 3 parts per
million (ppm)
of a total catalytic metal or a Dimensionless Modulus, Xd, > 0.
Further embodiments include caps and closures having at least one layer
containing an
ethylene interpolymer product comprising: (i) a first ethylene interpolymer;
(ii) a second
ethylene interpolymer; and (iii) optionally a third ethylene interpolymer;
where the
ethylene interpolymer product has a Dilution Index, Yd, less than 0 and 0.03
terminal
vinyl unsaturations per 100 carbon atoms and 3 parts per million (ppm) of a
total
catalytic metal or a Dimensionless Modulus, Xd, <0.
Additional embodiments include caps and closures having at least one layer
containing an ethylene interpolymer product comprising: (i) a first ethylene
interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a
third ethylene
interpolymer; where the ethylene interpolymer product has a Dimensionless
Modulus,
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Xd, > 0 and 3 parts per million (ppm) of a total catalytic metal and a
Dilution Index, Yd,
greater than 0 or 0.03 terminal vinyl unsaturations per 100 carbon atoms.
Additional embodiments include caps and closures having at least one layer
containing
an ethylene interpolymer product comprising: (i) a first ethylene
interpolymer; (ii) a
second ethylene interpolymer; and (iii) optionally a third ethylene
interpolymer; where
the ethylene interpolymer product has a Dimensionless Modulus, Xd, <0 and 3
parts
per million (ppm) of a total catalytic metal and a Dilution Index, Yd, less
than 0 or 0.03
terminal vinyl unsaturations per 100 carbon atoms
Embodiments also include caps and closures having at least one layer
containing an ethylene interpolymer product comprising: (i) a first ethylene
interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a
third ethylene
interpolymer; where the ethylene interpolymer product has a Dilution Index,
Yd, greater
than 0, a Dimensionless Modulus, Xd, > 0, 3 parts per million (ppm) of a total
catalytic
metal and 0.03 terminal vinyl unsaturations per 100 carbon atoms.
Embodiments also include caps and closures having at least one layer
containing an
ethylene interpolymer product comprising: (i) a first ethylene interpolymer;
(ii) a second
ethylene interpolymer; and (iii) optionally a third ethylene interpolymer;
where the
ethylene interpolymer product has a Dilution Index, Yd, less than 0, a
Dimensionless
Modulus, Xd, <0, 3 parts per million (ppm) of a total catalytic metal and 0.03
terminal vinyl unsaturations per 100 carbon atoms.
The ethylene interpolymer products disclosed here have a melt index from about
0.3 to about 20 dg/minute, a density from about 0.948 to about 0.968 g/cm3, a
Mw/Mn
from about 2 to about 25 and a CDBI50 from about 54% to about 98%; where melt
index
is measured according to ASTM D1238 (2.16 kg load and 190 C) and density is
measured according to ASTM D792.
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Further, the disclosed ethylene interpolymer products contain: (i) from about
15
to about 60 weight percent of a first ethylene interpolymer having a melt
index from
about 0.01 to about 200 dg/minute and a density from about 0.855 g/cm3 to
about 0.975
g/cm3; (ii) from about 30 to about 85 weight percent of a second ethylene
interpolymer
having a melt index from about 0.3 to about 1000 dg/minute and a density from
about
0.89 g/cm3 to about 0.975 g/cm3; and (iii) optionally from about 0 to about 30
weight
percent of a third ethylene interpolymer having a melt index from about 0.5 to
about
2000 dg/minute and a density from about 0.89 to about 0.975 g/cm3; where
weight
percent is the weight of the first, second or third ethylene polymer divided
by the weight
.. of ethylene interpolymer product.
Embodiments of this disclosure include caps and closures comprising one or
more ethylene interpolymer product synthesized in a solution polymerization
process;
where the ethylene interpolymer product may contain from 0 to about 1.0 mole
percent
of one or more a-olefins.
Further, the first ethylene interpolymer is synthesized using a single-site
catalyst
formulation and the second ethylene interpolymer is synthesized using a first
heterogeneous catalyst formulation. Embodiments of caps and closures may
contain
ethylene interpolymers products where a third ethylene interpolymer is
synthesized
using a first heterogeneous catalyst formulation or a second heterogeneous
catalyst
formulation.
The second ethylene interpolymer may be synthesized using a first in-line
Ziegler Natta catalyst formulation or a first batch Ziegler-Natta catalyst
formulation;
optionally, the third ethylene interpolymer is synthesized using the first in-
line Ziegler
Natta catalyst formulation or the first batch Ziegler-Natta catalyst
formulation. The
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optional third ethylene interpolymer may be synthesized using a second in-line
Ziegler
Natta catalyst formulation or a second batch Ziegler-Natta catalyst
formulation.
Embodiments of this disclosure include caps and closures containing an
ethylene interpolymer product, where the ethylene interpolymer product has 5 1
part
per million (ppm) of a metal A; where metal A originates from the single-site
catalyst
formulation; non-limiting examples of metal A include titanium, zirconium or
hafnium.
Further embodiments include caps and closures containing an ethylene
interpolymer product having a metal B and optionally a metal C; where the
total amount
of metal B and metal C is from about 3 to about 11 parts per million (ppm);
where metal
.. B originates from a first heterogeneous catalyst formulation and metal C
originates form
an optional second heterogeneous catalyst formation. Metals B and C are
independently selected from the following non-limiting examples: titanium,
zirconium,
hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten,
manganese,
technetium, rhenium, iron, ruthenium or osmium. Metals B and C may be the same
metal.
Additional embodiments of caps and closures contain ethylene interpolymer
products where the first ethylene interpolymer has a first Mw/Mn, the second
ethylene
interpolymer has a second Mw/Mn and the optional third ethylene has a third
Mw/Mn;
where the first Mw/Mn is lower than the second Mw/Mn and the optional third
Mw/Mn.
Embodiments also include ethylene interpolymer products where the blending of
the
second ethylene interpolymer and the third ethylene interpolymer form an
ethylene
interpolymer blend having a fourth Mw/Mn; where the fourth Mw/Mn is not
broader than
the second Mw/Mn. Additional ethylene interpolymer product embodiments are
characterized as having both the second Mw/Mn and the third Mw/Mn less than
about
4Ø
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Further, embodiments of caps and closures include ethylene interpolymer
products where the first ethylene interpolymer has a first CDBI50 from about
70 to about
98%, the second ethylene interpolymer has a second CDBI50 from about 45 to
about
98% and the optional third ethylene interpolymer has a third CDB150from about
35 to
about 98%. Other embodiments include ethylene interpolymer products where the
first
CDBI50 is higher than the second CDBI50; optionally the first CDBI50 is higher
than the
third CDBI50.
Embodiments also include cap and closures having a melt index from 0.4
dg/min to 5. 5.0 dg/min and a G'[@G"=500 Pa] from 40 Pa to 5. 70 Pa.
Additional
embodiments include caps and closures having a melt index from > 5.0 dg/min to
5. 20
dg/min and a G'[@G"=500 Pa] from 1 Pa to 5 35 Pa. Additional embodiments
include
caps and closures having a melt index from > 0.3 dg/min to 5 7 dg/min and a
G'[@G"=500 Pa] from 80 Pa to 5. 120 Pa.
Finally, a process to manufacture any one of the cap and closure embodiments
described above is disclosed, where the process comprises at least one
compression
molding step or one injection molding step.
Brief Description of Figures
The following Figures are presented for the purpose of illustrating selected
embodiments of this disclosure; it being understood, that the embodiments
shown do
not limit this disclosure.
Figure 1 plots G'[@G"=500 Pa] versus melt index of ethylene interpolymer
products Examples 1001 and 1002, Example 81 and 91; as well as Comparatives Q,
V,
R, Y and X. Examples 1001 and 1002 and Examples 81 and 91 (solid symbols) are
examples of ethylene interpolymer products disclosed herein. Comparatives Q
and R
are comparative caps and closure HDPE resins available from NOVA Chemicals
Inc.;
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CCs153 (0.9530 gcm3, 1.4 dg/min) and CCs757 (0.9589 g/cm3, 6.7 dg/min),
respectively, produced in a dual reactor solution process using a single-site
catalyst.
Comparative V is a commercial caps and closure HDPE resin available from The
Dow
Chemical Company, Continuum DMDA-1250 NT 7(0.957 g/cm3, 1.5 dg/min), produced
.. in a dual reactor gas phase process using a Ziegler-Natta catalyst.
Comparative X and
Y are a commercial caps and closure HDPE resins available from INEOS Olefins &
Polymers USA; INEOS HDPE J50-1000-178 (0.951 g/cm3, 11 dg/min) and INEOS
HDPE J60-800-178 (0.961 g/cm3, 7.9 dg/min), respectively.
Figure 2 is a plot of Dilution Index (Yd) ( having dimensions of degrees ( ))
and
Dimensionless Modulus (Xd) for:
Comparative S (open triangle, Yd = Xd = 0) is an ethylene interpolymer
comprising an ethylene interpolymer synthesized using an in-line Ziegler-Natta
catalyst in a solution process (rheological reference);
Examples 6, 101, 102, 103, 110, 115, 200, 201 (solid circle, Yd > 0 and Xd <0)
are ethylene interpolymer products as described in this disclosure comprising
a
first ethylene interpolymer synthesized using a single-site catalyst
formulation
and a second ethylene interpolymer synthesized using an in-line Ziegler-Natta
catalyst formulation in a solution process;
Examples 120, 130 and 131 (solid square, Yd > 0, Xd > 0) are ethylene
interpolymer products as described in this disclosure;
Comparatives D and E (open diamond, Yd < 0, Xd > 0) are ethylene
interpolymers comprising a first ethylene interpolymer synthesized using a
single-site catalyst formation and a second ethylene interpolymer synthesized
using a batch Ziegler-Natta catalyst formulation in a solution process; and
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Comparative A (open square, Yd > 0 and Xd <0) is an ethylene interpolymer
comprising a first and second ethylene interpolymer synthesized using a single-
site catalyst formation in a solution process.
Figure 3 illustrates a typical Van Gurp Palmen (VGP) plot of phase angle [O]
versus complex modulus [kPa].
Figure 4 plots the Storage modulus (G') and loss modulus (G") showing the
cross over frequency (ox and the two decade shift in phase angle to reach (0c
(0)c = 0.01
cox).
Figure 5 compares the amount of terminal vinyl unsaturations per 100 carbon
atoms (terminal vinyl/100 C) in the ethylene interpolymer products of this
disclosure
(solid circles) with Comparatives B, C, E, E2, G, H, H2, I and J (open
triangles).
Figure 6 compares the amount of total catalytic metal (ppm) in the ethylene
interpolymer products of this disclosure (solid circles) with Comparatives B,
C, E, E2, G,
H, H2, I and J (open triangles).
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
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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.
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.
The term "Dilution Index (Yd)" and "Dimensionless Modulus (Xd)" are based on
rheological measurements and are fully described in this disclosure.
The term "Gl@G"=500 Par (Pa) is a rheological measurement, i.e. the value of
the storage modulus G' (Pa) where the loss modulus G" is equal to 500 Pa.
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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.
As used herein, the term "ethylene polymer", refers to macromolecules produced
from ethylene monomers and optionally one or more additional monomers;
regardless
of the specific catalyst or specific process used to make the ethylene
polymer. In the
polyethylene art, the one or more additional monomers are called
"comonomer(s)" and
often include a-olefins. The term "homopolymer" refers to a polymer that
contains only
one type of monomer. Common ethylene polymers include high density
polyethylene
(HDPE), medium density polyethylene (MDPE), linear low density 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 (LOPE), ethylene vinyl acetate copolymers
(EVA),
ethylene alkyl acrylate copolymers, ethylene acrylic acid copolymers and metal
salts of
ethylene acrylic acid (commonly referred to as ionomers). The term ethylene
polymer
also includes block copolymers which may include 2 to 4 comonomers. The term
ethylene polymer also includes combinations of, or blends of, the ethylene
polymers
described above.
The term "ethylene interpolymer" refers to a subset of polymers within the
"ethylene polymer" group that excludes polymers produced in high pressure
polymerization processes; non-limiting examples of polymers produced in high
pressure
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processes include LDPE and EVA (the latter is a copolymer of ethylene and
vinyl
acetate).
The term "heterogeneous ethylene interpolymers" refers to a subset of polymers
in the ethylene interpolymer group that are produced using a heterogeneous
catalyst
formulation; non-limiting examples of which include Ziegler-Natta or chromium
catalysts.
The term "homogeneous ethylene interpolymer" refers to a subset of polymers in
the ethylene interpolymer group that are produced using metallocene or single-
site
catalysts. Typically, homogeneous ethylene interpolymers have narrow molecular
weight distributions, for example gel permeation chromatography (GPC) 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
C0BI50 of an ethylene interpolymer can be calculated from TREF curves
(Temperature
Rising Elution Fractionation); the TREF method is described in Wild, et al.,
J. Polym.
Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455. Typically the CDBI50
of
homogeneous ethylene interpolymers are greater than about 70%. In contrast,
the
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CDBI60 of a-olefin containing heterogeneous ethylene interpolymers are
generally lower
than the CDBI50 of homogeneous ethylene interpolymers.
It is well known to those skilled in the art, that homogeneous ethylene
interpolymers are frequently further subdivided into "linear homogeneous
ethylene
interpolymers" and "substantially linear homogeneous ethylene interpolymers."
These
two subgroups differ in the amount of long chain branching: more specifically,
linear
homogeneous ethylene interpolymers have less than about 0.01 long chain
branches
per 1000 carbon atoms; while substantially linear ethylene interpolymers 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. Hereafter, in this disclosure, the term
"homogeneous
ethylene interpolymer" refers to both linear homogeneous ethylene
interpolymers and
substantially linear homogeneous ethylene interpolymers.
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 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 commonly used in the plastic
industry;
non-limiting examples of other polymers commonly used include barrier resins
(EVOH),
tie resins, polyethylene terephthalate (PET), polyamides and the like.
As used herein the term "monolayer" refers a cap or closure where the wall
structure comprises a single layer.
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As used herein, the terms "hydrocarbyl'', "hydrocarbyl radical" or
"hydrocarbyl
group" refers to linear 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.
