Note: Descriptions are shown in the official language in which they were submitted.
ETHYLENE COPOLYMERS AND FILMS WITH EXCELLENT SEALING
PROPERTIES
FIELD OF THE DISCLOSURE
The present disclosure provides ethylene copolymer compositions
having a density of from 0.865 to 0.913 gicm3 which when blown into film
have excellent sealability. The ethylene copolymer compositions comprise a
first ethylene copolymer which may be made with a single site polymerization
catalyst, a second ethylene copolymer which may be made with a multi-site
polymerization catalyst; and optionally a third ethylene copolymer.
BACKGROUND OF THE DISCLOSURE
Multicomponent polyethylene compositions are well known in the art.
One method to access multicomponent polyethylene compositions is to use
two or more distinct polymerization catalysts in one or more polymerization
reactors. For example, the use of single site and Ziegler-Natta type
polymerization catalysts in at least two distinct solution polymerization
reactors is known. Such reactors may be configured in series or in parallel.
Solution polymerization processes are generally carried out at
temperatures above the melting point of the ethylene homopolymer or
copolymer product being made. In a typical solution polymerization process,
catalyst components, solvent, monomers and hydrogen are fed under
pressure to one or more reactors.
For solution phase ethylene polymerization, or ethylene
copolymerization, reactor temperatures can range from about 80 C to about
300 C while pressures generally range from about 3 MPag to about 45 MPag.
The ethylene homopolymer or copolymer produced remains dissolved in the
solvent under reactor conditions. The residence time of the solvent in the
reactor is relatively short, for example, from about 1 second to about 20
minutes. The solution process can be operated under a wide range of
process conditions that allow the production of a wide variety of ethylene
polymers. Post reactor, the polymerization reaction is quenched to prevent
further polymerization, by adding a catalyst deactivator, and optionally
passivated, by adding an acid scavenger. Once deactivated (and optionally
passivated), the polymer solution is passed to a polymer recovery operation
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(a devolatilization system) where the ethylene homopolymer or copolymer is
separated from process solvent, unreacted residual ethylene and unreacted
optional a-olefin(s).
Regardless of the manner of production, there remains a need to
improve the performance of multicomponent polyethylene compositions in film
applications.
SUMMARY OF THE DISCLOSURE
An embodiment in an ethylene copolymer composition comprising:
(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.8 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
wherein the ethylene copolymer composition has at least about 0.0015
parts per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
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An embodiment is a film layer comprising an ethylene copolymer
composition, the ethylene copolymer composition comprising:
(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.8 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
wherein the ethylene copolymer composition has at least about 0.0015
parts per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
In an embodiment a film layer is a blown film layer.
In an embodiment a blown film layer has a hot tack window (HTW) of at
least 45 C when measured at a film thickness of about 2 mil.
In an embodiment a blown film layer has a seal initiation temperature
(SIT) of less than 95 C when measured at a film thickness of about 2 mil.
In an embodiment a blown film layer has a hot tack onset temperature
(HTOT) of less than 88 C when measured at a film thickness of about 2 mil.
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In an embodiment a blown film layer has a dart impact strength of at
least 800 g/mil when measured at a film thickness of about 1 mil.
In an embodiment a blown film layer has a slow puncture resistance
value of at least 100 J/mm when measured at a film thickness of about 1 mil.
In an embodiment a blown film layer has a haze value of less than 6%
when measured at a film thickness of about 1 mil.
In an embodiment a film layer is a cast film layer.
In an embodiment a multilayer cast film structure has a seal initiation
temperature (SIT) of less than 90 C when measured at a film thickness of
about 2 mil.
An embodiment is a multilayer film structure comprising at least one
film layer comprising an ethylene copolymer composition, the ethylene
copolymer composition comprising:
(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.8 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
wherein the ethylene copolymer composition has at least about 0.0015
parts per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
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copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
An embodiment is a multilayer film structure comprising a sealant layer,
the sealant layer comprising an ethylene copolymer composition, the ethylene
copolymer composition comprising:
(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.8 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
wherein the ethylene copolymer composition has at least about 0.0015
parts per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
In an embodiment, a multilayer film structure has at least three film
layers.
In an embodiment, a multilayer film structure has at least five film
layers.
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In an embodiment, a multilayer film structure has at least seven film
layers.
In an embodiment, a multilayer film structure has at least nine film
layers.
In an embodiment, a multilayer film structure has nine film layers.
Brief Description of the Figures
Figure 1 shows the gel permeation chromatographs (GPC) with
refractive index detection of ethylene copolymer compositions made
according to the present disclosure.
Figures 2A-2F show the gel permeation chromatographs with Fourier
transform infra-red (GPC-FTIR) detection obtained for ethylene copolymer
compositions made according to the present disclosure. The comonomer
content, shown as the number of short chain branches per 1000 backbone
carbons (y-axis), is given relative to the copolymer molecular weight (x-
axis).
The upwardly sloping dashed line (from left to right) is the short chain
branching (in short chain branches per 1000 carbons atoms) determined by
FTIR. As can be seen in the Figures 2A-2F, for Inventive Examples 1-6, the
number of short chain branches initially increases at higher molecular weights
and then decreases again at still higher molecular weights, and hence the
comonomer incorporation is said to be "partially reversed" with a peak or
maximum present.
Figure 3 shows the CTREF profile obtained for an ethylene copolymer
composition made according to the present disclosure. In Figure 3, TPCTREF is
the peak elution temperature of the first ethylene copolymer in the CTREF
chromatogram.
Figure 4A shows the hot tack profiles for monolayer blown films made
using the ethylene copolymer compositions made according to the present
disclosure, while Figure 4B shows the hot tack profiles for monolayer blown
films made using comparative polyethylenes.
Figure 5 shows the hot tack profiles for coextruded cast films made
using the ethylene copolymer compositions made according to the present
disclosure as well as those for comparative polyethylenes.
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Figure 6 shows the hot tack profiles for multilayer blown films in which
a sealant layer was made with an ethylene copolymer composition made
according to the present disclosure or with a comparative polyethylene.
Definition of Terms
Other than in the examples or where otherwise indicated, all numbers
or expressions referring to quantities of ingredients, extrusion conditions,
etc.,
used in the specification and claims are to be understood as modified in all
instances by the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification and attached
claims are approximations that can vary depending upon the desired
properties that the various embodiments desire to obtain. At the very least,
and not as an attempt to limit the application of the doctrine of equivalents
to
the scope of the claims, each numerical parameter should at least be
construed in light of the number of reported significant digits and by
applying
ordinary rounding techniques. The numerical values set forth in the specific
examples are reported as precisely as possible. Any numerical values,
however, inherently contain certain errors necessarily resulting from the
standard deviation found in their respective testing measurements.
It should be understood that any numerical range recited herein is
intended to include all sub-ranges subsumed therein. For example, a range
of "1 to 10" is intended to include all sub-ranges between and including the
recited minimum value of 1 and the recited maximum value of 10; that is,
having a minimum value equal to or greater than 1 and a maximum value of
equal to or less than 10. Because the disclosed numerical ranges are
continuous, they include every value between the minimum and maximum
values. Unless expressly indicated otherwise, the various numerical ranges
specified in this application are approximations.
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
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amounts of the components actually used will conform to the maximum of 100
percent.
In order to form a more complete understanding of this disclosure the
following terms are defined and should be used with the accompanying
figures and the description of the various embodiments throughout.
As used herein, the term "monomer" refers to a small molecule that
may chemically react and become chemically bonded with itself or other
monomers to form a polymer.
As used herein, the term "a-olefin" or "alpha-olefin" is used to describe
a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon
atoms having a double bond at one end of the chain; an equivalent term is
"linear a-olefin". As used herein, the term "polyethylene" or "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. An "ethylene
homopolymer" is made using only ethylene as a polymerizable monomer.
The term "copolymer" refers to a polymer that contains two or more types of
monomer. An "ethylene copolymer" is made using ethylene and one or more
other types of polymerizable monomer. Common polyethylenes 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
polyethylene also includes polyethylene terpolymers which may include two or
more comonomers in addition to ethylene. The term polyethylene also
includes combinations of, or blends of, the polyethylenes described above.