Herein the term "R1" and its superscript form "R" refers to a first reactor in
a
continuous solution polymerization process; it being understood that R1 is
distinctly
different from the symbol R1; the latter is used in chemical formula, e.g.
representing a
hydrocarbyl group. Similarly, the term "R2" and it's superscript form "R2"
refers to a
second reactor; and the term "R3" and it's superscript form "R3" refers to a
third reactor.
DETAILED DESCRIPTION
Catalysts
Organometallic catalyst formulations that are efficient in polymerizing
olefins are
well known in the art. In the embodiments disclosed herein, at least two
catalyst
formulations are employed in a continuous solution polymerization process. One
of the
catalyst formulations is a single-site catalyst formulation that produces a
first ethylene
interpolymer. The other catalyst formulation is a heterogeneous catalyst
formulation
that produces a second ethylene interpolymer. Optionally a third ethylene
interpolymer
is produced using the heterogeneous catalyst formulation that was used to
produce the
second ethylene interpolymer, or a different heterogeneous catalyst
formulation may be
used to produce the third ethylene interpolymer. In the continuous solution
process, the
at least one homogeneous ethylene interpolymer and the at least one
heterogeneous
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ethylene interpolymer are solution blended and an ethylene interpolymer
product is
produced.
Single Site Catalyst Formulation
The catalyst components which make up the single site catalyst formulation are
not particularly limited, i.e. a wide variety of catalyst components can be
used. One
non-limiting embodiment of a single site catalyst formulation comprises the
following
three or four components: a bulky ligand-metal complex; an alumoxane co-
catalyst; an
ionic activator and optionally a hindered phenol. In Table 2A of this
disclosure: "(i)"
refers to the amount of "component (i)", i.e. the bulky ligand-metal complex
added to
R1; "(ii)" refers to "component (ii)", i.e. the alumoxane co-catalyst; "(iii)"
refers to
"component (iii)" i.e. the ionic activator; and "(iv)" refers to "component
(iv)", i.e. the
optional hindered phenol.
Non-limiting examples of component (i) are represented by formula (I):
(LA)aM(PI)b(Q)n (I)
wherein (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 the bulky ligand LA in formula (I) include
unsubstituted
or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands,
heteroatom
substituted and/or heteroatom containing cyclopentadienyl-type ligands.
Additional
non-limiting examples include, cyclopentaphenanthreneyl ligands, unsubstituted
or
substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted
fluorenyl
ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,
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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 rl-bonding to the metal M, such embodiments include both
113-
bonding and r15-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.
Non-limiting examples of metal M in formula (I) include Group 4 metals,
titanium,
zirconium and hafnium.
The phosphinimine ligand, PI, is defined by formula (II):
(RP)3 P = N - (II)
wherein the RP groups are independently selected from: a hydrogen atom; a
halogen atom; C1-20 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 silyl 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 06-10 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.
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The leaving group Q is 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
Q is an "activatable ligand," i.e. equivalent to the term "leaving group." 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 (I)
represents a neutral bulky ligand-metal complex. Non-limiting examples of Q
ligands
include a hydrogen atom, halogens, C1-20 hydrocarbyl radicals, 01-20 alkoxy
radicals, 05-
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, 06-
10 aryl or
10 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 (i) of the single site catalyst formulation
include structural, optical or enantiomeric isomers (meso and racemic isomers)
and
mixtures thereof of the bulky ligand-metal complexes described in formula (I)
above.
The second single site catalyst component, component (ii), is an alumoxane co-
catalyst that activates component (i) to a cationic complex. An equivalent
term for
"alumoxane" is "aluminoxane"; although the exact structure of this co-catalyst
is
uncertain, subject matter experts generally agree that it is an oligomeric
species that
contain repeating units of the general formula (III):
(R)2A10-(Al(R)-0)n-Al(R)2 (III)
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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 is methyl alunninoxane (or MAO) wherein
each R
group in formula (III) is a methyl radical.
The third catalyst component (iii) of the single site catalyst formation is an
ionic
activator. In general, ionic activators are comprised of a cation and a bulky
anion;
wherein the latter is substantially non-coordinating. Non-limiting examples of
ionic
activators are boron ionic activators that are four coordinate with four
ligands bonded to
the boron atom. Non-limiting examples of boron ionic activators include the
following
formulas (IV) and (V) shown below;
[R5r[B(R7)4]- (IV)
where B represents a boron atom, R5 is an aromatic hydrocarbyl (e.g. triphenyl
methyl cation) and each R7 is independently selected from phenyl radicals
which are
unsubstituted or substituted with from 3 to 5 substituents selected from
fluorine atoms,
C1-4 alkyl or alkoxy radicals which are unsubstituted or substituted by
fluorine atoms;
and a silyl radical of formula -Si(R9)3, where each R9 is independently
selected from
hydrogen atoms and C1-4 alkyl radicals; and compounds of formula (V);
[(R8)tZH][B(R7)4]- (V)
where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus
atom, t is 2 or 3 and R8 is selected from C1-8 alkyl radicals, phenyl radicals
which are
unsubstituted or substituted by up to three C1-4 alkyl radicals, or one R8
taken together
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with the nitrogen atom may form an anilinium radical and R7 is as defined
above in
formula (IV).
In both formula (IV) and (V), a non-limiting example of R7 is 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 include: 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(nn,m-dimethylphenyl)boron, tributylammonium tetra(p-
trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron,
tri(n-
butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylaniliniunn tetra(phenyl)boron,
N,N-
diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-
butylboron, N,N-
2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium
tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron,
triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium
tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron,
tropillium
tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl
borate,
benzene(diazonium)tetrakispentafluorophenyl borate, tropillium
tetrakis(2,3,5,6-
tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-
tetrafluorophenyl)borate,
benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium
tetrakis(3,4,5 -
trifluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-
trifluorophenyl)borate,
tropillium tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium
tetrakis(1 ,2,2-
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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
tetrafluorophenyI)-
borate. Readily available commercial ionic activators include N,N-
dimethylanilinium
tetrakispentafluorophenyl borate, and triphenylmethylium
tetrakispentafluorophenyl
borate.
The optional fourth catalyst component of the single site catalyst formation
is a
hindered phenol, component (iv). Non-limiting example of hindered phenols
include
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.
To produce an active single site catalyst formulation the quantity and mole
ratios
of the three or four components, (i) through (iv) are optimized as described
below.
Heterogeneous Catalyst Formulations
A number of heterogeneous catalyst formulations are well known to those
skilled
in the art, including, as non-limiting examples, Ziegler-Natta and chromium
catalyst
formulations.
In this disclosure, embodiments include an in-line and batch Ziegler-Natta
catalyst formulations. The term "in-line Ziegler-Natta catalyst formulation"
refers to the
continuous synthesis of a small quantity of active Ziegler-Natta catalyst and
immediately injecting this catalyst into at least one continuously operating
reactor,
where the catalyst polymerizes ethylene and one or more optional a-olefins to
form an
ethylene interpolymer. The terms "batch Ziegler-Natta catalyst formulation" or
"batch
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Ziegler-Natta procatalyst" refer to the synthesis of a much larger quantity of
catalyst or
procatalyst in one or more mixing vessels that are external to, or isolated
from, the
continuously operating solution polymerization process. Once prepared, the
batch
Ziegler-Natta catalyst formulation, or batch Ziegler-Natta procatalyst, is
transferred to a
catalyst storage tank. The term "procatalyst" refers to an inactive catalyst
formulation
(inactive with respect to ethylene polymerization); the procatalyst is
converted into an
active catalyst by adding an alkyl aluminum co-catalyst. As needed, the
procatalyst is
pumped from the storage tank to at least one continuously operating reactor,
where an
active catalyst is formed and polymerizes ethylene and one or more optional a-
olefins
to form an ethylene interpolymer. The procatalyst may be converted into an
active
catalyst in the reactor or external to the reactor.
A wide variety of chemical compounds can be used to synthesize an active
Ziegler-Natta catalyst formulation. The following describes various chemical
compounds that may be combined to produce an active Ziegler-Natta catalyst
formulation. Those skilled in the art will understand that the embodiments in
this
disclosure are not limited to the specific chemical compound disclosed.
An active Ziegler-Natta catalyst formulation may be formed from: a magnesium
compound, a chloride compound, a metal compound, an alkyl aluminum co-catalyst
and an aluminum alkyl. In Table 2A of this disclosure: "(v)" refers to
"component (v)"
the magnesium compound; the term "(vi)" refers to the "component (vi)" the
chloride
compound; "(vii)" refers to "component (vii)" the metal compound; "(viii)"
refers to
"component (viii)" alkyl aluminum co-catalyst; and "(ix)" refers to "component
(ix)" 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.
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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 Ito 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)n; where M represents a metal selected from Group 4 through
Group 8
of the Periodic Table, or mixtures of metals selected from Group 4 through
Group 8; 0
represents oxygen; and X represents chloride or bromide; n is an integer from
3 to 6
that satisfies the oxidation state of the metal. Additional non-limiting
examples of
suitable metal compounds include Group 4 to Group 8 metal alkyls, metal
alkoxides
(which may be prepared by reacting a metal alkyl with an alcohol) and mixed-
ligand
metal compounds that contain a mixture of halide, alkyl and alkoxide ligands.
In the
third step a solution of an alkyl aluminum co-catalyst (component (viii)) is
added to the
metal compound supported on the magnesium chloride. A wide variety of alkyl
aluminum co-catalysts are suitable, as expressed by formula (VI):
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Al(R4)p(0R5)q(X)r (VI)
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.
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Solution Polymerization Process: In-line Heterogeneous Catalyst Formulation
The ethylene interpolymer products disclosed herein, useful in the manufacture
of flexible and rigid articles, were produced in a continuous solution
polymerization
process. This solution process has been fully described in Canadian Patent
Application
No. CA 2,868,640, filed October 21, 2014 and entitled "SOLUTION POLYMERIZATION
PROCESS."
Embodiments of this process includes at least two continuously stirred
reactors,
R1 and R2 and an optional tubular reactor R3. Feeds (solvent, ethylene, at
least two
catalyst formulations, optional hydrogen and optional a-olefin) are feed to at
least two
reactor continuously. A single site catalyst formulation is injected into R1
and a first
heterogeneous catalyst formation is injected into R2 and optionally R3.
Optionally, a
second heterogeneous catalyst formulation is injected into R3_ The single site
catalyst
formulation includes an ionic activator (component (iii)), a bulky ligand-
metal complex
(component (i)), an alumoxane co-catalyst (component (ii)) and an optional
hindered
phenol (component (iv)), respectively.
R1 and R2 may be operated in series or parallel modes of operation. To be
more clear, in series mode 100% of the effluent from R1 flows directly into
R2. In
parallel mode, R1 and R2 operate independently and the effluents from R1 and
R2 are
combined downstream of the reactors.
A heterogeneous catalyst formulation is injected into R2. In one embodiment a
first in-line Ziegler-Natta catalyst formulation is injected into R2. A first
in-line Ziegler-
Natta catalyst formation is formed within a first heterogeneous catalyst
assembly by
optimizing the following molar ratios: (aluminum alkyl)/(magnesium compound)
or
(ix)/(v); (chloride cornpound)/(magnesium compound) or (vi)/(v); (alkyl
aluminum co-
catalyst)/(metal compound) or (viii)/(vii); and (aluminum alkyl)/(metal
compound) or
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CA 02957706 2017-02-13
(ix)/(vii); as well as the time these compounds have to react and equilibrate.
Within the
first heterogeneous catalyst assembly the time between the addition of the
chloride
compound and the addition of the metal compound (component (vii)) is
controlled;
hereafter HUT-1 (the first Hold-Up-Time). The time between the addition of
component
(vii) and the addition of the alkyl aluminum co-catalyst, component (viii), is
also
controlled; hereafter HUT-2 (the second Hold-Up-Time). 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 R2 is controlled; hereafter HUT-3 (the third
Hold-Up-
Time). Optionally, 100% the alkyl aluminum co-catalyst, may be injected
directly into
R2. Optionally, a portion of the alkyl aluminum co-catalyst may be injected
into the first
heterogeneous catalyst assembly and the remaining portion injected directly
into R2.
The quantity of in-line heterogeneous catalyst formulation added to R2 is
expressed as
the parts-per-million (ppm) of metal compound (component (vii)) in the reactor
solution,
hereafter "R2 (vii) (ppm)." Injection of the in-line heterogeneous catalyst
formulation
into R2 produces a second ethylene interpolymer in a second exit stream
(exiting R2).
Optionally the second exit stream is deactivated by adding a catalyst
deactivator. If the
second exit stream is not deactivated the second exit stream enters reactor
R3. One
embodiment of a suitable R3 design is a tubular reactor. Optionally, one or
more of the
following fresh feeds may be injected into R3; solvent, ethylene, hydrogen, a-
olefin and
a first or second heterogeneous catalyst formulation; the latter is supplied
from a
second heterogeneous catalyst assembly. The chemical composition of the first
and
second heterogeneous catalyst formulations may be the same, or different, i.e.
the
catalyst components ((v) through (ix)), mole ratios and hold-up-times may
differ in the
first and second heterogeneous catalyst assemblies. The second heterogeneous
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catalyst assembly generates an efficient catalyst by optimizing hold-up-times
and the
molar ratios of the catalyst components.
In reactor R3, a third ethylene interpolymer may, or may not, form. A third
ethylene interpolymer will not form if a catalyst deactivator is added
upstream of reactor
R3. A third ethylene interpolymer will be formed if a catalyst deactivator is
added
downstream of R3. The optional third ethylene interpolymer may be formed using
a
variety of operational modes (with the proviso that catalyst deactivator is
not added
upstream). Non-limiting examples of operational modes include: (a) residual
ethylene,
residual optional a-olefin and residual active catalyst entering R3 react to
form the third
ethylene interpolymer, or; (b) fresh process solvent, fresh ethylene and
optionally fresh
a-olefin are added to R3 and the residual active catalyst entering R3 forms
the third
ethylene interpolymer, or; (c) a second in-line heterogeneous catalyst
formulation is
added to R3 to polymerize residual ethylene and residual optional a-olefin to
form the
third ethylene interpolymer, or; (d) fresh process solvent, ethylene, optional
a-olefin and
a second in-line heterogeneous catalyst formulation are added to R3 to form
the third
ethylene interpolymer.
In series mode, R3 produces a third exit stream (the stream exiting R3)
containing the first ethylene interpolymer, the second ethylene interpolymer
and
optionally a third ethylene interpolymer. A catalyst deactivator may be added
to the
third exit stream producing a deactivated solution, with the proviso a
catalyst
deactivator is not added if a catalyst deactivator was added upstream of R3.