The term "heterogeneously branched polyethylene" refers to a subset
of polymers in the ethylene polymer group that are produced using a
heterogeneous catalyst system; non-limiting examples of which include
Ziegler-Natta or chromium catalysts, both of which are well known in the art.
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The term "homogeneously branched polyethylene" refers to a subset of
polymers in the ethylene polymer group that are produced using single-site
catalysts; non-limiting examples of which include metallocene catalysts,
phosphinimine catalysts, and constrained geometry catalysts all of which are
well known in the art.
Typically, homogeneously branched polyethylenes have narrow
molecular weight distributions, for example gel permeation chromatography
(GPC) Mw/Mn values of less than about 2.8, especially less than about 2.3,
although exceptions may arise; Mw and Mn refer to weight and number
average molecular weights, respectively. In contrast, the Mw/Mn of
heterogeneously branched ethylene polymers are typically greater than the
Mw/Mn of homogeneous polyethylene. In general, homogeneously branched
ethylene polymers also have a narrow composition 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 polymer, as well as to differentiate ethylene polymers produced with
different catalysts or processes. The "CDBI5o" is defined as the percent of
ethylene polymer whose composition is within 50 weight percent (wt%) of the
median comonomer composition; this definition is consistent with that
described in WO 93/03093 assigned to Exxon Chemical Patents Inc. The
CD6150 of an ethylene copolymer 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 CD6150 of homogeneously branched ethylene polymers are
greater than about 70% or greater than about 75%. In contrast, the CD6150 of
a-olefin containing heterogeneously branched ethylene polymers are
generally lower than the CD6150 of homogeneous ethylene polymers. For
example, the CDBI50 of a heterogeneously branched ethylene polymer may
be less than about 75%, or less than about 70%.
It is well known to those skilled in the art, that homogeneously
branched ethylene polymers are frequently further subdivided into "linear
homogeneous ethylene polymers" and "substantially linear homogeneous
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ethylene polymers". These two subgroups differ in the amount of long chain
branching: more specifically, linear homogeneous ethylene polymers have
less than about 0.01 long chain branches per 1000 carbon atoms; while
substantially linear ethylene polymers 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
"homogeneously branched polyethylene" or "homogeneously branched
ethylene polymer" refers to both linear homogeneous ethylene polymers and
substantially linear homogeneous ethylene polymers.
The term "thermoplastic" refers to a polymer that becomes liquid when
heated, will flow under pressure and solidify when cooled. Thermoplastic
polymers include ethylene polymers as well as other polymers used in the
plastic industry; non-limiting examples of other polymers commonly used in
film applications include barrier resins (EVOH), tie resins, polyethylene
terephthalate (PET), polyamides and the like.
As used herein the term "monolayer film" refers to a film containing a
single layer of one or more thermoplastics.
As used herein the term "multilayer film" or "multilayer film structure"
refers to a film comprised of more than one thermoplastic layer, or optionally
non-thermoplastic layers. Non-limiting examples of non-thermoplastic
materials include metals (foil) or cellulosic (paper) products. One or more of
the thermoplastic layers within a multilayer film (or film structure) may be
comprised of more than one thermoplastic.
As used herein, the term "tie resin" refers to a thermoplastic that when
formed into an intermediate layer, or a "tie layer" within a multilayer film
structure, promotes adhesion between adjacent film layers that are dissimilar
in chemical composition.
As used herein, the term "sealant layer" refers to a layer of
thermoplastic film that is capable of being attached to a second substrate,
forming a leak proof seal. A "sealant layer" may be a skin layer or the
innermost layer in a multilayer film structure.
As used herein, the term "adhesive lamination" and the term "extrusion
lamination" describes continuous processes through which two or more
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substrates, or webs of material, are combined to form a multilayer product or
sheet; wherein the two or more webs are joined using an adhesive or a
molten thermoplastic film, respectively.
As used herein, the term "extrusion coating" describes a continuous
process through which a molten thermoplastic layer is combined with, or
deposited on, a moving solid web or substrate. Non-limiting examples of
substrates include paper, paperboard, foil, monolayer plastic film, multilayer
plastic film or fabric. The molten thermoplastic layer could be monolayer or
multilayer.
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.
As used herein, the term "aryl" group includes phenyl, naphthyl, pyridyl
and other radicals whose molecules have an aromatic ring structure; non-
limiting examples include naphthylene, phenanthrene and anthracene. An
"arylalkyl" group is an alkyl group having an aryl group pendant there from;
non-limiting examples include benzyl, phenethyl and tolylmethyl; an
"alkylaryl"
is an aryl group having one or more alkyl groups pendant there from; non-
limiting examples include tolyl, xylyl, mesityl and cumyl.
As used herein, the phrase "heteroatom" includes any atom other than
carbon and hydrogen that can be bound to carbon. A "heteroatom-containing
group" is a hydrocarbon radical that contains a heteroatom and may contain
one or more of the same or different heteroatoms. In one embodiment, a
heteroatom-containing group is a hydrocarbyl group containing from 1 to 3
atoms selected from the group consisting of boron, aluminum, silicon,
germanium, nitrogen, phosphorous, oxygen and sulfur. Non-limiting
examples of heteroatom-containing groups include radicals of imines, amines,
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oxides, phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines,
thioethers, and the like. The term "heterocyclic" refers to ring systems
having
a carbon backbone that comprise from 1 to 3 atoms selected from the group
consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous,
oxygen and sulfur.
As used herein the term "unsubstituted" means that hydrogen radicals
are bounded to the molecular group that follows the term unsubstituted. The
term "substituted" means that the group following this term possesses one or
more moieties (non hydrogen radicals) that have replaced one or more
hydrogen radicals in any position within the group; non-limiting examples of
moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl
groups, carboxyl groups, silyl groups, amine groups, phosphine groups,
alkoxy groups, phenyl groups, naphthyl groups, Ci to C30 alkyl groups, C2 to
C3O alkenyl groups, and combinations thereof. Non-limiting examples of
substituted alkyls and aryls include: acyl radicals, alkyl silyl radicals,
alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,
dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals,
carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals,
acylamino radicals, arylamino radicals and combinations thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the present disclosure, an ethylene copolymer composition will
comprise a first ethylene copolymer having a density, dl; a second ethylene
copolymer having a density, d2; and optionally a third ethylene copolymer
having a density, d3; wherein the density of the second ethylene copolymer is
equal to or greater than the density of the first ethylene copolymer. Each of
these ethylene copolymer components and the ethylene copolymer
composition of which they are a part are further described below.
The First Ethylene Copolymer
In an embodiment of the disclosure, the first ethylene copolymer is
made with a single site catalyst, non-limiting examples of which include
phosphinimine catalysts, metallocene catalysts, and constrained geometry
catalysts, all of which are well known in the art.
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In an embodiment of the disclosure, the first ethylene copolymer is
made with a single site catalyst, having hafnium, Hf as the active metal
center.
In embodiments of the disclosure, alpha-olefins which may be
copolymerized with ethylene to make the first ethylene copolymer may be
selected from the group comprising 1-propene, 1-butene, 1-pentene, 1-
hexene and 1-octene and mixtures thereof.
In an embodiment of the disclosure, the first ethylene copolymer is a
homogeneously branched ethylene copolymer.
In an embodiment of the disclosure, the first ethylene copolymer is an
ethylene/1-octene copolymer.
In an embodiment of the disclosure, the first ethylene copolymer is
made with a metallocene catalyst.
In an embodiment of the disclosure, the first ethylene copolymer is
made with a bridged metallocene catalyst.
In an embodiment of the disclosure, the first ethylene copolymer is
made with a bridged metallocene catalyst having the formula I:
R1
R4 \V
m-Q
/ R3
rN5
R2
(I)
In Formula (1): M is a group 4 metal selected from titanium, zirconium
or hafnium; G is a group 14 element selected from carbon, silicon,
germanium, tin or lead; Ri is a hydrogen atom, a C1-20 hydrocarbyl radical, a
C1-20 alkoxy radical or a C6-io aryl oxide radical; R2 and R3 are
independently
selected from a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy
radical or a C6-10 aryl oxide radical; R4 and R5 are independently selected
from
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a hydrogen atom, an unsubstituted C1-20 hydrocarbyl radical, a substituted C1-
20 hydrocarbyl radical, a C1-20 alkoxy radical or a C6-10 aryl oxide radical;
and Q
is independently an activatable leaving group ligand.