The deactivated solution passes through a pressure let down device, a heat
exchanger and a passivator is added forming a passivated solution. The
passivated
solution passes through a series of vapor liquid separators and ultimately the
ethylene
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interpolymer product enters polymer recover. 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.
Embodiments of the manufactured articles disclosed herein, may also be formed
from ethylene interpolymer products synthesized using a batch Ziegler-Natta
catalyst.
Typically, a first batch Ziegler-Natta procatalyst is injected into R2 and the
procatalyst is
activated within R2 by injecting an alkyl aluminum co-catalyst forming a first
batch
Ziegler-Natta catalyst. Optionally, a second batch Ziegler-Natta procatalyst
is injected
into R3.
Additional Solution Polymerization Process Parameters
A variety of solvents may be used as the process solvent; non-limiting
examples
include linear, branched or cyclic C5 to Ci2 alkanes. Non-limiting examples of
a-olefins
include 03 to Cio a-olefins. It is well known to individuals of ordinary
experience 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.
In operating the continuous solution polymerization process total amount of
ethylene supplied to the process can be portioned or split between the three
reactors
RI, R2 and R3. This operational variable is referred to as the Ethylene Split
(ES), i.e.
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"ESR1", "ESR2" and "ESR3" refer to the weight percent of ethylene injected in
R1, R2 and
R3, respectively, with the proviso that ESR1+ ESR2+ ESR3 = 100%. The ethylene
concentration in each reactor is also controlled. The R1 ethylene
concentration is
defined as the weight of ethylene in reactor 1 divided by the total weight of
everything
added to reactor 1; the R2 ethylene concentration (wt%) and R3 ethylene
concentration
(wt%) are defined similarly. The total amount of ethylene converted in each
reactor is
monitored. The term "Qm" refers to the percent of the ethylene added to R1
that is
converted into an ethylene interpolymer by the catalyst formulation. Similarly
0' and
QR3 represent the percent of the ethylene added to R2 and R3 that was
converted into
ethylene interpolymer, in the respective reactor. 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 product]+[weight of unreacted ethylene]). 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 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%.
In the continuous polymerization processes described, polymerization is
terminated by adding a catalyst deactivator. The catalyst deactivator
substantially
stops the polymerization reaction by changing active catalyst species to
inactive forms.
Suitable deactivators are well known in the art, non-limiting examples
include: amines
(e.g. U.S. Pat. No. 4,803,259 to Zboril et al.); alkali or alkaline earth
metal salts of
carboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.); water (e.g.
U.S. Pat. No.
.. 4,731,438 to Bernier et al.); hydrotalcites, alcohols and carboxylic acids
(e.g. U.S. Pat.
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No. 4,379,882 to Miyata); or a combination thereof (U.S. Pat No. 6,180,730 to
Sibtain et
al.).
Prior to entering the vapor/liquid separator, a passivator or acid scavenger
is
added to deactivated solution. Suitable passivators are well known in the art,
non-
limiting examples include alkali or alkaline earth metal salts of carboxylic
acids or
hydrotalcites.
In this disclosure, the number of solution reactors is not particularly
important,
with the proviso that the continuous solution polymerization process comprises
at least
two reactors that employ at least one single-site catalyst formulation and at
least one
heterogeneous catalyst formulation.
First Ethylene Interpolymer
The first ethylene interpolymer is produced with a single-site catalyst
formulation.
If the optional a-olefin is not added to reactor 1 (R1), then the ethylene
interpolymer
produced in R1 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 symbol "al" refers to the density of the first
ethylene
interpolymer produced in R1. The upper limit on al may be about 0.975 g/cm3;
in some
cases about 0.965 g/cm3; and in other cases about 0.955 g/cm3. The lower limit
on al
may be about 0.855 g/cm3; in some cases about 0.865 g/cm3; and in other cases
about
0.875 g/cm3.
Methods to determine the CDBI50 (Composition Distribution Branching Index) of
an ethylene interpolymer are well known to those skilled in the art. The
CDBI50,
expressed as a percent, is defined as the percent of the ethylene interpolymer
whose
comonomer composition is within 50% of the median comonomer composition. It is
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also well known to those skilled in the art that the CDBI50 of ethylene
interpolymers
produced with single-site 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
(produced
with a single-site catalyst formulation) may be about 98%, in other cases
about 95%
and in still other cases about 90%. The lower limit on the CDB150 of the first
ethylene
interpolymer may be about 70%, in other cases about 75% and in still other
cases
about 80%.
As is well known to those skilled in the art the Mw/Mn of ethylene
interpolymers
produced with single site catalyst formulations are lower relative to ethylene
interpolymers produced with heterogeneous catalyst formulations. Thus, in the
embodiments disclosed, the first ethylene interpolymer has a lower Mw/Mn
relative to
the second ethylene interpolymer, where the second ethylene interpolymer is
produced
with a heterogeneous catalyst formulation. The upper limit on the Mw/Mn of the
first
ethylene interpolymer may be about 2.8, in other cases about 2.5 and in still
other
cases about 2.2. The lower limit on the Mw/Mn the first ethylene interpolymer
may be
about 1.7, in other cases about 1.8 and in still other cases about 1.9.
The first ethylene interpolymer contains catalyst residues that reflect the
chemical composition of the single-site catalyst formulation used. Those
skilled in the
art will understand that catalyst residues are typically quantified by the
parts per million
of metal in the first ethylene interpolymer, where metal refers to the metal
in component
(i), i.e. the metal in the "bulky ligand-metal complex;" hereafter (and in the
claims) this
metal will be referred to "metal A." As recited earlier in this disclosure,
non-limiting
examples of metal A include Group 4 metals, titanium, zirconium and hafnium.
The
upper limit on the ppm of metal A in the first ethylene interpolymer may be
about 1.0
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ppm, in other cases about 0.9 ppm and in still other cases about 0.8 ppm. The
lower
limit on the ppm of metal A in the first ethylene interpolymer may be about
0.01 ppm, in
other cases about 0.1 ppm and in still other cases about 0.2 ppm.
The amount of hydrogen added to R1 can vary over a wide range allowing the
continuous solution process to produce first ethylene interpolymers that
differ greatly in
melt index, hereafter 121 (melt index is measured at 190 C using a 2.16 kg
load
following the procedures outlined in ASTM D1238). The quantity of hydrogen
added to
R1 is expressed as the parts-per-million (ppm) of hydrogen in R1 relative to
the total
mass in reactor R1; hereafter H211 (ppm). The upper limit on 121 may be about
200
.. dg/min, in some cases about 100 dg/min; in other cases about 50 dg/min; and
in still
other cases about 1 dg/min. The lower limit on 121 may be about 0.01 dg/min;
in some
cases about 0.05 dg/min; in other cases about 0.1 dg/min; and in still other
cases about
0.5 dg/min.
The upper limit on the weight percent (wt%) of the first ethylene interpolymer
in
the ethylene interpolymer product may be about 60 wt%, in other cases about 55
wt%
and in still other cases about 50 wt%. The lower limit on the wt % of the
first ethylene
interpolymer in the ethylene interpolymer product may be about 15 wt%, in
other cases
about 25 wt%, and in still other cases about 30 wt%.
Second Ethylene Interpolymer
If optional a-olefin is not added to reactor 2 (R2) either by adding fresh a-
olefin
to R2 (or carried over from R1) then the ethylene interpolymer produced in R2
is an
ethylene homopolymer. If an optional a-olefin is present in R2, the following
weight
ratio is one parameter to control the density of the second ethylene
interpolymer
produced in R2: ((a-olefin)/(ethylene))R2. Hereafter, the symbol "a2" refers
to the
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density of the ethylene interpolymer produced in R2. The upper limit on cy2
may be
about 0.975 g/cm3; in some cases about 0.965 g/cm3; and in other cases about
0.955
g/cm3. Depending on the heterogeneous catalyst formulation used, the lower
limit on
G2 may be about 0.89 g/cm3; in some cases about 0.90 g/cm3; and in other cases
about
0.91 g/cm3.
A heterogeneous catalyst formulation is used to produce the second ethylene
interpolymer. If the second ethylene interpolymer contains an a-olefin, the
CDBI50 of
the second ethylene interpolymer is lower relative to the CDBI50 of the first
ethylene
interpolymer that was produced with a single-site catalyst formulation. In an
embodiment of this disclosure, the upper limit on the CDBI50 of the second
ethylene
interpolymer (that contains an a-olefin) may be about 70%, in other cases
about 65%
and in still other cases about 60%. In an embodiment of this disclosure, the
lower limit
on the CDBI50 of the second ethylene interpolymer (that contains an a-olefin)
may be
about 45%, in other cases about 50% and in still other cases about 55%. If an
a-olefin
is not added to the continuous solution polymerization process the second
ethylene
interpolymer is an ethylene homopolymer. In the case of a homopolymer, which
does
not contain a-olefin, one can still measure a CDBI50 using TREF. In the case
of a
homopolymer, the upper limit on the CDBI50 of the second ethylene interpolymer
may
be about 98%, in other cases about 96% and in still other cases about 95%. The
lower
limit on the CDBI50 may be about 88%, in other cases about 89% and in still
other
cases about 90%. It is well known to those skilled in the art that as the a-
olefin content
in the second ethylene interpolymer approaches zero, there is a smooth
transition
between the recited C0BI50 limits for the second ethylene interpolymers (that
contain an
a-olefin) and the recited CDBI50 limits for the second ethylene interpolymers
that are
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ethylene homopolymers. Typically, the CDBI50 of the first ethylene
interpolymer is
higher than the CDBI50 of the second ethylene interpolymer.
The Mw/Mn of second ethylene interpolymer is higher than the Mw/Mn of the
first
ethylene interpolymer. The upper limit on the Mw/Mn of the second ethylene
interpolymer may be about 4.4, in other cases about 4.2 and in still other
cases about
4Ø The lower limit on the Mw/Mn of the second ethylene interpolymer may be
about
2.2. Mw/Mn's of 2.2 are observed when the melt index of the second ethylene
interpolymer is high, or when the melt index of the ethylene interpolymer
product is
high, e.g. greater than 10 g/10 minutes. In other cases the lower limit on the
Mw/Mn of
the second ethylene interpolymer may be about 2.4 and in still other cases
about 2.6.
The second ethylene interpolymer contains catalyst residues that reflect the
chemical composition of heterogeneous catalyst formulation. Those skilled in
the art
will understand that heterogeneous catalyst residues are typically quantified
by the
parts per million of metal in the second ethylene interpolymer, where the
metal refers to
.. the metal originating from component (vii), i.e. the "metal compound;"
hereafter (and in
the claims) this metal will be referred to as "metal B." As recited earlier in
this
disclosure, non-limiting examples of metal B include metals selected from
Group 4
through Group 8 of the Periodic Table, or mixtures of metals selected from
Group 4
through Group 8. The upper limit on the ppm of metal B in the second ethylene
interpolymer may be about 12 ppm, in other cases about 10 ppm and in still
other cases
about 8 ppm. The lower limit on the ppm of metal B in the second ethylene
interpolymer may be about 0.5 ppm, in other cases about 1 ppm and in still
other cases
about 3 ppm. While not wishing to be bound by any particular theory, in series
mode of
operation it is believed that the chemical environment within the second
reactor
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deactivates the single site catalyst formulation, or; in parallel mode of
operation the
chemical environment within R2 deactivates the single site catalyst formation.
The amount of hydrogen added to R2 can vary over a wide range which allows
the continuous solution process to produce second ethylene interpolymers that
differ
greatly in melt index, hereafter 122. The quantity of hydrogen added is
expressed as the
parts-per-million (ppm) of hydrogen in R2 relative to the total mass in
reactor R2;
hereafter H2R2 (ppm). The upper limit on 122 may be about 1000 dg/min; in some
cases
about 750 dg/min; in other cases about 500 dg/min; and in still other cases
about 200
dg/min. The lower limit on 122 may be about 0.3 dg/min, in some cases about
0.4
dg/min, in other cases about 0.5 dg/min, and in still other cases about 0.6
dg/min.
The upper limit on the weight percent (wt%) of the second ethylene
interpolymer
in the ethylene interpolymer product may be about 85 wt%, in other cases about
80
wt% and in still other cases about 70 wt%. The lower limit on the wt % of the
second
ethylene interpolymer in the ethylene interpolymer product may be about 30
wt%; in
other cases about 40 wt% and in still other cases about 50 wt%.
Third Ethylene Interpolymer
A third ethylene interpolymer is not produced in R3 if a catalyst deactivator
is
added upstream of R3. If a catalyst deactivator is not added and optional a-
olefin is not
present then the third ethylene interpolymer produced in R3 is an ethylene
homopolymer. If a catalyst deactivator is not added and optional a-olefin is
present in
R3, the following weight ratio determines the density of the third ethylene
interpolymer:
((a-olefin)/(ethylene))R3. In the continuous solution polymerization process
((a-
olefin)/(ethylene))R3 is one of the control parameter used to produce a third
ethylene
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interpolymer with a desired density. Hereafter, the symbol "u3" refers to the
density of
the ethylene interpolymer produced in R3. The upper limit on 63 may be about
0.975
9/cm3; in some cases about 0.965 g/cm3; and in other cases about 0.955 g/cm3.
Depending on the heterogeneous catalyst formulations used, the lower limit on
cy3 may
be about 0.89 g/cm3, in some cases about 0.90 9/cm3; and in other cases about
0.91
9/cm3. Optionally, a second heterogeneous catalyst formulation may be added to
R3.
Typically, the upper limit on the CDBI50 of the optional third ethylene
interpolymer
(containing an a-olefin) may be about 65%, in other cases about 60% and in
still other
cases about 55%. The CDBI50 of an a-olefin containing optional third ethylene
.. interpolymer will be lower than the CDBI50 of the first ethylene
interpolymer produced
with the single-site catalyst formulation. Typically, the lower limit on the
CDBI50 of the
optional third ethylene interpolymer (containing an a-olefin) may be about
35%, in other
cases about 40% and in still other cases about 45%. If an c'-olefin is not
added to the
continuous solution polymerization process the optional third ethylene
interpolymer is
.. an ethylene homopolymer. In the case of an ethylene homopolymer the upper
limit on
the CDBI50 may be about 98%, in other cases about 96% and in still other cases
about
95%. The lower limit on the CDBI50 may be about 88%, in other cases about 89%
and
in still other cases about 90%. Typically, the CDBI50 of the first ethylene
interpolymer is
higher than the CDBI50 of the third ethylene interpolymer and second ethylene
interpolymer.
The upper limit on the Mw/Mn of the optional third ethylene interpolymer may
be
about 5.0, in other cases about 4.8 and in still other cases about 4.5. The
lower limit on
the Mw/Mn of the optional third ethylene interpolymer may be about 2.2, in
other cases
about 2.4 and in still other cases about 2.6. The Mw/Mn of the optional third
ethylene
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interpolymer is higher than the Mw/Mn of the first ethylene interpolymer. When
blended
together, the second and third ethylene interpolymer have a fourth Mw/Mn which
is not
broader than the Mw/Mn of the second ethylene interpolymer.
The catalyst residues in the optional third ethylene interpolymer reflect the
chemical composition of the heterogeneous catalyst formulation(s) used, i.e.
the first
and optionally a second heterogeneous catalyst formulation. The chemical
compositions of the first and second heterogeneous catalyst formulations may
be the
same or different; for example a first component (vii) and a second component
(vii) may
be used to synthesize the first and second heterogeneous catalyst formulation.
As
recited above, "metal B" refers to the metal that originates from the first
component (vii).
Hereafter, "metal C" refers to the metal that originates from the second
component (vii).
Metal B and optional metal C may be the same, or different. Non-limiting
examples of
metal B and metal C include metals selected from Group 4 through Group 8 of
the
Periodic Table, or mixtures of metals selected from Group 4 through Group 8.
The
upper limit on the ppm of (metal B + metal C) in the optional third ethylene
interpolymer
may be about 12 ppm, in other cases about 10 ppm and in still other cases
about 8
ppm. The lower limit on the ppm of (metal B + metal C) in the optional third
ethylene
interpolymer may be about 0.5 ppm, in other cases about 1 ppm and in still
other cases
about 3 ppm.
Optionally hydrogen may be added to R3. Adjusting the amount of hydrogen in
R3, hereafter H2R3 (ppm), allows the continuous solution process to produce
third
ethylene interpolymers that differ widely in melt index, hereafter 123. The
upper limit on
123 may be about 2000 dg/min; in some cases about 1500 dg/min; in other cases
about
1000 dg/min; and in still other cases about 500 dg/min. The lower limit on 123
may be
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about 0.5 dg/min, in some cases about 0.6 dg/min, in other cases about 0.7
dg/min,
and in still other cases about 0.8 dg/min.
The upper limit on the weight percent (wt%) of the optional third ethylene
interpolymer in the ethylene interpolymer product may be about 30 wt%, in
other cases
about 25 wt% and in still other cases about 20 wt%. The lower limit on the wt
% of the
optional third ethylene interpolymer in the ethylene interpolymer product may
be 0 wt%,
in other cases about 5 wt% and in still other cases about 10 wt%.
Ethylene Interpolymer Product
The upper limit on the density of the ethylene interpolymer product suitable
for
caps or closures about 0.970 g/cm3; in some cases about 0.969 g/cm3; and in
other
cases about 0.968 g/cm3. The lower limit on the density of the ethylene
interpolymer
product suitable for caps or closures may be about 0.945 g/cm3; in some cases
about
0.947 g/cm3; and in other cases about 0.948 g/cm3.
The upper limit on the CDBI50 of the ethylene interpolymer product may be
about
97%, in other cases about 90% and in still other cases about 85%. An ethylene
interpolymer product with a CDBI50 of 97% may result if an a-olefin is not
added to the
continuous solution polymerization process; in this case, the ethylene
interpolymer
product is an ethylene homopolymer. The lower limit on the CDBI50 of an
ethylene
interpolymer may be about 50%, in other cases about 55% and in still other
cases
about 60%.
The upper limit on the Mw/Mn of the ethylene interpolymer product may be about
6, in other cases about 5 and in still other cases about 4. The lower limit on
the Mw/Mn
of the ethylene interpolymer product may be 2.0, in other cases about 2.2 and
in still
other cases about 2.4.
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The catalyst residues in the ethylene interpolymer product reflect the
chemical
compositions of: the single-site catalyst formulation employed in R1; the
first
heterogeneous catalyst formulation employed in R2; and optionally the first or
optionally
the first and second heterogeneous catalyst formulation employed in R3. In
this
.. disclosure, catalyst residues were quantified by measuring the parts per
million of
catalytic metal in the ethylene interpolymer products. In addition, the
elemental
quantities (ppm) of magnesium, chlorine and aluminum were quantified.
Catalytic
metals originate from two or optionally three sources, specifically: 1) "metal
A" that
originates from component (i) that was used to form the single-site catalyst
formulation;
.. (2) "metal B" that originates from the first component (vii) that was used
to form the first
heterogeneous catalyst formulation; and (3) optionally "metal C" that
originates from the
second component (vii) that was used to form the optional second heterogeneous
catalyst formulation. Metals A, B and C may be the same or different. In this
disclosure
the term "total catalytic metal" is equivalent to the sum of catalytic metals
A+B+C.
Further, in this disclosure the terms "first total catalytic metal" and
"second total catalyst
metal" are used to differentiate between the first ethylene interpolymer
product of this
disclosure and a comparative "polyethylene composition" that were produced
using
different catalyst formulations.
The upper limit on the ppm of metal A in the ethylene interpolymer product may
be about 0.6 ppm, in other cases about 0.5 ppm and in still other cases about
0.4 ppm.
The lower limit on the ppm of metal A in the ethylene interpolymer product may
be
about 0.001 ppm, in other cases about 0.01 ppm and in still other cases about
0.03
ppm. The upper limit on the ppm of (metal B + metal C) in the ethylene
interpolymer
product may be about 11 ppm, in other cases about 9 ppm and in still other
cases
about 7 ppm. The lower limit on the ppm of (metal B + metal C) in the ethylene
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interpolymer product may be about 0.5 ppm, in other cases about 1 ppm and in
still
other cases about 3 ppm.
In some embodiments, ethylene interpolymers may be produced where the
catalytic metals (metal A, metal B and metal C) are the same metal; a non-
limiting
example would be titanium. In such embodiments, the ppm of (metal B + metal C)
in
the ethylene interpolymer product is calculated using equation (VII):
ppm') = ((ppm(A+B+c)_ (fA x ppmpv¨
( r ) (VII)
where: ppm(B) is the calculated ppm of (metal B + metal C) in the ethylene
interpolymer product; ppm() is the total ppm of catalyst residue in the
ethylene
interpolymer product as measured experimentally, i.e. (metal A ppm + metal B
ppm +
metal C ppm); fA represents the weight fraction of the first ethylene
interpolymer in the
ethylene interpolymer product, fA may vary from about 0.15 to about 0.6; and
ppmA
represents the ppm of metal A in the first ethylene interpolymer. In equation
(VII) ppm'
is assumed to be 0.35 ppm.
Embodiments of the ethylene interpolymer products disclosed herein have lower
catalyst residues relative to the polyethylene polymers described in US
6,277,931.
Higher catalyst residues in U.S. 6,277,931 increase the complexity of the
continuous
solution polymerization process; an example of increased complexity includes
additional purification steps to remove catalyst residues from the polymer. In
contrast,
in the present disclosure, catalyst residues are not removed. In this
disclosure, the
upper limit on the "total catalytic metal," i.e. the total ppm of (metal A ppm
+ metal B
ppm + optional metal C ppm) in the ethylene interpolymer product may be about
11
ppm, in other cases about 9 ppm and in still other cases about 7. The lower
limit on the
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total ppm of catalyst residuals (metal A + metal B + optional metal C) in the
ethylene
interpolymer product may be about 0.5 ppm, in other cases about 1 ppm and in
still
other cases about 3 ppm.
The upper limit on melt index of the ethylene interpolymer product may be
about
15 dg/min; in some cases about 14 dg/min; in other cases about 12 dg/min; and
in still
other cases about 10 dg/min. The lower limit on the melt index of the ethylene
interpolymer product may be about 0.5 dg/min, in some cases about 0.6 dg/min;
in
other cases about 0.7 dg/min; and in still other cases about 0.8 dg/min.
For Area III ethylene interpolymer products, as shown in Figure 1, the upper
limit on the
melt index of the ethylene interpolymer product may be about 8 dg/min, in some
cases
about 7dg/min; in other cases about 5 dg/min; and in still other cases about 3
dg/min.
The lower limit on the melt index of the ethylene interpolymer product may be
about
0.3, in some cases about 0.4 dg/min, in some cases about 0.5 dg/min, in other
cases
about 0.6 dg/min, and in still other cases about 0.7 dg/min.
A computer generated ethylene interpolymer product is illustrated in Table 1.
This simulations was based on fundamental kinetic models (with kinetic
constants
specific for each catalyst formulation) as well as feed and reactor
conditions. The
simulation was based on the configuration of the solution pilot plant
described below,
which was used to produce the examples of ethylene interpolymer products
disclosed
herein. Simulated Example 13 was synthesized using a single-site catalyst
formulation
(PIC-1) in R1 and an in-line Ziegler-Natta catalyst formulation in R2 and R3.
Table 1
discloses a non-limiting example of the density, melt index and molecular
weights of the
first, second and third ethylene interpolymers produced in the three reactors
(R1, R2
and R3); these three interpolymers are combined to produce Simulated Example
13
(the ethylene polymer product). As shown in Table 1, the Simulated Example 13
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product has a density of 0.9169 g/cm3, a melt index of 1.0 dg/min, a branch
frequency
of 12.1 (the number of C6-branches per 1000 carbon atoms (1-octene comonomer))
and a Mw/Mn of 3.11. Simulated Example 13 comprises: a first, second and third
ethylene interpolymer having a first, second and third melt index of 0.31
dg/min, 1.92
dg/min and 4.7 dg/min, respectively; a first, second and third density of
0.9087 g/cm3,
0.9206 g/cm3 and 0.9154 9/cm3, respectively; a first, second and third Mw/Mn
of 2.03
Mw/Mn, 3.29 Mw/Mn and 3.28 Mw/Mn, respectively; and a first, second and third
CDBI50
of 90 to 95%, 55 to 60% and 45 to 55%, respectively. The simulated production
rate of
Simulated Example 13 was 90.9 kg/hr and the R3 exit temperature was 217.1 C.
Ethylene Interpolymer Products Suitable for Caps and Closures
Tables 2A through 2C summarize solution pilot plant process conditions used to
manufacture the following ethylene interpolymer products: Example 81 and
Comparative Example 20 had a target density of about 0.953 g/cm3 and a target
melt
index of about 1.5 dg/min; Example 91 and Comparative Example 30 had a target
density of about 0.958 g/cm3 and a target melt index of about 7.0 dg/min; and
Example
1001 and Example 1002 had a target density of about 0.955 g/cm3 and a target
melt
index of about 0.6 dg/min. Examples 81, 91, 1001 and 1002 were manufactured
using
a single-site catalyst formulation in reactor 1 and an in-line Ziegler-Natta
catalyst
formulation in reactor 2. Comparative Examples 20 and 30 were manufactured
using a
single-site catalyst formulation in both reactors 1 and 2. The production rate
of Example
81 was 15% higher relative to Comparative Example 20. The production rate of
Example 91 was 26% higher relative to Comparative Example 30. Examples (81,
91,
1001 and 1002) and Comparative Examples (20 and 30) were all produced with
reactor
1 and 2 configured in series, i.e. the effluent from reactor 1 flowed directly
into reactor
2. In all examples the comonomer used was 1-octene.
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Table 3 compares the physical properties of Example 81 with Comparatives Q
and V. Comparatives Q is a commercial caps and closure ethylene interpolymer
available from NOVA Chemicals Inc. designated CCs153-A (0.9530 gcm3 and 1.4
dg/min), which was produced in a dual reactor solution process using a single-
site
.. catalyst. Comparative V is a commercial caps and closure ethylene
interpolymer
available from The Dow Chemical Company, Continuum DMDA-1250 NT 7 (0.9550
g/cm3, 1.5 dg/min), produced in a dual reactor gas phase process using a
Ziegler-Natta
catalyst, which was produced in a dual reactor gas phase process using a batch
Ziegler-Natta catalyst formulation.
As shown in Figure 1, the rectangle defined by Area I, defines a melt index
region that ranges from about 0.4 dg/min to 5 5 dg/min. Within Area I, the
disclosed
ethylene interpolymer product, Example 81, has a value of G'[ G"=500Pa] that
is
desirable in the manufacture of caps and closures using compression molding
processes. Specifically, Example 81 has GI@G"=500Pa] values from 40 Pa to 5 70
.. Pa; and these values are intermediate between Comparative Q and Comparative
V.
Elaborating, polymer melt elasticity, as measured by the storage modulus G',
affects
the compression molding manufacturing process. Generally, the higher the G',
the
higher the die swell of a polymer melt. A melt index of less than 5 for
ethylene
interpolymers is useful in the production of caps and closures using
continuous
compression molding (CCM) processes. CCM uses a nozzle with a specified
diameter
to extrude a specific quantity of polymer melt, followed by high-speed knife
cutting to
form a molten pellet. The pellet is then placed into a mold and compression
molded to
form a closure. The proper die swell characteristics (controlled through the
proper
selection of the G' value), which is possessed by Example 81 are advantageous
in the
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selection of a nozzle and controlling die swell, thus improving the CCM
process, for
example, reducing or eliminating the undesirable phenomenon of pellet
bouncing.
Table 3 compares the physical properties of Example 91 with Comparatives R, Y
and X. Comparative R is a commercial caps and closure ethylene interpolymer
available from NOVA Chemicals Inc. designated CCs757 (0.9530 gcm3 and 1.4
dg/min), which was produced in a dual reactor solution process using a single-
site
catalyst. Comparatives Y and X are commercial caps and closure ethylene
interpolymer available from INEOS Olefins & Polymers USA; INEOS HDPE J50-1000-
178 and INEOS HDPE J60-800-178, respectively.
As shown in Figure 1, the rectangle defined by Area II, defines a melt index
region that ranges from > 5 dg/min to 5 20 dg/min. Within Area II, the
disclosed
ethylene interpolymer product, Example 91, has a value of Gl@G"=500Pa] that is
desirable in the manufacture of caps and closures using injection molding
processes.