In an embodiment, R4 and R5 are independently an aryl group.
In an embodiment, R4 and R5 are independently a phenyl group or a
substituted phenyl group.
In an embodiment, R4 and R5 are a phenyl group.
In an embodiment, R4 and R5 are independently a substituted phenyl
group.
In an embodiment, R4 and R5 are a substituted phenyl group, wherein
the phenyl group is substituted with a substituted silyl group.
In an embodiment, R4 and R5 are a substituted phenyl group, wherein
the phenyl group is substituted with a trialkyl silyl group.
In an embodiment, R4 and R5 are a substituted phenyl group, wherein
the phenyl group is substituted at the para position with a trialkylsilyl
group. In
an embodiment, R1 and R2 are a substituted phenyl group, wherein the phenyl
group is substituted at the para position with a trimethylsilyl group. In an
embodiment, R1 and R2 are a substituted phenyl group, wherein the phenyl
group is substituted at the para position with a triethylsilyl group.
In an embodiment, R4 and R5 are independently an alkyl group.
In an embodiment, R4 and R5 are independently an alkenyl group.
In an embodiment, Ri is hydrogen.
In an embodiment, Ri is an alkyl group.
In an embodiment, Ri is an aryl group.
In an embodiment, Ri is an alkenyl group.
In an embodiment, R2 and R3 are independently a hydrocarbyl group
having from 1 to 30 carbon atoms.
In an embodiment, R2 and R3 are independently an aryl group.
In an embodiment, R2 and R3 are independently an alkyl group.
In an embodiment, R2 and R3 are independently an alkyl group having
from 1 to 20 carbon atoms.
In an embodiment, R2 and R3 are independently a phenyl group or a
substituted phenyl group.
In an embodiment, R2 and R3 are a tert-butyl group.
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In an embodiment, R2 and R3 are hydrogen.
In an embodiment M is hafnium, Hf.
In an embodiment of the disclosure, the first ethylene copolymer is
made with a bridged metallocene catalyst having the formula I:
Ri
R4
G ¨ Q
R5/ R3
µ141111
R2 ilk
(I)
In Formula (I): G is a group 14 element selected from carbon, silicon,
germanium, tin or lead; Ri is a hydrogen atom, a C1-20 hydrocarbyl radical, a
C1-20 alkoxy radical or a C6-10 aryl oxide radical; R2 and R3 are
independently
selected from a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy
radical or a C6-10 aryl oxide radical; R4 and R5 are independently selected
from
a hydrogen atom, an unsubstituted C1-20 hydrocarbyl radical, a substituted C1-
hydrocarbyl radical, a CI-20 alkoxy radical or a C6-10 aryl oxide radical; and
Q
15 is independently an activatable leaving group ligand.
In the current disclosure, the term "activatable", means that the ligand
Q may be cleaved from the metal center M via a protonolysis reaction or
abstracted from the metal center M by suitable acidic or electrophilic
catalyst
activator compounds (also known as "co-catalyst" compounds) respectively,
20 examples of which are described below. The activatable ligand Q may also
be transformed into another ligand which is cleaved or abstracted from the
metal center M (e.g. a halide may be converted to an alkyl group). Without
wishing to be bound by any single theory, protonolysis or abstraction
reactions generate an active "cationic" metal center which can polymerize
olefins.
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In embodiments of the present disclosure, the activatable ligand, Q is
independently selected from the group consisting of a hydrogen atom; a
halogen atom; a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical, and a C6-10
aryl or aryloxy radical, where each of the hydrocarbyl, alkoxy, aryl, or aryl
oxide radicals may be un-substituted or further substituted by one or more
halogen or other group; a C1-8 alkyl; a C1-8 alkoxy; a C6-10 aryl or aryloxy;
an
amido or a phosphido radical, but where Q is not a cyclopentadienyl. Two Q
ligands may also be joined to one another and form for example, a substituted
or unsubstituted diene ligand (e.g. 1,3-butadiene); or a delocalized
heteroatom containing group such as an acetate or acetamidinate group. In a
convenient embodiment of the disclosure, each Q is independently selected
from the group consisting of a halide atom, a C1-4 alkyl radical and a benzyl
radical. Particularly suitable activatable ligands Q are monoanionic such as a
halide (e.g. chloride) or a hydrocarbyl (e.g. methyl, benzyl).
In an embodiment of the disclosure, the single site catalyst used to
make the first ethylene copolymer is
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dichloride
having the molecular formula: [(2,7-tBu2F1u)Ph2C(Cp)HfC12].
In an embodiment of the disclosure the single site catalyst used to
make the first ethylene copolymer is
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dimethyl
having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].
In addition to the single site catalyst molecule per se, an active single
site catalyst system may further comprise one or more of the following: an
alkylaluminoxane co-catalyst and an ionic activator. The single site catalyst
system may also optionally comprise a hindered phenol.
Although the exact structure of alkylaluminoxane is uncertain, subject
matter experts generally agree that it is an oligomeric species that contain
repeating units of the general formula:
(R)2A10-(Al(R)-0)n-Al(R)2
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 alkylaluminoxane is methylaluminoxane (or
MAO) wherein each R group is a methyl radical.
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In an embodiment of the disclosure, R of the alkylaluminoxane, is a
methyl radical and m is from 10 to 40.
In an embodiment of the disclosure, the co-catalyst is modified
methylaluminoxane (MMAO).
It is well known in the art, that the alkylaluminoxane can serve dual
roles as both an alkylator and an activator. Hence, an alkylaluminoxane co-
catalyst is often used in combination with activatable ligands such as
halogens.
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 shown below;
[R5][B(R7)4]-
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
[(R8)2H][B(R7)4]-
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 with the nitrogen atom may form an anilinium radical and R7
is as defined above.
In both formula 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(perfluorophenyOboron with anilinium and trityl (or triphenylmethylium).
Additional non-limiting examples of ionic activators include: triethylammonium
tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-
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butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,
trimethylammonium tetra(o-tolyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-
dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron,
tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-
dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron,
N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-
pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium
tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron,
triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium
tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron,
tropillium tetrakispentafluorophenyl borate, triphenylmethylium
tetrakispentafluorophenyl borate,
benzene(diazonium)tetrakispentafluorophenyl borate, tropillium
tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-
tetrafluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-
trifluorophenyl)borate, tropillium tetrakis(3,4,5 -trifluorophenyl)borate,
benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium
tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium tetrakis(1 ,2,2-
trifluoroethenyl)borate, benzene(diazonium) tetrakis(1,2,2-
trifluoroethenyl)borate, tropillium tetrakis(2,3,4,5-tetrafluorophenyl)borate,
triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, and
benzene(diazonium) tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily
available commercial ionic activators include N,N-dimethylanilinium
tetrakispentafluorophenyl borate, and triphenylmethylium
tetrakispentafluorophenyl borate.
Non-limiting example of hindered phenols include butylated phenolic
antioxidants, butylated hydroxytoluene, 2,6-di-tertiarybuty1-4-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 system the quantity and mole
ratios of the three or four components: the single site catalyst, the
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alkylaluminoxane, the ionic activator, and the optional hindered phenol are
optimized.
In an embodiment of the disclosure, the single site catalyst used to
make the first ethylene copolymer produces no long chain branches, and/or
the first ethylene copolymer will contain no measurable amounts of long chain
branches.
In an embodiment of the disclosure, the single site catalyst used to
make the first ethylene copolymer produces long chain branches, and the first
ethylene copolymer will contain long chain branches, hereinafter `LCB'. LCB
is a well-known structural phenomenon in ethylene copolymers and well
known to those of ordinary skill in the art. Traditionally, there are three
methods for LCB analysis, namely, nuclear magnetic resonance spectroscopy
(NMR), for example see J.C. Randall, J Macromol. Sci., Rev. Macromol.