Specifically, Example 91 has GI@G"=500Pa] values from .?. 1 Pa to 5 35 Pa; and
these
.. values are lower than Comparatives R, Y and X. Elaborating, higher melt
indexes (5 to
dg/min) are useful for cap and closure manufacturing in injection molding
processes,
i.e. higher melt indexes reduce residual stresses (crystallized into the part)
that may
cause warped surface within the cap or closure. Lower melt elasticity, as
indicated by
lower G' values, increases the degree of polymer chain relaxation, which
dissipates
20 residual stresses, allowing the production of caps and closures having
the required
shape and dimensions. Certainly, caps and closures having the expected
dimensions,
or the "as designed" dimensions, are advantageous in downstream processing;
e.g. in
downstream processes where bottles are filled and the cap or closure is fitted
to the
bottle. Currently commercial polyethylene materials which combine the
properties of a
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homogeneous ethylene interpolymer and a heterogeneous ethylene interpolymer do
not
exist in the 5 to 20 melt index range.
Table 3 compares the physical properties of Examples 1001 and 1002 with all
the other
Examples and Comparatives disclosed herein.
As shown in Figure 1, the rectangle defined by Area III, defines a melt index
region that
ranges from > 0.3 dg/min to 5_ 8 dg/min. Within Area III, the disclosed
ethylene
interpolymer product, Examples 1001 and 1002, have a value of GI@G"=500Pa]
that is
desirable for continuous compression molding or injection molding.
Specifically,
Example 1001 and 102 and similar materials have a GI@G"=500Pa] values from 80
Pa to 5_ 120 Pa, which differs from the Examples that fall into the range of
Areas land II
and the Comparatives
Dilution Index (Yd) of Ethylene Interpolymer Products
In Figure 2 the Dilution Index (Yd, having dimensions of (degrees)) and
Dimensionless Modulus (Xd) are plotted for several embodiments of the ethylene
interpolymer products disclosed herein (the solid symbols), as well as
comparative
ethylene interpolymer products, i.e. Comparative A, D, E and S. Further,
Figure 2
defines the following three quadrants:
Type I: Yd >0 and Xd < 0;
Type II: Yd > 0 and Xd 0; and
Type III: Yd < 0 and Xd > O.
Type IV polymers are not shown in Fig 2 but are demonstrated by Examples
1001 and 1002 shown in Table 4; Type IV ethylene interpolymer products have Yd
<0
and Xd <0. As shown in Fig 1, Type IV ethylene interpolymer products fall into
Area III
Area Ill ethylene interpolymer products are advantageous in continuous
compression
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molding given the following attributes, a melt index > 0.3 dg/min to 8 dg/min
and a
GMG"=500 Pa] from .? 80 Pa to 5 120 Pa.
AREA III
The data plotted in Figure 2 is also tabulated in Table 4. In Figure 2,
Comparative S
(open triangle) was used as the rheological reference in the Dilution Index
test protocol.
Comparative S is an ethylene interpolymer product comprising an ethylene
interpolymer
synthesized using an in-line Ziegler-Natta catalyst in one solution reactor,
i.e. SCLAIR*
FP120-C which is an ethylene/1-octene interpolymer available from NOVA
Chemicals
Company (Calgary, Alberta, Canada). Comparatives D and E (open diamonds, Yd <
0,
Xd > 0) are ethylene interpolymer products comprising a first ethylene
interpolymer
synthesized using a single-site catalyst formation and a second ethylene
interpolymer
synthesized using a batch Ziegler-Natta catalyst formulation employing a dual
reactor
solution process, i.e. Elite 5100G and Elite 5400G, respectively, both
ethylene/1-
octene interpolymers available from The Dow Chemical Company (Midland,
Michigan,
USA). Comparative A (open square, Yd > 0 and Xd < 0) was an ethylene
interpolymer
product comprising a first and second ethylene interpolymer synthesized using
a single-
site catalyst formation in a dual reactor solution process, i.e. SURPASS
FPs117-C
which is an ethylene/1-octene interpolymer available from NOVA Chemicals
Company
(Calgary, Alberta, Canada).
The following defines the Dilution Index (Yd) and Dimensionless Modulus (Xd).
In
addition to having molecular weights, molecular weight distributions and
branching
structures, blends of ethylene interpolymers may exhibit a hierarchical
structure in the
melt phase. In other words, the ethylene interpolymer components may be, or
may not
be, homogeneous down to the molecular level depending on interpolymer
miscibility
and the physical history of the blend. Such hierarchical physical structure in
the melt is
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expected to have a strong impact on flow and hence on processing and
converting, as
well as the end-use properties of manufactured articles. The nature of this
hierarchical
physical structure between interpolymers can be characterized.
The hierarchical physical structure of ethylene interpolymers can be
characterized using melt rheology. A convenient method can be based on the
small
amplitude frequency sweep tests. Such rheology results are expressed as the
phase
angle 6 as a function of complex modulus G*, referred to as van Gurp-Palmen
plots (as
described in M. Van Gurp, J. Palmen, Rheol. Bull. (1998) 67(1): 5-8; and Dealy
J,
Plazek D. Rheol. Bull. (2009) 78(2): 16-31). For a typical ethylene
interpolymer, the
phase angle 6 increases toward its upper bound of 900 with G* becoming
sufficiently
low. A typical VGP plot is shown in Figure 3. The VGP plots are a signature of
resin
architecture. The rise of 6 toward 90 is monotonic for an ideally linear,
monodisperse
interpolymer. The 8(G*) for a branched interpolymer or a blend containing a
branched
interpolymer may show an inflection point that reflects the topology of the
branched
interpolymer (see S. Trinkle, P. Walter, C. Friedrich, Rheo. Acta (2002) 41:
103-113).
The deviation of the phase angle 6 from the monotonic rise may indicate a
deviation
from the ideal linear interpolymer either due to presence of long chain
branching if the
inflection point is low (e.g., 8 20 ) or a blend containing at least two
interpolymers
having dissimilar branching structure if the inflection point is high (e.g., 6
70 ).
For commercially available linear low density polyethylenes, inflection points
are
not observed, with the exception of some commercial polyethylenes that contain
a
small amount of long chain branching (LCB). To use the VGP plots regardless of
presence of LCB, an alternative is to use the point where the frequency coc is
two
decades below the cross-over frequency coc, i.e., w = 0.01w. The cross-over
point is
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taken as the reference as it is known to be a characteristic point that
correlates with MI,
density and other specifications of an ethylene interpolymer. The cross-over
modulus
is related to the plateau modulus for a given molecular weight distribution
(see S. Wu. J
Polym Sci, Polym Phys Ed (1989) 27:723; M.R. Nobile, F. Cocchini. Rheol Acta
(2001)
40:111). The two decade shift in phase angle 8isto find the comparable points
where
the individual viscoelastic responses of constituents could be detected. This
two
decade shift is shown in Figure 4. The complex modulus Gc* for this point is
normalized
to the cross-over modulus, Gx*/(12), as (12-)Gc*Ig to minimize the variation
due to
overall molecular weight, molecular weight distribution and the short chain
branching.
As a result, the coordinates on VGP plots for this low frequency point at NG =
0.01w,,
namely (V2)Gc.*IG,* and ac characterize the contribution due to blending.
Similar to the
inflection points, the closer the ((/-2-) Gc*IG; , oc) point is toward the 90
upper bound, the
more the blend behaves as if it were an ideal single component.
As an alternative way to avoid interference due to the molecular weight,
molecular
weight distribution and the short branching of the ethylene 8, interpolymer
ingredients,
the coordinates (G c* , e) are compared to a reference sample of interest to
form the
following two parameters:
"Dilution Index (Yd)"
Yd = 8, ¨ (C0 ¨ C1ec2I1G)
"Dimensionless Modulus (Xd)"
Xd =10g(G0*.oiwciGn
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The constants Co, Ci, and C2 are determined by fitting the VGP data 5(G*) of
the
reference sample to the following equation:
6 = Co ¨ Ciec21nG*
Gr* is the complex modulus of this reference sample at its 8, = (0.010),).
When
an ethylene interpolymer, synthesized with an in-line Ziegler-Natta catalyst
employing
one solution reactor, having a density of 0.920 g/cm3 and a melt index (MI or
12) of 1.0
dg/min is taken as a reference sample, the constants are:
Co = 93.43
Ci = 1.316
C2 = 0.2945
Cr* = 9432 Pa.
The values of these constants can be different if the rheology test protocol
differs
from that specified herein.
These regrouped coordinates (Xd, Yd) from (G,* , 6" c) allows comparison
between
ethylene interpolymer products disclosed herein with Comparative examples. The
regrouped Gc* [kPa] values disclosed in Table 4 are equivalent to the
Go*.01,,, term in the
formulae to calculate the Dimensionless Modulus (Xd).
The Dilution Index (Yd) reflects whether the blend behaves like a simple blend
of
linear ethylene interpolymers (lacking hierarchical structure in the melt) or
shows a
distinctive response that reflects a hierarchical physical structure within
the melt. The
lower the Yd, the more the sample shows separate responses from the ethylene
interpolymers that comprise the blend; the higher the Yd the more the sample
behaves
like a single component, or single ethylene interpolymer.
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Returning to Figure 2: Type I (upper left quadrant) ethylene interpolymer
products of this disclosure (solid symbols) have Yd > 0; in contrast, Type III
(lower right
quadrant) comparative ethylene interpolymers, Comparative D and E have Yd < 0.
In
the case of Type I ethylene interpolymer products (solid circles), the first
ethylene
interpolymer (single-site catalyst) and the second ethylene interpolymer (in-
line Ziegler
Natta catalyst) behave as a simple blend of two ethylene interpolymers and a
hierarchical structure within the melt does not exist. However, in the case of
Comparatives D and E (open diamonds), the melt comprising a first ethylene
interpolymer (single-site catalyst) and a second ethylene interpolymer (batch
Ziegler
Natta catalyst) possesses a hierarchical structure.
The ethylene interpolymer products of this disclosure fall into one of two
quadrants: Type I with Xd <0, or; Type II with Xd > 0. The Dimensionless
Modulus (Xd),
reflects differences (relative to the reference sample) that are related to
the overall
molecular weight, molecular weight distribution (Mw/Mn) and short chain
branching. Not
wishing to be bound by theory, conceptually, the Dimensionless Modulus (Xd)
may be
considered to be related to the Mw/Mn and the radius of gyration (<Rg>2) of
the ethylene
interpolymer in the melt. Conceptually, increasing Xd has similar effects as
increasing
Mw/Mn and/or <Rg>2, without the risk of including lower molecular weight
fraction and
sacrificing certain related properties.
Relative to Comparative A (recall that Comparative A comprises a first and
second ethylene interpolymer synthesized with a single-site catalyst) the
solution
process disclosed herein enables the manufacture of ethylene interpolymer
products
having higher Xd. Not wishing to be bound by theory, as Xd increases the
macromolecular coils of higher molecular weight fraction are more expanded
(conceptually higher <R9>2) and upon crystallization the probability of tie
chain
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formation is increased resulting in higher toughness properties. The
polyethylene art is
replete with disclosures that correlate higher toughness (for example improved
ESCR
and/or PENT in molded articles) with an increasing probability of tie chain
formation.
In the Dilution Index testing protocol, the upper limit on Yd may be about 20,
in
some cases about 15 and is other cases about 13. The lower limit on Yd may be
about
-30, in some cases -25, in other cases -20 and in still other cases -15.
In the Dilution Index testing protocol, the upper limit on Xd is 1.0, in some
cases
about 0.95 and in other cases about 0.9. The lower limit on Xci is -2, in some
cases -1.5
and in still other cases -1Ø
Terminal Vinyl Unsaturation of Ethylene Interpolymer Products
The ethylene interpolymer products of this disclosure are further
characterized
by a terminal vinyl unsaturation greater than or equal to 0.03 terminal vinyl
groups per
100 carbon atoms 0.03 terminal vinyls/100 C); as determine via Fourier
Transform
Infrared (FTIR) spectroscopy according to ASTM D3124-98 and ASTM D6248-98.
Figure 5 compares the terminal vinyl/100 C content of the ethylene
interpolymers
of this disclosure with several Comparatives. The data shown in Figure 5 is
also
tabulated in Tables 5A and 5B. All of the comparatives in Figure 5 and Tables
5A and
5B are Elite products available from The Dow Chemical Company (Midland,
Michigan,
USA); Elite products are ethylene interpolymers produced in a dual reactor
solution
process and comprise an interpolymer synthesized using a single-site catalyst
and an
interpolymer synthesized using a batch Ziegler-Natta catalyst: Comparative B
is Elite
5401G; Comparative C is Elite 5400G; Comparative E and E2 are Elite 5500G;
Comparative G is Elite 5960; Comparative H and H2 are Elite 5100G; Comparative
I is
Elite 59403; and Comparative J is Elite 5230G.
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As shown in Figure 5 the average terminal vinyl content in the ethylene
interpolymer of this disclosure was 0.045 terminal vinyls/100 C; the terminal
vinyl
unsaturation of Example 81 and 91 were close to this average, i.e. 0.044 and
0.041
terminal vinyl/100 C, respectively. The terminal vinyl unsaturation of Example
1001 and
1002 were close to this average, i.e. 0.045 terminal vinyl/100 C. In contrast,
the
average terminal vinyl content in the Comparative samples was 0.023 terminal
vinyls/100 C. Similar to Examples 81 and 91, the Comparatives shown in Figure
5 also
comprise a first ethylene interpolymer synthesized with a single-site catalyst
formulation
and a second ethylene interpolymer synthesized with a heterogeneous catalyst
formulation. Statistically, at the 99.999% confidence level, the ethylene
interpolymers
of this disclosure are significantly different from the Comparatives of Figure
5; i.e. a t-
Test assuming equal variances shows that the means of the two populations
(0.045
and 0.023 terminal vinyls/100 C) are significantly different at the 99.999%
confidence
level (t(obs) = 12.891 > 3.510 t(crit two tail); or p-value = 4.84x10-17 <
0.001 a (99.999%
confidence)).
Catalyst Residues (Total Catalytic Metal)
The ethylene interpolymer products of this disclosure are further
characterized
by having ?.. 3 parts per million (ppm) of total catalytic metal (Ti), where
the quantity of
catalytic metal was determined by Neutron Activation Analysis (N.A.A.) as
specified
herein.
Figure 6 compares the total catalytic metal content of the disclosed ethylene
interpolymers with several Comparatives. Figure 6 data is also tabulated in
Tables 6A
and 6B. All of the comparatives in Figure 6 and Tables 6A and 6B are Elite
products
available from The Dow Chemical Company (Midland, Michigan, USA), for
additional
detail see the section above.
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As shown in Figure 6 the average total catalytic metal content in the ethylene
interpolymers of this disclosure was 7.02 ppm of titanium. Although elemental
analysis
(N.A.A.) was not completed on Examples 81 and 91, Figure 5 clearly shows that
7.02
ppm of titanium is a reasonable estimate (as reported in Table 3) for residual
titanium in
Examples 81 and 91. In contrast, the average total catalytic metal in the
Comparative
samples shown in Figure 6 was 1.63 ppm of titanium. Statistically, at the
99.999%
confidence level, the ethylene interpolymers of this disclosure are
significantly different
from the Comparatives, i.e. a t-Test assuming equal variances shows that the
means of
the two populations (7.02 and 1.63 ppm titanium) are significantly different
at the
99.999% confidence level, i.e. (t(obs) = 12.71 > 3.520 t(crit two tail); or p-
value =
1.69x10-16 < 0.001 a (99.999% confidence)).
Rigid Manufactured Articles
There is a need for ethylene interpolymer products having optimized density,
melt index and G'[@G"=500 Pa] for compression molding processes. Further,
there is
a need for ethylene interpolymer products having optimized density, melt index
and
G'[@G"=500 Pa] for injection molding processes. There is also a need to
improve the
stiffness of caps and closures articles, while maintaining or increasing the
Environmental Stress Crack Resistance (ESCR). The various embodiments of
ethylene interpolymer products disclosed herein are well suited to satisfy
some or all
these needs.
Additional non-limiting applications where the disclosed ethylene interpolymer
products may be used include: deli containers, margarine tubs, trays, cups,
lids, bottles,
bottle cap liners, pails, crates, drums, bumpers, industrial bulk containers,
industrial
vessels, material handling containers, playground equipment, recreational
equipment,
safety equipment, wire and cable applications (power cables, communication
cables
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and conduits), tubing and hoses, pipe applications (pressure pipe and non-
pressure
pipe, e.g. natural gas distribution, water mains, interior plumbing, storm
sewer, sanitary
sewer, corrugated pipes and conduit), foamed articles (foamed sheet or bun
foam),
military packaging (equipment and ready meals), personal care packaging
(diapers and
sanitary products), cosmetic, pharmaceutical and medical packaging, truck bed
liners,
pallets and automotive dunnage. The rigid manufactured articles summarized in
this
paragraph contain one or more of the ethylene interpolymer products having
improved
heat deflection temperature (HDT), faster crystallization rate (reduced t112)
and higher
melt strength. Such rigid manufactured articles may be fabricated using the
conventional injection molding, compression molding and blow molding
techniques.
The desired physical properties of rigid manufactured articles depend on the
application of interest. Non-limiting examples of desired properties include:
elasticity
(G'), stiffness, flexural modulus (1% and 2% secant modulus); tensile
toughness;
environmental stress crack resistance (ESCR); slow crack growth resistance
(PENT);
abrasion resistance; shore hardness; heat deflection temperature (HOT); VICAT
softening point; IZOD impact strength; ARM impact resistance; Charpy impact
resistance; and color (whiteness and/or yellowness index).
Additives and Adjuvants
The ethylene interpolymer products and the caps and closures claimed 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 or a mixture of more than one nucleating agent, and combinations
thereof.
Testing Methods
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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. 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. In this disclosure, melt index was expressed
using the
units of g/10 minutes or g/10 min or dg/minutes or dg/min. These units are
equivalent.
Environmental Stress Crack Resistance (ESCR)
ESCR was determined according to ASTM D1693-13 (November 1,2013).
Condition B was used, with a specimen thickness with the range of 1.84 to 1.97
mm
(0.0725 to 0.0775 in) and a notch depth in the range of 0.30 to 0.40 mm (0.012
to 0.015
in). The concentration of Igepal used was 10 volume%.
Gel Permeation Chromatography (GPC)
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Ethylene interpolymer product molecular weights, Mn, Mw and Mz, as well the as
the polydispersity (Mw/Mn), were determined using ASTM D6474-12 (December 15,
2012). This method illuminates the molecular weight distributions of ethylene
interpolymer products by high temperature gel permeation chromatography (GPC).
The
method uses commercially available polystyrene standards to calibrate the GPC.
Unsaturation Content
The quantity of unsaturated groups, i.e. double bonds, in an ethylene
interpolymer product was determined according to ASTM D3124-98 (vinylidene
unsaturation, published March 2011) and ASTM 06248-98 (vinyl and trans
unsaturation, published July 2012). An ethylene interpolymer sample was: a)
first
subjected to a carbon disulfide extraction to remove additives that may
interfere with
the analysis; b) the sample (pellet, film or granular form) was pressed into a
plaque of
uniform thickness (0.5 mm); and c) the plaque was analyzed by FTIR.
Comonomer Content
The quantity of comonomer in an ethylene interpolymer product was determined
by FTIR (Fourier Transform Infrared spectroscopy) according to ASTM D6645-01
(published January 2010).
Composition Distribution Branching Index (CDBI)
The "Composition Distribution Branching Index" or "CDBI" of the disclosed
Examples and Comparative Examples were determined using a crystal-TREF unit
commercially available form Polymer ChAR (Valencia, Spain). The acronym "TREF"
refers to Temperature Rising Elution Fractionation. A sample of ethylene
interpolymer
product (80 to 100 mg) was placed in the reactor of the Polymer ChAR crystal-
TREF
unit, the reactor was filled with 35 ml of 1,2,4-trichlorobenzene (TCB),
heated to 150 C
and held at this temperature for 2 hours to dissolve the sample. An aliquot of
the TCB
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solution (1.5 mL) was then loaded into the Polymer ChAR TREF column filled
with
stainless steel beads and the column was equilibrated for 45 minutes at 110 C.
The
ethylene interpolymer product was then crystallized from the TCB solution, in
the TREF
column, by slowly cooling the column from 110 C to 30 C using a cooling rate
of
0.09 C per minute. The TREF column was then equilibrated at 30 C for 30
minutes.
The crystallized ethylene interpolymer product was then eluted from the TREF
column
by passing pure TCB solvent through the column at a flow rate of 0.75
mL/minute as
the temperature of the column was slowly increased from 30 C to 120 C using a
heating rate of 0.25 C per minute. Using Polymer ChAR software a TREF
distribution
curve was generated as the ethylene interpolymer product was eluted from the
TREF
column, i.e. a TREF distribution curve is a plot of the quantity (or
intensity) of ethylene
interpolymer eluting from the column as a function of TREF elution
temperature. A
CDBIso was calculated from the TREF distribution curve for each ethylene
interpolymer
product analyzed. The "CDBIso" is defined as the percent of ethylene
interpolymer
.. whose composition is within 50% of the median comonomer composition (25% on
each
side of the median comonomer composition). It is calculated from the TREF
composition distribution curve and the normalized cumulative integral of the
TREF
composition distribution curve. Those skilled in the art will understand that
a calibration
curve is required to convert a TREF elution temperature to comonomer content,
i.e. the
amount of comonomer in the ethylene interpolymer 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.
Heat Deflection Temperature
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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.
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).
Neutron Activation Analysis (NAA)
Neutron Activation Analysis, hereafter NAA, was used to determine catalyst
residues in ethylene interpolymers and was performed 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
aging, the
.. gamma-ray spectrum of the sample was recorded using a germanium
semiconductor
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gamma-ray detector (Ortec model GEM55185, Advanced Measurement Technology
Inc., Oak Ridge, TN, USA) and a multichannel analyzer (Ortec model DSPEC Pro).
The amount of each element in the sample was calculated from the gamma-ray
spectrum and recorded in parts per million relative to the total weight of the
ethylene
interpolymer sample. The N.A.A. system was calibrated with Specpure standards
(1000 ppm solutions of the desired element (greater than 99% pure)). One mL of
solutions (elements of interest) were pipetted onto a 15 mm x 800 mm
rectangular
paper filter and air dried. The filter paper was then placed in a 1.4 mL
polyethylene
irradiation vial and analyzed by the N.A.A. system. Standards are used to
determine
the sensitivity of the N.A.A. procedure (in counts/pg).
Color Index
The Whiteness Index (WI) and Yellowness Index (YI) of ethylene interpolymer
products were measured according to ASTM E313-10 (approved in 2010) using a
BYK
Gardner Color-View colorimeter.
Dilution Index (Yd) Measurements
A series of small amplitude frequency sweep tests were run on each sample
using an Anton Paar MCR501 Rotational Rheometer equipped with the "TruGapTm
Parallel Plate measuring system." A gap of 1.5 mm and a strain amplitude of
10% were
used throughout the tests. The frequency sweeps were from 0.05 to 100 rad/s at
the
intervals of seven points per decade. The test temperatures were 170 , 190 ,
210 and
230 C. Master curves at 190 C were constructed for each sample using the
Rheoplus/32 V3.40 software through the Standard TTS (time-temperature
superposition) procedure, with both horizontal and vertical shift enabled.
The Yd and Xd data generated are summarized in Table 4. The flow properties
of the ethylene interpolymer products, e.g., the melt strength and melt flow
ratio (MFR)
61
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are well characterized by the Dilution Index (Yd) and the Dimensionless
Modulus (Xd) as
detailed below. In both cases, the flow property is a strong function of Yd
and Xd in
addition a dependence on the zero-shear viscosity. For example, the melt
strength
(hereafter MS) values of the disclosed Examples and the Comparative Examples
were
found to follow the same equation, confirming that the characteristic VGP
point
((ff)G,* / Gx* , gc) and the derived regrouped coordinates (Xd, Yd) represent
the structure
well:
MS = a00 + aidogrio ¨ a20(90 ¨ 15,) ¨ a30((V-2-)Gc*/G;)
¨a40(90 ¨
where
aoo = -33.33; aio = 9.529; azo = 0.03517; a30= 0.894; a40= 0.02969
and
r2= 0.984 and the average relative standard deviation was 0.85%. Further, this
relation
can be expressed in terms of the Dilution Index (Yd) and the Dimensionless
Modulus
(Xd):
MS = a() + ai/ogno + a2Yd + a3Xd + a4YdXd
where
ao = 33.34; ai = 9.794; az = 0.02589; a3= 0.1126; a4= 0.03307
and
r2= 0.989 and the average relative standard deviation was 0.89%.
The MFR of the disclosed Examples and the Comparative samples were found
to follow a similar equation, further confirming that the dilution parameters
Yd and Xd
show that the flow properties of the disclosed Examples differ from the
reference and
Comparative Examples:
62
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MFR = bo ¨ bilogno ¨ b2Yd ¨ b3Xd
where
bo = 53.27; bi = 6.107; b2 = 1.384; b3= 20.34
and
r2 = 0.889 and the average relative standard deviation and 3.3%.
Further, the polymerization process and catalyst formulations disclosed herein
allow the production of ethylene interpolymer products that can be converted
into
flexible manufactured articles that have a desired balance of physical
properties (i.e.
several end-use properties can be balanced (as desired) through
multidimensional
optimization); relative to comparative polyethylenes of comparable density and
melt
index.
Gi[@G"=500Pa] Parameter
The GI@G"=500Pa] parameter was generated using conventional rheological
equipment and data processing techniques that is well known to those of
ordinary
experience in the art. The rheological data was generated on a Rheometrics RDS-
II
(Rheometrics Dynamic Spectrometer II), which is a Strain Control Rotational
Rheometer. The ethylene interpolymer sample analyzed was in the form of a
compression molded sample disk; the sample disk is placed in the heated
chamber of
the RDS-II, between two parallel plate test fixtures; one fixture is attached
to an
actuator and the other to a transducer. The testing is carried out over a
range of
frequencies, typically from 0.05 to 100 rad/s, at a fixed strain and a
constant
temperature of 190 C. This test generates the following data which
characterizes the
elastic and viscous attributes of a polymer melt: real, elastic or storage
modulus (G'),
the viscous or loss modulus (G"), complex viscosity ri* and tan 6 as a
function of
frequency (dynamic oscillation). The G'[@G"=500Pa] parameter was determined as
63
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follows: G' is plotted as a function of G" (those with ordinary experience in
the art
generally refer to this plot as a Cole-Cole plot) and GI@G"=500Pa] is simply
the G'
value (Pa) where G" is equal to 500 Pa. Sample plaques were prepared as
follows: (a)
for samples having a melt index less than 1.0 dg/min, about 5.5g of ethylene
.. interpolymer was compression molded at 190 C into a 1.8 mm thick circular
plaque and
using a circular punch a 2.5 cm diameter sample disk was punched from the
circular
plaque and loaded into the RDS-II, or; (b) for samples having a melt index
greater than
or equal to 1.0 dg/min, about 2.8 g ethylene interpolymer was compression
molded at
190 C into a 0.9 mm thick circular plaque and using a circular punch a 2.8 cm
diameter
sample disk was punched from the circular plaque and loaded into the RDS-II.
The
finished plaque should be bubble-free, impurity-free, and have a smooth
surface free of
any defect.
Tensile Properties
The following tensile properties were determined using ASTM D882-12 (August
1, 2012): tensile break strength (MPa), elongation at yield (%),yield strength
(MPa),
ultimate elongation (%), ultimate strength (MPa) and 1 and 2% secant modulus
(MPa).
Flexural Properties
Flexural properties, i.e. 2% flexural secant modulus was determined using ASTM
D790-10 (published in April 2010).
IZOD Impact Strength
IZOD impact strength (ft-lbs/in) was determined using ASTM D256-05 (published
January 2005) using a lzod impact pendulum-like tester.
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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 sample is determined gravimetrically.
EXAMPLES
Polymerization
The following examples are presented for the purpose of illustrating selected
embodiments of this disclosure, it being understood, that the examples
presented do
not limit the claims presented.
Embodiments of ethylene interpolymer products disclosed herein were produced
in a continuous solution polymerization pilot plant comprising reactors
arranged in a
series configuration. 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 4.8 gallons (18 L). Examples of
ethylene
interpolymer products were produced using an R1 pressure from about 14 MPa to
about 18 MPa; R2 was operated at a lower pressure to facilitate continuous
flow from
R1 to R2. R1 and R2 were operated in series mode, wherein the first exit
stream from
R1 flows directly into R2. Both CSTR's were agitated to give conditions in
which the
reactor contents were well mixed. The process was operated continuously by
feeding
fresh process solvent, ethylene, 1-octene and hydrogen to the reactors.