Chem. Phys. 1989, 29, 201; triple detection SEC equipped with a DRI, a
viscometer and a low-angle laser light scattering detector, for example see
W.W. Yau and D.R. Hill, Int. J. Polym. Anal. Charact. 1996; 2:151; and
rheology, for example see W.W. Graessley, Acc. Chem. Res. 1977, 10, 332-
339. In this disclosure, a long chain branch is macromolecular in nature, i.e.
long enough to be seen in an NMR spectra, triple detector SEC experiments
or rheological experiments.
In an embodiment of the disclosure, the first ethylene copolymer
contains long chain branching characterized by the LCBF disclosed herein. In
embodiments of the disclosure, the upper limit on the LCBF of the first
ethylene copolymer may be about 0.5, in other cases about 0.4 and in still
other cases about 0.3 (dimensionless). In embodiments of the disclosure, the
lower limit on the LCBF of the first ethylene copolymer may be about 0.001, in
other cases about 0.0015 and in still other cases about 0.002 (dimensionless).
The first ethylene copolymer may contain catalyst residues that reflect
the chemical composition of the catalyst formulation used to make it. Those
skilled in the art will understand that catalyst residues are typically
quantified
by the parts per million of metal, in for example the first ethylene copolymer
(or the ethylene copolymer composition; see below), where the metal present
originates from the metal in the catalyst formulation used to make it. Non-
limiting examples of the metal residue which may be present include Group 4
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metals, titanium, zirconium and hafnium. In embodiments of the disclosure,
the upper limit on the ppm of metal in the first ethylene copolymer may be
about 3.0 ppm, in other cases about 2.0 ppm and in still other cases about 1.5
ppm. In embodiments of the disclosure, the lower limit on the ppm of metal in
the first ethylene copolymer may be about 0.03 ppm, in other cases about
0.09 ppm and in still other cases about 0.15 ppm.
In an embodiment of the disclosure, the first ethylene copolymer has a
density of from 0.855 to 0.926 g/cm3, a molecular weight distribution, Mw/Mn
of
from 1.7 to 2.3, and a melt index, 12 of from 0.1 to 20 g/10min.
In an embodiment of the disclosure, the first ethylene copolymer has a
density of from 0.855 to 0.913 g/cm3, a molecular weight distribution, Mw/Mn
of
from 1.7 to 2.3, and a melt index, 12 of from 0.1 to 20 g/10min.
In embodiments of the disclosure, the upper limit on the molecular
weight distribution, Mw/Mn of the first ethylene copolymer may be about 2.8,
or
about 2.5, or about 2.4, or about 2.3, or about 2.2. In embodiments of the
disclosure, the lower limit on the molecular weight distribution, Mw/Mn of the
first ethylene copolymer may be about 1.6, or about 1.7, or about 1.8, or
about
1.9.
In embodiments of the disclosure, the first ethylene copolymer has a
molecular weight distribution, Mw/Mn of < 2.3, or 5 2.3, or < 2.1, or 5 2.1,
or <
2.0, or 5 2.0, or about 2Ø In embodiments of the disclosure, the first
ethylene copolymer has a molecular weight distribution, Mw/Mn of from about
1.7 to about 2.3, or from about 1.8 to about 2.3 or from about 1.8 to about
2.2.
In an embodiment of the disclosure, the first ethylene copolymer has
from 1 to 150 short chain branches per thousand carbon atoms (SCB1). In
further embodiments, the first ethylene copolymer has from 3 to 100 short
chain branches per thousand carbon atoms (SCB1), or from 5 to 100 short
chain branches per thousand carbon atoms (SCB1), or from 5 to 75 short
chain branches per thousand carbon atoms (SCB1), or from 10 to 75 short
chain branches per thousand carbon atoms (SCB1), or from 5 to 50 short
chain branches per thousand carbon atoms (SCB1), or from 10 to 50 short
chain branches per thousand carbon atoms (SCB1), or from 15 to 75 short
chain branches per thousand carbon atoms (SCB1). In still further
embodiments, the first ethylene copolymer has from 15 to 50 short chain
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branches per thousand carbon atoms (SCB1), or from 20 to 75 short chain
branches per thousand carbon atoms (SCB1), or from 20 to 50 short chain
branches per thousand carbon atoms (SCB1), or from 5 to 40 short chain
branches per thousand carbon atoms (SCB1), or from 10 to 40 short chain
branches per thousand carbon atoms (SCB1), or from 15 to 40 short chain
branches per thousand carbon atoms (SCB1), or from 20 to 35 short chain
branches per thousand carbon atoms (SCB1).
The short chain branching (i.e. the short chain branching per thousand
backbone carbon atoms, SCB1) is the branching due to the presence of an
alpha-olefin comonomer in the ethylene copolymer and will for example have
two carbon atoms for a 1-butene comonomer, or four carbon atoms for a 1-
hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.
In an embodiment of the disclosure, the number of short chain
branches per thousand carbon atoms in the first ethylene copolymer (SCB1),
is greater than the number of short chain branches per thousand carbon
atoms in the second ethylene copolymer (SCB2).
In an embodiment of the disclosure, the number of short chain
branches per thousand carbon atoms in the first ethylene copolymer (SCB1),
is greater than the number of short chain branches per thousand carbon
atoms in the third ethylene copolymer (SCB3).
In an embodiment of the disclosure, the number of short chain
branches per thousand carbon atoms in the first ethylene copolymer (SCB1),
is greater than the number of short chain branches per thousand carbon
atoms in each of the second ethylene copolymer (SCB2) and the third
ethylene copolymer (SCB3).
In embodiments of the disclosure, the upper limit on the density, dl of
the first ethylene copolymer may be about 0.941 g/cm3; in some cases about
0.936 g/cm3; in other cases about 0.931 g/cm3, in still other cases about
0.926
g/cm3, in yet still other cases about 0.921 g/cm3, or about 0.918 g/cm3, or
about 0.913 g/cm3, or about 0.912 g/cm3, or about 0.910 g/cm3. In
embodiments of the disclosure, the lower limit on the density, dl of the first
ethylene copolymer may be about 0.855 g/cm3, in some cases about 0.865
g/cm3, and; in other cases about 0.875 g/cm3.
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In embodiments of the disclosure the density, dl of the first ethylene
copolymer may be from about 0.855 g/cm3 to about 0.941 g/cm3, or from
about 0.855 g/cm3 to about 0.936 g/cm3, or from about 0.855 g/cm3 to about
0.931 g/cm3, or from about 0.855 g/cm3 to about 0.926 g/cm3, or from about
0.855 g/cm3 to about 0.921 g/cm3, or from about 0.855 g/cm3 to about 0.914
g/cm3, or from about 0.855 g/cm3 to about 0.913 g/cm3, or from about 0.855
g/cm3 to about 0.912 g/cm3, or from about 0.855 g/cm3 to about 0.910 g/cm3,
or from about 0.855 g/cm3 to about 0.906 g/cm3, or from about 0.865 g/cm3 to
about 0.941 g/cm3, or from about 0.865 g/cm3 to about 0.936 g/cm3, or from
about 0.865 g/cm3 to about 0.931 g/cm3, or from about 0.865 g/cm3 to about
0.926 g/cm3, or from about 0.865 g/cm3 to about 0.921 g/cm3, or from about
0.865 g/cm3 to about 0.914 g/cm3, or from about 0.865 g/cm3 to about 0.913
g/cm3, or from about 0.865 g/cm3 to about 0.912 g/cm3, or from about 0.865
g/cm3 to about 0.910 g/cm3, or from about 0.865 g/cm3 to about 0.906 g/cm3,
or from 0.875 g/cm3 to about 0.941 g/cm3, or from about 0.875 g/cm3 to about
0.936 g/cm3, or from about 0.875 g/cm3 to about 0.931 g/cm3, or from about
0.875 g/cm3 to about 0.926 g/cm3, or from about 0.875 g/cm3 to about 0.921
g/cm3, or from about 0.875 g/cm3 to about 0.914 g/cm3, or from about 0.875
g/cm3 to about 0.913 g/cm3, or from about 0.875 g/cm3 to about 0.912 g/cm3,
or from about 0.875 g/cm3 to about 0.910 g/cm3, or from about 0.875 g/cm3 to
about 0.906 g/cm3, or from about 0.885 g/cm3 to about 0.941 g/cm3, or from
about 0.885 g/cm3 to about 0.936 g/cm3, or from about 0.885 g/cm3 to about
0.931 g/cm3, or from about 0.885 g/cm3 to about 0.926 g/cm3, or from about
0.885 g/cm3 to about 0.921 g/cm3, or from about 0.885 g/cm3 to about 0.914
g/cm3, or from about 0.885 g/cm3 to about 0.913 g/cm3, or from about 0.885
g/cm3 to about 0.912 g/cm3, or from about 0.885 g/cm3 to about 0.910 g/cm3,
or from about 0.885 g/cm3 to about 0.906 g/cm3.
In an embodiment of the disclosure, the density of the first ethylene
copolymer, dl is equal to or less than the density of the second ethylene
copolymer, d2.
In an embodiment of the disclosure, the density of the first ethylene
copolymer, dl is less than the density of the second ethylene copolymer, d2.
In embodiments of the disclosure, the upper limit on the CDBI50 of the
first ethylene copolymer may be about 98 weight%, in other cases about 95
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wt% and in still other cases about 90 wt%. In embodiments of the disclosure,
the lower limit on the CDBI50 of the first ethylene copolymer may be about 70
weight%, in other cases about 75 wt% and in still other cases about 80 wt%.
In embodiments of the disclosure the melt index of the first ethylene
copolymer 121 may be from about 0.01 dg/min to about 100 dg/min, or from
about 0.01 dg/min to about 75 dg/min, or from about 0.1 dg/min to about 100
dg/min, or from about 0.1 dg/min to about 70 dg/min, or from about 0.01
dg/min to about 50 dg/min, or from about 0.1 dg/min to about 50 dg/min, or
from about 0.1 dg/min to about 25 dg/min, or from about 0.1 dg/min to about
20 dg/min, or from about 0.1 dg/min to about 15 dg/min, or from about 0.1 to
about 10 dg/min, or about 0.1 to about 5 dg/min, or from about 0.1 to 2.5
dg/min, or less than about 5 dg/min, or less than about 3 dg/min, or less than
about 1.0 dg/min, or less than about 0.75 dg/min.
In an embodiment of the disclosure, the first ethylene copolymer has a
weight average molecular weight, Mw of from about 50,000 to about 300,000,
or from about 50,000 to about 250,000, or from about 60,000 to about
250,000, or from about 70,000 to about 250,000, or from about 75,000 to
about 200,000, or from about 75,000 to about 175,000; or from about 70,000
to about 175,000, or from about 75,000 to about 150,000.
In an embodiment of the disclosure, the first ethylene copolymer has a
weight average molecular weight, Mw which is greater than the weight
average molecular weight, Mw of the second ethylene copolymer.
In embodiments of the disclosure, the upper limit on the weight percent
(wt%) of the first ethylene copolymer in the ethylene copolymer composition
(i.e. the weight percent of the first ethylene copolymer based on the total
weight of the first, the second and the third ethylene copolymer) may be about
80 wt%, or about 75 wt%, or about 70 wt%, or about 65 wt%, or about 60
wt%, or about 55 wt%, or about 50 wt%, or about 45 wt%, or about 40 wt%.
In embodiments of the disclosure, the lower limit on the wt% of the first
ethylene copolymer in the ethylene copolymer composition may be about 5
wt%, or about 10 wt%, or about 15 wt%, or about 20 wt%, or about 25 wt%, or
about 30 wt%, or in other cases about 35 wt%.
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The Second Ethylene Copolymer
In an embodiment of the disclosure, the second ethylene copolymer is
made with a multi-site catalyst system, non-limiting examples of which include
Ziegler-Natta catalysts and chromium catalysts, both of which are well known
in the art.
In embodiments of the disclosure, alpha-olefins which may be
copolymerized with ethylene to make the second ethylene copolymer may be
selected from the group comprising 1-propene, 1-butene, 1-pentene, 1-
hexene and 1-octene and mixtures thereof.
In an embodiment of the disclosure, the second ethylene copolymer is
a heterogeneously branched ethylene copolymer.
In an embodiment of the disclosure, the second ethylene copolymer is
an ethylene/1-octene copolymer.
In an embodiment of the disclosure, the second ethylene copolymer is
made with a Ziegler-Natta catalyst system.
Ziegler-Natta catalyst systems are well known to those skilled in the
art. A Ziegler-Natta catalyst may be an in-line Ziegler-Natta catalyst system
or a batch Ziegler-Natta catalyst system. The term "in-line Ziegler-Natta
catalyst system" refers to the continuous synthesis of a small quantity of an
active Ziegler-Natta catalyst system and immediately injecting this catalyst
into at least one continuously operating reactor, wherein the catalyst
polymerizes ethylene and one or more optional a-olefins to form an ethylene
polymer. The terms "batch Ziegler-Natta catalyst system" or "batch 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 system, or batch Ziegler-Natta
procatalyst, is transferred to a catalyst storage tank. The term "procatalyst"
refers to an inactive catalyst system (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, wherein an active
catalyst polymerizes ethylene and one or more optional a-olefins to form a
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ethylene copolymer. The procatalyst may be converted into an active catalyst
in the reactor or external to the reactor, or on route to the reactor.
A wide variety of compounds can be used to synthesize an active
Ziegler-Natta catalyst system. The following describes various compounds
that may be combined to produce an active Ziegler-Natta catalyst system.
Those skilled in the art will understand that the embodiments in this
disclosure
are not limited to the specific compounds disclosed.
An active Ziegler-Natta catalyst system may be formed from: a
magnesium compound, a chloride compound, a metal compound, an alkyl
aluminum co-catalyst and an aluminum alkyl. As will be appreciated by those
skilled in the art, Ziegler-Natta catalyst systems may contain additional
components; a non-limiting example of an additional component is an electron
donor, e.g. amines or ethers.
A non-limiting example of an active in-line (or batch) Ziegler-Natta
catalyst system can be prepared as follows. In the first step, a solution of a
magnesium compound is reacted with a solution of a chloride compound to
form a magnesium chloride support suspended in solution. Non-limiting
examples of magnesium compounds include Mg(R1)2; wherein the R1 groups
may be the same or different, linear, branched or cyclic hydrocarbyl radicals
containing 1 to 10 carbon atoms. Non-limiting examples of chloride
compounds include R2CI; wherein R2 represents a hydrogen atom, or a linear,
branched or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. In the
first step, the solution of magnesium compound may also contain an
aluminum alkyl. 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 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
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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 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:
Al(R4)p(0R9)q(X)r
wherein the R4 groups may be the same or different, hydrocarbyl groups
having from 1 to 10 carbon atoms; the OR9 groups may be the same or
different, alkoxy or aryloxy groups wherein R9 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 (or batch) Ziegler-Natta catalyst system, 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.
In an embodiment of the disclosure, the second ethylene copolymer
has a density of from 0.875 to 0.936 g/cm3; a molecular weight distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min.
In embodiments of the disclosure, the second ethylene copolymer has
a molecular weight distribution, Mw/Mn of 2.3, or > 2.3, or 2.5, or > 2.5, or
2.7, or > 2.7, or ?. 2.9, or > 2.9, or 3.0, or 3Ø In embodiments of the
disclosure, the second ethylene copolymer has a molecular weight
distribution, Mw/Mn of from 2.3 to 6.0, or from 2.3 to 5.5, or from 2.3 to
5.0, or
from 2.3 to 4.5, or from 2.3 to 4.0, or from 2.3 to 3.5, or from 2.3 to 3.0,
or
from 2.5 to 5.0, or from 2.5 to 4.5, or from 2.5 to 4.0, or from 2.5 to 3.5,
or
from 2.7 to 5.0, or from 2.7 to 4.5, or from 2.7 to 4.0, or from 2.7 to 3.5,
or
from 2.9 to 5.0, or from 2.9 to 4.5, or from 2.9 to 4.0, or from 2.9 to 3.5.
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In an embodiment of the disclosure, the second ethylene copolymer
has from 1 to 100 short chain branches per thousand carbon atoms (SCB2).