The single site catalyst components used were: component (i), cyclopentadienyl
tri(tertiary butyl)phosphinimine titanium dichloride, (Cp[(t-Bu)3PNI]TiC12),
hereafter PIC-
1; component (ii), methylaluminoxane (MA0-07); component (iii), trityl
tetrakis(pentafluoro-phenyl)borate; and component (iv), 2,6-di-tert-butyl-4-
ethylphenol.
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The single site catalyst component solvents used were methylpentane for
components
(ii) and (iv) and xylene for components (i) and (iii). The quantity of PIC-1
added to R1,
"R1 (i) (ppm)" is shown in Table 2A; to be clear, in Example 81 in Table 2A,
the solution
in R1 contained 0.13 ppm of component (i), i.e. PIC-1. The mole ratios of the
single
site catalyst components employed to produce Example 81 were: R1 (ii)/(i) mole
ratio =
100, i.e. [(MA0-07)/(PIC-1)]; R1 (iv)/(ii) mole ratio = 0.0, i.e. [(2,6-di-
tert-butyl-4-
ethylphenol)/(MA0-07)]; and R1 (iii)/(i) mole ratio = 1.1, i.e. [(trityl
tetrakis(pentafluoro-
phenyl)borate)/(PIC-1)].
The in-line Ziegler-Natta catalyst formulation was prepared from the following
components: component (v), butyl ethyl magnesium; component (vi), tertiary
butyl
chloride; component (vii), titanium tetrachloride; component (viii), diethyl
aluminum
ethoxide; and component (ix), triethyl aluminum. Methylpentane was used as the
catalyst component solvent. The in-line Ziegler-Natta catalyst formulation was
prepared using the following steps. In step one, a solution of
triethylaluminum and
dibutylmagnesium ((triethylaluminum)/(dibutylmagnesium) molar ratio of 20) was
combined with a solution of tertiary butyl chloride and allowed to react for
about 30
seconds (HUT-1); in step two, a solution of titanium tetrachloride was added
to the
mixture formed in step one and allowed to react for about 14 seconds (HUT-2);
and in
step three, the mixture formed in step two was allowed to reactor for an
additional 3
seconds (HUT-3) prior to injection into R2. The in-line Ziegler-Natta
procatalyst
formulation was injected into R2 using process solvent, the flow rate of the
catalyst
containing solvent was about 49 kg/hr. The in-line Ziegler-Natta catalyst
formulation
was formed in R2 by injecting a solution of diethyl aluminum ethoxide into R2.
The
quantity of titanium tetrachloride "R2 (vii) (ppm)" added to reactor 2 (R2) is
shown in
Table 2A; to be clear in Example 81 the solution in R2 contained 3.99 ppm of
TiCI4.
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The mole ratios of the in-line Ziegler-Natta catalyst components are also
shown in
Table 2A, specifically: R2 (vi)/(v) mole ratio, i.e. [(tertiary butyl
chloride)/(butyl ethyl
magnesium)]; R2 (viii)/(vii) mole ratio, i.e. [(diethyl aluminum
ethoxide)/(titanium
tetrachloride)]; and R2 (ix)/(vii) mole ratio, i.e. Rtriethyl
aluminum)/(titanium
tetrachloride)]. To be clear, in Example 81, the following mole ratios were
used to
synthesize the in-line Ziegler-Natta catalyst: R2 (vi)/(v) mole ratio = 1.83;
R2 (viii)/(vii)
mole ratio = 1.35; and R2 (ix)/(vii) mole ratio = 0.35. In all of the Examples
disclosed,
100% of the diethyl aluminum ethoxide was injected directly into R2.
In Example 81 (single-site catalyst formulation in R1 + in-line Ziegler-Natta
catalyst in R2) the ethylene interpolymer product was produced at a production
rate of
93.5 kg/h; in contrast, in Comparative Example 20 (single-site catalyst
formulation in
both R1 and R2) the maximum production rate of the comparative ethylene
interpolymer product was 74 kg/h.
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 2A-2C: average reactor residence times were: about 61
seconds in R1, about 73 seconds in R2 and about 50 seconds in R3 (the volume
of R3
was about 4.8 gallons (18L)).
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
titanium and
aluminum added to the polymerization process; to be clear, the moles of
octanoic acid
67
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added = 0.5 x (moles titanium + moles aluminum); this mole ratio was
consistently used
in all examples.
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. DHT-4V (hydrotalcite), supplied by
Kyowa
Chemical Industry Co. LTD, Tokyo, Japan was used as a passivator, or acid
scavenger,
in the continuous solution process. A slurry of DHT-4V in process solvent was
added
prior to the first V/L separator. The molar amount of DHT-4V added was about
10-fold
higher than the molar amount of chlorides added to the process; the chlorides
added
were titanium tetrachloride and tertiary butyl chloride.
Prior to pelletization the ethylene interpolymer product was stabilized by
adding
about 500 ppm of Irganox 1076 (a primary antioxidant) and about 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.
Tables 2B and 2C disclose additional solution process parameters, e.g.
ethylene
and 1-octene splits between the reactors, reactor temperatures and ethylene
conversions, etc. recorded during the production of Example 81 and Comparative
Example 20. In Comparative Example 20, the single-site catalyst formulation
was
injected into both reactor R1 and reactor R2 and ESR1 was 45%, i.e. percent of
ethylene
allocated to reactor 1. In Example 81, the single site catalyst formulation
was injected
into R1, the in-line Ziegler-Natta catalyst formulation was injected into R2
and ES R1 was
35%.
6g
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TABLE 1
Computer generated Simulated Example 13: single-site catalyst formulation in
R1
(PIC-1) and an in-line Ziegler-Natta catalyst formulation in R2 and R3
Reactor 1 Reactor 2
Reactor 3 (R3) Simulated
Simulated Physical (R1) (R2) Second
Third Ethylene Example
Property First Ethylene Ethylene
Interpolymer 13
Interpolymer Interpolymer
Weight Percent (%) 36.2 56.3 7.5 100
Mn 63806 25653 20520 31963
Mw 129354 84516 67281 99434
Mz 195677 198218 162400 195074
Polydispersity
2.03 3.29 3.28 3.11
(Mw/Mn)
Branch Frequency
(C6 Branches per 12.6 11.4 15.6 12.1
1000C)
CD8160( /0) (range) 90 to 95 55 to 60 45 to 55 65 to 70
Density (g/cm3) 0.9087 0.9206 0.9154 0.9169
Melt Index (dg/min) 0.31 1.92 4.7 1.0
69
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TABLE 2A
Continuous solution polymerization process parameters for ethylene
interpolymer products Examples 81, 91, 1001, and 1002
and Comparative Example 20 and Comparative Example 30
Comparative Comparative
Sample Code Example 81 Example 91
Example1001 Example 1002
Example 20 Example 30
R1 Catalyst PIC-1 PIC-1 PIC-1 PIC-1
PIC-1 PIC-1
R2 Catalyst ZN PIC-1 ZN PIC-1
ZN ZN ci
o
tv
R1 (i) (ppm) 0.13 0.08 0.31 0.14
0.05 0.10 w
u,
-..,
.4
0
_
R1 (ii)/(i) mole ratio 100.0 100.0 100.0 100.0
149.5 125.0 0,
ts,
0
1-,
R1 (iv)/(ii) mole ratio 0.0 0.3 0.0 0.3
0.1 0.1
I
0
ts)
I
R1 (iii)/(i) mole ratio 1.10 1.2 1.10 1.17
1.40 1.30
R2 (i) (ppm) 0 0.22 0 0.45
0 0
R2 (ii)/(i) mole ratio 0 25 0 25
0 0
R2 (iv)/(ii) mole ratio 0 0.3 0 0.3
0 0
R2 (iii)/(i) mole ratio 0 1.27 0 1.5
0 0
R2 (vii) (ppm) 3.99 0 4.50 0
7.50 7.50
R2 (vi)/(v) mole ratio 1.83 0 1.83 0
2.07 2.07
R2 (viii)/(vii) mole
1.35 0 1.35 0
1.33 1.35
ratio
R2 (ix)/(vii) mole
0.35 0 0.35 0
0.35 0.35
ratio
Prod. Rate (kg/h) 93.5 74.0 93.3 81.2
81.0 87.5 ci
o
tv
w
I
-4
-4
o
(3)
tv
o
i--,
--.3
1
o
tv
I
I-,
La
71
2016 034 USA-NONP
TABLE 2B
Additional solution process parameters for ethylene interpolymer products
Examples 81, 91, 10011 and 1002 and
Comparative Example 20 and Comparative Example 30
Comparative Comparative
Sample Code Example 81 Example 91
Example1001 Example 1002
Example 20 Example 30
R3 volume (L) 18 18 18 18
18 18
ESR1 (%) 35 45 40 45
25.0 28.0 0
NJ
C.0
ESR2 (%) 65 55 60 55
75 72 CJ1
-,/
-,/
0
0)
ESR3 (%) 0 0 0 0
0 0 " 0
cb
r.)
R1 ethylene
7,s,
9.69 9.5 10.49 10.8
8.69 8.40
concentration (wt%)
R2 ethylene
16.1 13.3 16.0 14.4 14.9 14.8
concentration (wt%)
R3 ethylene
16.1 13.3 16.0 14.4 14.9 14.8
concentration (wt%)
72
2016 034 USA-NONP
((octene)/(ethylene))
0.03 0.044 0.014 0.007
0.021 0.013
in R1 (wt%)
OSR1 (%) 100 100 100 100 100
100
OSR2 (%) 0 0 0 0 0
0
0 0 0 0
0 0
H2R1 (ppm) 0.50 1.65 2.40 2.94
0.20 0.22
0
H2'2 (ppm) 80.0 27.90 79.97 10.59 40.18
40.01
0
CJ1
-,1
-,1
_______________________________________________________________________________
___________________ 1
H2R3 (ppm) 0 0 0 0 0
0 0
0
N.,
0
Prod. Rate (kg/h) 93.5 74.0 93.3 81.2
81.0 87.5
c b
Ws
73
TABLE 2C
Additional solution process parameters for ethylene interpolymer products
Examples 81, 91, 1001, and 1002 and
Comparative Example 20 and Comparative Example 30
Comparative Comparative
Sample Code Example 81 Example 91
Example1001 Example 1002
Example 20 Example 30
R1 total solution rate
342.2 379.2 358.6 359.9 234.2 295.9
(kg/h)
0
R2 total solution rate
257.8 220.8 241.4 240.1 313.4 304.0
0
0,
(kg/h)
0
R3 solution rate
ts,
0 0 0 0
0 0
(kg/h)
Overall total solution
600.0 600 600.0 600 547.6 599.9
rate (kg/h)
R1 inlet temp ( C) 30 30 30
35.0 45.6
74
R2 inlet temp ( C) 30 30 30 30
35.0 35.0
R3 inlet temp( C) 130 130 130 130
130 130
R1 Mean temp ( C) 153.0 144.0 162.4 162.3
132.6 128.5
R2 Mean temp ( C) 211.6 186.6 212.1 202.2
212.5 210.3
R3 exit temp (actual)
221.3 188.4 222.4 206.6 - -
( C)
P R3 exit temp (calc)
0
224.4 191.5 224.4 205.2 - -
u,
-..,
(0C)
.4
0
0,
QR1(0/0) 91.5 90.0 90.9 93.0
84.85 93.40 ts,
0
1--,
1
QR2 (0/0) 79.7 79.0 78.7 83.0
88.48 85.01 0
rs,
4,
QR2+R3 (%) 90.9 87.3 90.9 89.1 -
-
QR3 (0/0) 55.1 39.3 57.1 36.1 -
-
cl-r (0/0) 93.8 92.4 94.2 93.7
98.44 97.19
Prod. Rate (kg/h) 93.5 74.0 93.3 81.2
81.0 87.5
1
TABLE 3
Physical properties of ethylene interpolymer product Examples 81, 91, 1001,
and 1002 and Comparative Q, V, R, Y and X
Example Comp. Comp. Example Comp. Comp. Comp.
Sample Code
Example1001 Example 1002
81 Q V 91 R Y X
Density (g/cm3) 0.9533 0.9530 0.9550 0.9589 0.9580 0.9600 0.9490
0.9550 0.9558
ci
Melt Index, 12
1.61 1.40 1.50 6.72 7.03 8.52 10.9
0.56 0.65 0
,,
w
(dg/min)
u,
-..,
.4
0
0,
Melt Flow Ratio
ts,
50 57 66 30.4 37 26.1 22.4
112 74.6 0
1-,
-.4
I
(121/12)
0
ts)
I
I--,
Stress
1.43 1.35 1.58 1.29 1.32 1.29 1.23
1.88 1.66
Exponent
Zero Shear
Viscosity 190 C 7959 6249 9733 1424 1464 1080
28120 26240
(Pa-s) 1924
76
Crossover
Frequency 69.89 58.51 43.45 431.6 298.3
568.9 7.89 19.60
190 C (rad/s) 431.1
G'[@ G"=500
64 38 74 32 38 62
108.9 116.8
Pa] (Pa) 102
Comonomer Octene octene hexene Octene octene butene
Octene Octene
Comonomer
ci
o
tv
Content 0.3 0.5 0.5 0.2 0.3 0.0 0.5
0.2 <0.1 w
u,
-..,
.4
0
(mole %)
0,
ts,
0
1--,
Internal
I
0.002 0.002 0.000 0.002 0.005 0.004 0.001
0.001 0.001 0
ts,
i
Unsat/100C
1--,
Side Chain
0.0 0.0 0.009 0.0 0.0 0.0 0.0
0 0
Unsat/100C
Terminal
0.044 0.008 0.017 0.041 0.01 0.017 0.017
0.045 0.045
Unsat/100C
77
Ti (ppm) 6.4 0.35a 0.95 6.7 0.35a 10.7 7.3
Mw 98234 91691 106992 66128 62792 63567 61071
131184 124461
Mz 357665 277672 533971 167030 162875 181472 153014
582129 456564
TABLE 3 (Cont.)