In further embodiments, the second ethylene copolymer has from 1 to 50
short chain branches per thousand carbon atoms (SCB2), or from 1 to 30
short chain branches per thousand carbon atoms (SCB2), or from 1 to 25
short chain branches per thousand carbon atoms (SCB2), or from 3 to 50
short chain branches per thousand carbon atoms (SCB2), or from 5 to 50
short chain branches per thousand carbon atoms (SCB2), or from 3 to 30
short chain branches per thousand carbon atoms (SCB2), or from 5 to 30
short chain branches per thousand carbon atoms (SCB2), or from 3 to 25
short chain branches per thousand carbon atoms (SCB2), or from 5 to 25
short chain branches per thousand carbon atoms (SCB2).
The short chain branching (i.e. the short chain branching per thousand
backbone carbon atoms, SCB2), is the branching due to the presence of
alpha-olefin comonomer in the ethylene copolymer and will for example have
two carbon atoms for a 1-butene comonomer, or four carbon atoms for a 1-
hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.
In embodiments of the disclosure, the upper limit on the density, d2 of
the second ethylene copolymer may be about 0.945 g/cm3; in some cases
about 0.941 g/cm3 and; in other cases about 0.936 g/cm3. In embodiments of
the disclosure, the lower limit on the density, d2 of the second ethylene
copolymer may be about 0.865 g/cm3, in some cases about 0.875 g/cm3, and;
in other cases about 0.885 g/cm3.
In embodiments of the disclosure the density, d2 of the second
ethylene copolymer may be from about 0.875 g/cm3 to about 0.945 g/cm3, or
from about 0.875 g/cm3 to about 0.941 g/cm3, or from about 0.875 g/cm3 to
about 0.936 g/cm3, or from about 0.875 g/cm3to about 0.931 g/cm3, or from
about 0.875 g/cm3 to about 0.929 g/cm3, or from about 0.875 g/cm3 to about
0.926 g/cm3, or from about 0.885 g/cm3 to about 0.945 g/cm3, or from about
0.885 g/cm3 to about 0.941 g/cm3, or from about 0.885 g/cm3 to about 0.936
g/cm3, or from about 0.885 g/cm3 to about 0.931 g/cm3, or from about 0.885
g/cm3 to about 0.929 g/cm3, or from about 0.885 g/cm3 to about 0.926 g/cm3,
or from about 0.895 g/cm3 to about 0.945 g/cm3, or from about 0.895 g/cm3 to
about 0.941 g/cm3, or from about 0.895 g/cm3 to about 0.936 g/cm3, or from
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about 0.895 g/cm3to about 0.931 g/cm3, or from about 0.895 g/cm3 to about
0.929 g/cm3, or from about 0.895 g/cm3 to about 0.926 g/cm3, or from about
0.910 g/cm3 to about 0.945 g/cm3, or from about 0.910 g/cm3 to about 0.941
g/cm3, or from about 0.910 g/cm3 to about 0.936 g/cm3, or from about 0.910
g/cm3 to about 0.931 g/cm3, or from about 0.910 g/cm3 to about 0.929 g/cm3,
or from about 0.910 g/cm3 to about 0.926 g/cm3.
In an embodiment of the disclosure, the density of the second ethylene
copolymer, d2 is equal to or greater than the density of the first ethylene
copolymer, dl.
In an embodiment of the disclosure, the density of the second ethylene
copolymer, d2 is greater than the density of the first ethylene copolymer, dl.
In an embodiment of the disclosure, the second ethylene copolymer
has a composition distribution breadth index, CDBI50 of less than 75 weight%
or 70 weight percent or less. In further embodiments of the disclosure, the
second ethylene copolymer has a CDBI5o of 65 wt% or less, or 60 wt% or
less, or 55 wt% or less, or 50 wt% or less, or 45 wt% or less.
In embodiments of the disclosure the melt index of the second ethylene
copolymer, 122 may be from about 0.1 dg/min to about 1,000 dg/min, or from
about 0.5 dg/min to about 500 dg/min, or from about 0.5 dg/min to about 100
dg/min, or from about 0.3 dg/min to about 100 dg/min, or from about 1.0
dg/min to about 500 dg/min, or from about 1.0 dg/min to about 75 dg/min, or
from about 0.5 dg/min to about 75 dg/min, or from about 0.3 dg/min to about
75 dg/min, or from about 0.5 dg/min to about 50 dg/min, or from about 0.3
dg/min to about 50 dg/min, or from about 0.5 dg/min to about 30 dg/min, or
from about 0.3 dg/min to about 30 dg/min, or from about 0.5 dg/min to about
25 dg/min, or from about 0.3 dg/min to about 25 dg/min, or from about 0.1
dg/min to about 25 dg/min, or from about 0.1 dg/min to about 15 dg/min, or
from about 0.5 dg/min to about 15 dg/min, or from about 0.3 dg/min to about
15 dg/min, or from about 0.1 dg/min to about 10 dg/min, or from about 0.5
dg/min to about 10 dg/min, or from about 0.3 dg/min to about 10 dg/min, or
from about 1.0 dg/min to about 30 dg/min, or from about 1.0 dg/min to about
25 dg/min, from about 1.0 dg/min to about 15 dg/min, or from about 1.0
dg/min to about 10 dg/min.
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In an embodiment of the disclosure, the second ethylene copolymer
has a weight average molecular weight, Mw of from about 25,000 to about
250,000, or from about 25,000 to about 200,000, or from about 30,000 to
about 150,000, or from about 40,000 to about 150,000, or from about 50,000
to about 130,000, or from about 50,000 to about 110,000.
In an embodiment of the disclosure, the weight average molecular
weight of the second ethylene copolymer is less than the weight average
molecular weight of the first ethylene copolymer.
In embodiments of the disclosure, the upper limit on the weight percent
(wt%) of the second ethylene copolymer in the ethylene copolymer
composition (i.e. the weight percent of the second ethylene copolymer based
on the total weight of the first, the second and the third ethylene
copolymers)
may be about 85 wt%, or about 80 wt%, or about 70 wt%, or about 65 wt%, in
other cases about 60 wt%. In embodiments of the disclosure, the lower limit
on the wt% of the second ethylene copolymer in the ethylene copolymer
composition may be about 5 wt%, or about 10 wt%, or about 15 wt%, or about
wt%, or about 25 wt%, or about 30 wt%, or about 35 wt%, or about 40
wt%, or about 45 wt%, or in other cases about 50 wt%.
In embodiments of the disclosure, the second ethylene copolymer has
20 no long chain branching present or does not have any detectable levels
of
long chain branching.
The Third Ethylene Copolymer
In an embodiment of the disclosure, the third ethylene copolymer is
made with a single site catalyst, non-limiting examples of which include
phosphinimine catalysts, metallocene catalysts, and constrained geometry
catalysts, all of which are well known in the art.
In an embodiment of the disclosure, the third ethylene copolymer is
made with a multi-site catalyst system, non-limiting examples of which include
Ziegler-Natta catalysts and chromium catalysts, both of which are well known
in the art.
In embodiments of the disclosure, alpha-olefins which may be
copolymerized with ethylene to make the third ethylene copolymer may be
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selected from the group comprising 1-propene, 1-butene, 1-pentene, 1-
hexene and 1-octene and mixtures thereof.
In an embodiment of the disclosure, the third ethylene copolymer is a
homogeneously branched ethylene copolymer.
In an embodiment of the disclosure, the third ethylene copolymer is an
ethylene/1-octene copolymer.
In an embodiment of the disclosure, the third ethylene copolymer is
made with a metallocene catalyst.
In an embodiment of the disclosure, the third ethylene copolymer is
made with a Ziegler-Natta catalyst.
In an embodiment of the disclosure, the third ethylene copolymer is a
heterogeneously branched ethylene copolymer.
In embodiments of the disclosure, the third ethylene copolymer has no
long chain branching present or does not have any detectable levels of long
chain branching.
In an embodiment of the disclosure, the third ethylene copolymer will
contain long chain branches, hereinafter `LCB'. LCB is a well-known
structural phenomenon in polyethylenes and well known to those of ordinary
skill in the art. Traditionally, there are three methods for LCB analysis,
namely, nuclear magnetic resonance spectroscopy (NMR), for example see
J.C. Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201;
triple detection SEC equipped with a DRI, a viscometer and a low-angle laser
light scattering detector, for example see W.W. Yau and D.R. Hill, Int. J.
Polym. Anal. Charact. 1996; 2:151; and rheology, for example see W.W.
Graessley, Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long
chain branch is macromolecular in nature, i.e. long enough to be seen in an
NMR spectra, triple detector SEC experiments or rheological experiments.
In an embodiment of the disclosure, the third ethylene copolymer
contains long chain branching characterized by the LCBF disclosed herein. In
embodiments of the disclosure, the upper limit on the LCBF of the third
ethylene copolymer may be about 0.5, in other cases about 0.4 and in still
other cases about 0.3 (dimensionless). In embodiments of the disclosure, the
lower limit on the LCBF of the third ethylene copolymer may be about 0.001,
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in other cases about 0.0015 and in still other cases about 0.002
(dimensionless).
In embodiments of the disclosure, the upper limit on the molecular
weight distribution, Mw/Mn of the third ethylene copolymer may be about 2.8,
or about 2.5, or about 2.4, or about 2.3, or about 2.2. In embodiments of the
disclosure, the lower limit on the molecular weight distribution, Mw/Mn of the
third ethylene copolymer may be about 1.4, or about 1.6, or about 1.7, or
about 1.8, or about 1.9.
In embodiments of the disclosure, the third ethylene copolymer has a
molecular weight distribution, Mw/Mn of < 2.3, or 2.3, or < 2.1, or s 2.1, or
<
2.0, or 2.0, or about 2Ø In embodiments of the disclosure, the first
ethylene copolymer has a molecular weight distribution, Mw/Mn of from about
1.7 to about 2.3, or from about 1.8 to about 2.3, or from about 1.8 to 2.2.
In embodiments of the disclosure, the third ethylene copolymer has a
molecular weight distribution, Mw/Mn of 2.3, or > 2.3, or 2.5, or > 2.5, or
2.7, or > 2.7, or 2.9, or > 2.9, or 3.0, or 3Ø In embodiments of the
disclosure, the third ethylene copolymer has a molecular weight distribution,
Mw/Mn of from 2.3 to 6.5, or from 2.3 to 6.0, or from 2.3 to 5.5, or from 2.3
to
5.0, or from 2.3 to 4.5, or from 2.3 to 4.0, or from 2.3 to 3.5, or from 2.3
to 3.0,
or from 2.5 to 5.0, or from 2.5 to 4.5, or from 2.5 to 4.0, or from 2.5 to
3.5, or
from 2.7 to 5.0, or from 2.7 to 4.5, or from 2.7 to 4.0, or from 2.7 to 3.5,
or
from 2.9 to 5.0, or from 2.9 to 4.5, or from 2.9 to 4.0, or from 2.9 to 3.5.
In embodiments of the disclosure, the third ethylene copolymer has a
molecular weight distribution, Mw/Mn of from 2.0 to 6.5, or from 2.3 to 6.5,
or
from 2.3 to 6.0, or from 2.0 to 6Ø
In embodiments of the disclosure, the upper limit on the density, d3 of
the third ethylene copolymer may be about 0.975 g/cm3; in some cases about
0.965 g/cm3 and; in other cases about 0.955 g/cm3, in yet other cases about
0.945 g/cm3 In embodiments of the disclosure, the lower limit on the density,
d3 of the third ethylene copolymer may be about 0.855 g/cm3, in some cases
about 0.865 g/cm3, and; in other cases about 0.875 g/cm3.
In embodiments of the disclosure the density, d3 of the third ethylene
copolymer may be from about 0.875 g/cm3 to about 0.965 g/cm3, or from
about 0.875 g/cm3 to about 0.960 g/cm3, or from about 0.875 g/cm3 to 0.950
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g/cm3, from about 0.865 g/cm3 to about 0.945 g/cm3, or from about 0.865
g/cm3 to about 0.940 g/cm3, or from about 0.865 g/cm3 to about 0.936 g/cm3,
or from about 0.865 g/cm3 to about 0.932 g/cm3, or from about 0.865 g/cm3 to
about 0.926 g/cm3, or from about 0.865 g/cm3 to about 0.921 g/cm3, or from
about 0.865 g/cm3 to about 0.918 g/cm3, or from about 0.875 g/cm3 to about
0.916 g/cm3, or from about 0.875 g/cm3 to about 0.916 g/cm3, or from about
0.865 g/cm3 to about 0.912 g/cm3, or from about 0.880 g/cm3 to about 0.912
g/cm3, or from about 0.890 g/cm3 to about 0.916 g/cm3, or from about 0.900
g/cm3 to about 0.916 g/cm3, or from about 0.880 g/cm3 to about 0.916 g/cm3,
or from about 0.880 g/cm3 to about 0.918 g/cm3, or from about 0.880 g/cm3 to
about 0.921 g/cm3, or from about 0.880 g/cm3 to about 0.926 g/cm3, or from
about 0.880 g/cm3 to about 0.932 g/cm3, or from about 0.880 g/cm3 to about
0.936 g/cm3.
In embodiments of the disclosure, the upper limit on the CDBI50 of the
third ethylene copolymer may be about 98 weight%, in other cases about 95
wt% and in still other cases about 90 wt%. In embodiments of the disclosure,
the lower limit on the CDBI50 of the third ethylene copolymer may be about 70
weight%, in other cases about 75 wt% and in still other cases about 80 wt%.
In an embodiment of the disclosure, the third ethylene copolymer is an
ethylene copolymer which has a composition distribution breadth index,
CDBI50 of less than 75 wt%, or 70 wt% or less. In further embodiments of the
disclosure, the third ethylene copolymer is an ethylene copolymer which has a
CDBI50 of 65 wt% or less, or 60 wt% or less, or 55 wt% or less, or 50 wt% or
less, or 45 wt% or less.
In embodiments of the disclosure the melt index of the third ethylene
copolymer 123 may be from about 0.01 dg/min to about 1000 dg/min, or from
about 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min to about
100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or from about 0.01
dg/min to about 25 dg/min, or from about 0.01 dg/min to about 10 dg/min, or
from about 0.01 dg/min to about 5 dg/min, or from about 0.01 dg/min to about
3 dg/min, or from about 0.01 dg/min to about 1 dg/min, or less than about 5
dg/min, or less than about 3 dg/min, or less than about 1.0 dg/min, or less
than about 0.75 dg/min, or less than about 0.50 dg/min.
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In embodiments of the disclosure the melt index of the third ethylene
copolymer 123 may be from about 0.1 dg/min to about 1000 dg/min, or from
about 0.2 dg/min to about 500 dg/min, or from about 0.3 dg/min to about 200
dg/min.
In an embodiment of the disclosure, the third ethylene copolymer has a
weight average molecular weight, Mw of from about 50,000 to about 300,000,
or from about 50,000 to about 250,000, or from about 60,000 to about
250,000, or from about 70,000 to about 250,000, or from about 75,000 to
about 200,000, or from about 80,000 to about 275,000; or from about 80,000
to about 250,000, or from about 80,000 to about 200,000, or from about
80,000 to about 175,000.
In embodiments of the disclosure, the upper limit on the weight percent
(wt%) of the third ethylene copolymer in the ethylene copolymer composition
(i.e. the weight percent of the third ethylene copolymer based on the total
weight of the first, the second and the third ethylene copolymer) may be about
60 wt%, or about 55 wt%, or 50 wt%, in other cases about 45 wt%, in other
cases about 40 wt%, or about 35 wt%, or about 30 wt%, or about 25 wt%, or
about 20 wt%. In embodiments of the disclosure, the lower limit on the wt% of
the third ethylene copolymer in the final ethylene copolymer composition may
be 0 wt%, or about 1 wt%, or about 3 wt%, or about 5 wt%, or about 10 wt%,
or about 15 wt%.