Physical properties of ethylene interpolymer product Examples 81, 91, 1001,
and 1002 and Comparative
Q, V, R, Y and X
ci
o
tv
Example Comp. Comp. Example Comp. Comp.
Example Example w
u,
-..,
Sample Code Comp. X
.4
0
81 Q V 91 R Y
1001 1002 0,
ts,
0
1--,
-.4
Polydispersity
i
0
5.62 7.38 10.45 3.54 4.41 3.73 2.99
6.62 5.33 ts)
1
Index (Mw/Mn)
1--,
VICAT Soft. Pt.
129.1 126.4 126.8 129.3 127.0 124.5
129.1 129
( C): Plaque
lElong. at Yield
9 9 9 8 9 8 9
9 9
(yo )
78
lYield Strength
27.3 27.0 28.5 30.0 29.5 31.0 25.4
28.9 29.4
(MPa)
lUltimate Elong.
958 899 870 1109 891 763 1143
539 671
(0/0)
lUltimate
35.9 31.4 26.8 22.4 19.0 16.0 16.8
17.1 25.1
Strength (MPa)
1Sec Mod 1%
n
1720 1393 1036 1813 1852 1171
1356 1428 0
t.,
(MPa) 1746
,0
0,
-..,
..,
0
"Sec Mod 2%
0,
t.,
1052 944 904 1158 1154 857
1000 1035 0
(MPa) 1155
1155
1
0
tN)
I
2Flex Secant
1-
w
1305 1272 1372 1531 1352 1599 1161
1358 1397
Mod. 1% (MPa)
h
2Flex Secant
1091 1070 1167 1272 1160 1361 1008
1123 1152
Mod. 2% (MPa)
79
2Flex Tangent
1619 1630 1636 1881 1605 1870 1356 1729 1777
Mod. (MPa)
2Flexural
37.9 37.2 40.4 41.9 40.1 44.6 36.0 39.4 40
Strength (MPa)
Izod Impact (ft-
1.6 1.5 1.5 1.0 0.9 0.7
2 3.4
lb/in)
a average: database on Ti (ppm) in SURPASS products (NOVA Chemicals) As
determined by ASTM D882-12 2 As determined by ASTM D790-10
0
t.)
TABLE 4
Ul
=.1
0
Dilution Index (Yd) and Dimensionless Modulus Data (Xd) for selected
embodiments of ethylene interpolymers of this ts,
0
disclosure (Examples), relative to Comparative S. A, D and E. (MFR = melt flow
rate (121/12); MS = melt strength)
0
ts,
Density MI MS rlo G N oc
Sample Code MFR G*c
[kPa] Xd Yd
[g/cm3] [dg/min] [cN] [kPa=s] [MPa]
Comp. S 0.9176 0.86 29.2 6.46 11.5 1.50
9.43 74.0 0.00 0.02
Comp. A 0.9199 0.96 29.6 5.99 10.6 1.17
5.89 80.1 -0.20 3.66
Example 6 0.9152 0.67 23.7 7.05 12.9 1.57
7.89 79.6 -0.08 4.69
Example 101 0.9173 0.95 26.3 5.73 9.67 0.84 7.64
79.0 -0.09 3.93
Example 102 0.9176 0.97 22.6 5.65 9.38 1.46 7.46
79.5 -0.10 4.29
Example 103 0.9172 0.96 25.3 5.68 9.38 1.44 7.81
79.3 -0.08 4.29
Example 110 0.9252 0.98 23.9 5.57 9.41 1.64 8.90
78.1 -0.03 3.8
Example 115 0.9171 0.75 23.4 6.83 12.4 1.48 8.18
79.2 -0.06 4.44
Example 200 0.9250 1.04 24.2 5.33 8.81 0.97 8.97
78.9 -0.02 4.65
Example 201 0.9165 1.01 27.1 5.43 8.75 0.85 6.75
79.7 -0.15 3.91
Example 120 0.9204 1.00 24.0 5.99 10.2 1.45 13.5
73.6 0.16 1.82
0
Example 130 0.9232 0.94 22.1 6.21 10.4 0.97 11.6
75.7 0.09 3.02 0,
ts,
0
Example 131 0.9242 0.95 22.1 6.24 10.7 1.02 11.6
75.3 0.09 2.59
0
ts,
Comp. D 0.9204 0.82 30.6 7.61 15.4 1.58 10.8
70.4 0.06 -2.77
Comp. E 0.9161 1.00 30.5 7.06 13.8 1.42 10.4
70.5 0.04 -2.91
Example1001 0.9550 0.56 112 4.82 28.12 0.90 1.78
74.1 -0.73 -7.41
Example 1002 0.9558 0.65 74.6 4.81 26.24 1.16 3.62
70.2 -0.42 -8.57
81
TABLE 5A
Unsaturation data of several embodiments of the disclosed ethylene
interpolymers, as well as Comparative B, C, E, E2, G,
H, H2, I and J; as determined by ASTM 03124-98 and ASTM D6248-98
Density Melt Index Melt Flow Stress
Unsaturations per 100 C
Sample Code
(g/cm3) 12 (dg/min) Ratio (121/12) Exponent
Internal Side Chain Terminal
Example 11 0.9113 0.91 24.8 1.24 0.009
0.004 0.037
Example 6 0.9152 0.67 23.7 1.23 0.008
0.004 0.038 ci
o
tv
Example 4 0.9154 0.97 37.1 1.33 0.009
0.004 0.047 w
u,
-..,
.4
0
Example 7 0.9155 0.70 25.7 1.24 0.008
0.005 0.042 0,
ts,
0
1--,
Example 2 0.9160 1.04 27.0 1.26 0.009
0.005 0.048
I
0
ts)
I
Example 5 0.9163 1.04 25.9 1.23 0.008
0.005 0.042 1--,
Example 3 0.9164 - 0.9 29.2 1.27 0.009
0.004 0.049
Example 53 0.9164 0.9 29.2 1.27 0.009
0.004 0.049
Example 51 0.9165 1.01 28.0 1.26 0.009
0.003 0.049
Example 201 0.9165 1.01 27.1 1.22 0.008
0.007 0.048
82
Example 1 0.9169 0.88 23.4 1.23 0.008
0.005 0.044
Example 52 0.9169 0.85 29.4 1.28 0.008
0.002 0.049
Example 55 0.9170 0.91 29.8 1.29 0.009
0.004 0.050
Example 115 0.9171 0.75 23.4 1.22 0.007
0.003 0.041
Example 43 0.9174 1.08 24.2 1.23 0.007
0.007 0.046
Comparative E2 0.9138 1.56 24.1 1.26 0.006
0.007 0.019
Comparative E 0.9144 1.49 25.6 1.29 0.004
0.005 0.024 ci
o
tv
Comparative J 0.9151 4.2 21.8 1.2 0.006
0.002 0.024 w
u,
-..,
.4
0
Comparative C 0.9161 1 30.5 1.35 0.004
0.004 0.030 0,
ts,
0
1--,
-.4
I Comparative B 0.9179 1.01 30.2 ' 1.33
0.004 0.002 0.025 0
ts,
i
1--,
Comparative H2 0.9189 0.89 30.6 1.36 0.004
0.002 0.021
Comparative H 0.9191 0.9 29.6 1.34 0.004
0.003 0.020
Comparative I 0.9415 0.87 62 1.61 0.002
0.000 0.025
Comparative G 0.9612 0.89 49 1.58 0.000
0.000 0.023
Example1001 0.9550 0.56 112 1.88 0.001
0.000 0.045
83
Example 1002 0.9558 0.65 74.6 1.66 0.001
0.000 0.045
TABLE 5B
Additional unsaturation data of several embodiments of the disclosed ethylene
interpolymers; as determined by ASTM
D3124-98 and ASTM D6248-98
Density Melt Index Melt Flow
Unsaturations per 100 C
Sample Code S.Ex.
(g/cm3) 12 (dg/min) Ratio (121/12) Internal
Side Chain Terminal ci
o
Example 8 0.9176 4.64 27.2 1.25 0.009
0.001 0.048 "
w
u,
-..,
.4
Example 42 0.9176 0.99 23.9 1.23 0.007
0.006 0.046 0
0,
ts,
0
Example 102 0.9176 0.97 22.6 1.24 0.007
0.005 0.044 1--,
-.4
I
0
ts)
I
Example 54 0.9176 0.94 29.9 1.29 0.009
0.002 0.049 1--,
Example 41 0.9178 0.93 23.8 1.23 0.007
0.006 0.046
Example 44 0.9179 0.93 23.4 1.23 0.007
0.007 0.045
Example 9 0.9190 0.91 40.3 1.38 0.008
0.003 0.052
Example 200 0.9250 1.04 24.2 1.24 0.006
0.005 0.050
84
Example 60 0.9381 4.57 22.2 1.23 0.005
0.002 0.053
Example 61 0.9396 4.82 20.2 1.23 0.002
0.002 0.053
Example 62 0.9426 3.5 25.4 1.26 0.002
0.002 0.052
Example 70 0.9468 1.9 32.3 1.34 0.001
0.002 0.042
Example 71 0.9470 1.61 34.8 1.35 0.001
0.001 0.048
Example 72 0.9471 1.51 31.4 1.34 0.001
0.002 0.043
Example 73 0.9472 1.51 31.6 1.35 0.001
0.002 0.047 ci
o
tv
Example 80 0.9528 1.53 41.1 1.38 0.002
0.000 0.035 w
u,
-..,
.4
0
Example 81 0.9533 1.61 50 1.43 0.002
0.000 0.044 0,
ts,
0
1--,
Example 82 0.9546 1.6 59.6 1.5 0.001
0.000 0.045
I
0
ts)
I
Example 90 0.9588 7.51 29 1.28 0.001
0.000 0.042 1--,
Example 91 0.9589 6.72 30.4 1.29 0.002
0.000 0.041
Example 20 0.9596 1.21 31.3 1.35 0.002
0.001 0.036
Example 21 0.9618 1.31 38.3 1.39 0.002
0.001 0.037
Example 22 0.9620 1.3 51 1.49 0.002
0.001 0.041
Example 23 0.9621 0.63 78.9 1.68 0.002
0.001 0.042
Example 24 0.9646 1.98 83 1.79 0.001
0.001 0.052
TABLE 6A
Neutron Activation Analysis (NAA) catalyst residues in several embodiments of
the disclosed ethylene interpolymers, as
well as Comparatives G, I. J, B, C, E, E2, H and H2
Melt Index 12 N.A.A.
Elemental Analysis (ppm)
Sample Code Density (g/cm3)
ci
(dg/min) Ti Mg
Cl Al 0
w
u,
-..,
Example 60 0.9381 4.57 9.0 140
284 127 .4
0
0,
ts,
Example 62 0.9426 3.50 9.2 179
358 94 0
1--,
-.4
I
0
Example 70 0.9468 1.90 6.2 148
299 99 "
i
1--,
Example 71 0.9470 1.61 6.8 168
348 87
Example 72 0.9471 1.51 5.8 178
365 88
Example 73 0.9472 1.51 7.2 142
281 66
Example 80 0.9528 1.53 4.3 141
288 82
86
Example 81 0.9533 1.61 6.4 163
332 82
Example 82 0.9546 1.60 5.8 132
250 95
Example 90 0.9588 7.51 6.7 143
286 94
_
Example 91 0.9589 6.72 6.7 231
85 112
_
Example 1 0.9169 0.88 6.1 199
99 97
Example 2 0.9160 1.04 7.4 229
104 112
Example 3 0.9164 0.90 7.3 268
137 129 ci
o
tv
Comparative G 0.9612 0.89 1.6
17.2 53 11 w
u,
-..,
.4
0
Comparative I 0.9415 0.87 2.3 102
24 53 0,
ts,
0
1--,
Comparative J 0.9151 4.20 1.4 <2
0.6 7.9
I
0
ts)
I
I--,
Comparative B 0.9179 1.01 0.3
13.7 47 9.3
Comparative C 0.9161 1.00 2.0 9.0
25 5.4
Comparative E2 0.9138 1.56 1.2 9.8
32.2 6.8
Comparative E 0.9144 1.49 1.3 '
14.6 48.8 11.3
Comparative H 0.9191 0.90 2.2
14.6 48.8 11.3
87
Comparative H2 0.9189 0.89 2.2 253
122 130
Example1001 0.955 0.56 12.8 325
166 154
Example 1002 0.9558 0.65 13.1 333
168 156
TABLE 6B
Additional Neutron Activation Analysis (NAA) catalyst residues in several
embodiments of the disclosed ethylene
interpolymers
ci
o
tv
w
ul
-4
Melt Index 12 N.A.A. Elemental
Analysis (ppm) .4
0
Sample Code Density (g/cm3)
0,
(dg/min) Ti Mg
Cl Al 0
1--,
-.4
I
0
Example 4 0.9154 0.97 9.6 287
45 140 "
i
1--,
Example 5 0.9163 1.04 6.7 261
70 131
Example 6 0.9152 0.67 5.2 245
48 119
Example 7 0.9155 0.70 7.7 365
102 177
Example 8 0.9176 4.64 7.6 234
86 117
88
Example 9 0.9190 0.91 6.4 199 78
99
Example 51 0.9165 1.01 5.9 207 73
106
Example 52 0.9169 0.85 5.2 229
104 112
Example 53 0.9164 0.90 7.3 347
101 167
Example 54 0.9176 0.94 7.5 295
100 146
Example 55 0.9170 0.91 7.1 189
101 90
Example 41 0.9178 0.93 7.2 199
103 92 ci
o
tv
Example 42 0.9176 0.99 7.5 188
104 86 w
u,
-..,
.4
0
Example 43 0.9174 1.08 7.4 192
101 91 0,
ts,
0
1--,
Example 44 0.9179 0.93 7.2 230
121 110
I
0
ts)
I
Example 102 0.9176 0.97 9.5 239 60
117 1--,
Example 115 0.9171 0.75 5.1 258
115 130
Example 61 0.9396 4.82 8.3 352 96
179
Example 10 0.9168 0.94 7.8 333 91
170
Example 120 0.9204 1.00 7.3 284 75
149
89
Example 130 0.9232 0.94 5.8 292
114 147
Example 131 0.9242 0.95 8.6 81.4
173 94
Example 200 0.9250 1.04 6.3 90.1
190 104
ci
0
N)
W
Ul
-4
=.1
0
01
ts)
0
I--,
-.4
I
0
ts)
I
I--,
(A)