The Ethylene Copolymer Composition
The polyethylene compositions disclosed herein can be made using
any well-known techniques in the art, including but not limited to melt
blending, solution blending, or in-reactor blending to bring together a first
ethylene copolymer, a second ethylene copolymer and optionally a third
ethylene copolymer.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made using a single site catalyst in a first reactor to give a
first
ethylene copolymer, and a multi-site catalyst is used in a second reactor to
give a second ethylene copolymer.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made using a single site catalyst in a first reactor to give a
first
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ethylene copolymer, a multi-site catalyst is used in a second reactor to give
a
second ethylene copolymer, and a multi-site catalyst is used in a third
reactor
to give a third ethylene copolymer.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made using a single site catalyst in a first reactor to give a
first
ethylene copolymer, a multi-site catalyst is used in a second reactor to give
a
second ethylene copolymer, and a single site catalyst is used in a third
reactor
to give a third ethylene copolymer.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first reactor by
polymerizing ethylene and an alpha olefin with a single site catalyst; and
forming a second ethylene copolymer in a second reactor by polymerizing
ethylene and an alpha olefin with a multi-site catalyst.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first reactor by
polymerizing ethylene and an alpha olefin with a single site catalyst; forming
a
second ethylene copolymer in a second reactor by polymerizing ethylene and
an alpha olefin with a multi-site catalyst, and forming a third ethylene
copolymer in a third reactor by polymerizing ethylene and an alpha olefin with
a multi-site catalyst.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first reactor by
polymerizing ethylene and an alpha olefin with a single site catalyst; forming
a
second ethylene copolymer in a second reactor by polymerizing ethylene and
an alpha olefin with a multi-site catalyst, and forming a third ethylene
copolymer in a third reactor by polymerizing ethylene and an alpha olefin with
a single site catalyst.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; and forming a second ethylene copolymer in a
second solution phase polymerization reactor by polymerizing ethylene and
an alpha olefin with a multi-site catalyst.
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In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a multi-site catalyst.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a single site catalyst.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; and forming a second ethylene copolymer in a
second solution phase polymerization reactor by polymerizing ethylene and
an alpha olefin with a multi-site catalyst, where the first and second
solution
phase polymerization reactors are configured in series with one another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; and forming a second ethylene copolymer in a
second solution phase polymerization reactor by polymerizing ethylene and
an alpha olefin with a multi-site catalyst, where the first and second
solution
phase polymerization reactors are configured in parallel with one another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
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solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a multi-site catalyst, where the first and second solution
phase polymerization reactors are configured in series with one another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a multi-site catalyst, where at least the first and second
solution phase polymerization reactors are configured in series with one
another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a multi-site catalyst, where the first, second and third
solution
phase polymerization reactors are configured in series with one another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a multi-site catalyst, where each of the first, second and
third
solution phase polymerization reactors are configured in parallel to one
another.
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In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a multi-site catalyst, where the first and second solution
phase reactors are configured in series to one another, and the third solution
phase reactor is configured in parallel to the first and second reactors.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a single site catalyst, where at least the first and second
solution phase polymerization reactors are configured in series with one
another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a single site catalyst, where the first, second and third
solution phase polymerization reactors are configured in series with one
another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
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solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a single site catalyst, where each of the first, second and
third solution phase polymerization reactors are configured in parallel to one
another.
In an embodiment, the ethylene copolymer composition of the present
disclosure is made by forming a first ethylene copolymer in a first solution
phase polymerization reactor by polymerizing ethylene and an alpha olefin
with a single site catalyst; forming a second ethylene copolymer in a second
solution phase polymerization reactor by polymerizing ethylene and an alpha
olefin with a multi-site catalyst, and forming a third ethylene copolymer in a
third solution phase polymerization reactor by polymerizing ethylene and an
alpha olefin with a single site catalyst, where the first and second solution
phase reactors are configured in series to one another, and the third solution
phase reactor is configured in parallel to the first and second reactors.
In an embodiment, the solution phase polymerization reactor used as a
first solution phase reactor, a second solution phase reactor, or a third
solution phase reactor is a continuously stirred tank reactor or a tubular
reactor.
In an embodiment, the solution phase polymerization reactor used as a
first solution phase reactor, a second solution phase reactor, or a third
solution phase reactor is a continuously stirred tank reactor.
In an embodiment, the solution phase polymerization reactor used as a
first solution phase reactor, a second solution phase reactor, or a third
solution phase reactor is a tubular reactor.
In an embodiment, the solution phase polymerization reactor used as a
first solution phase reactor and a second solution phase reactor is a
continuously stirred tank reactor, and the solution phase polymerization
reactor used as a third solution phase reactor is a tubular reactor.
In solution polymerization, the monomers are dissolved/dispersed in
the solvent either prior to being fed to the reactor (or for gaseous monomers
the monomer may be fed to the reactor so that it will dissolve in the reaction
mixture). Prior to mixing, the solvent and monomers are generally purified to
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remove potential catalyst poisons such as water, oxygen or metal impurities.
The feedstock purification follows standard practices in the art, e.g.
molecular
sieves, alumina beds and oxygen removal catalysts are used for the
purification of monomers. The solvent itself as well (e.g. methyl pentane,
cyclohexane, hexane or toluene) is preferably treated in a similar manner.
The feedstock may be heated or cooled prior to feeding to the reactor.
Generally, the catalyst components may be premixed in the solvent for
the reaction or fed as separate streams to the reactor. In some instances
premixing it may be desirable to provide a reaction time for the catalyst
components prior to entering the reaction. Such an "in line mixing" technique
is described in a number of patents in the name of DuPont Canada Inc. (e.g.
U.S. Pat. No. 5,589,555 issued Dec. 31, 1996).
Solution polymerization processes for the polymerization or
copolymerization of ethylene are well known in the art (see for example U.S.
Pat. Nos. 6,372,864 and 6,777,509). These processes are conducted in the
presence of an inert hydrocarbon solvent. In a solution phase polymerization
reactor, a variety of solvents may be used as the process solvent; non-
limiting
examples include linear, branched or cyclic C5 to C12 alkanes. Non-limiting
examples of a-olefins include 1-propene, 1-butene, 1-pentene, 1-hexene and
1-octene. Suitable catalyst component solvents include aliphatic and
aromatic hydrocarbons. Non-limiting examples of aliphatic catalyst
component solvents include linear, branched or cyclic C5-12 aliphatic
hydrocarbons, e.g. pentane, methyl pentane, hexane, heptane, octane,
cyclohexane, cyclopentane, methylcyclohexane, hydrogenated naphtha or
combinations thereof. Non-limiting examples of aromatic catalyst component
solvents include benzene, toluene (methylbenzene), ethylbenzene, o-xylene
(1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4-
dimethylbenzene), mixtures of xylene isomers, hemellitene (1,2,3-
trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene
(1,3,5-trimethylbenzene), mixtures of trimethylbenzene isomers, prehenitene
(1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), mixtures
of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene
and combinations thereof.
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The polymerization temperature in a conventional solution process may
be from about 80 C to about 300 C. In an embodiment of the disclosure the
polymerization temperature in a solution process is from about 120 C to about
250 C. The polymerization pressure in a solution process may be a "medium
pressure process", meaning that the pressure in the reactor is less than about
6,000 psi (about 42,000 kiloPascals or kPa). In an embodiment of the
disclosure, the polymerization pressure in a solution process may be from
about 10,000 to about 40,000 kPa, or from about 14,000 to about 22,000 kPa
(i.e. from about 2,000 psi to about 3,000 psi).
Suitable monomers for copolymerization with ethylene include C3-20
mono- and di-olefins. Preferred comonomers include C3-12 alpha olefins
which are unsubstituted or substituted by up to two C1-6 alkyl radicals, C8-12
vinyl aromatic monomers which are unsubstituted or substituted by up to two
substituents selected from the group consisting of C1_4 alkyl radicals, C4-12
straight chained or cyclic diolefins which are unsubstituted or substituted by
a
C1-4 alkyl radical. Illustrative non-limiting examples of such alpha-olefins
are
one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-
decene, styrene, alpha methyl styrene, and the constrained-ring cyclic olefins
such as cyclobutene, cyclopentene, dicyclopentadiene norbornene, alkyl-
substituted norbornenes, alkenyl-substituted norbornenes and the like (e.g. 5-
methylene-2-norbornene and 5-ethylidene-2-norbornene, bicyclo-(2,2,1)-
hepta-2,5-diene).
In an embodiment of the disclosure, the ethylene copolymer
composition has at least 1 mole percent of one or more than one alpha olefin.
In an embodiment of the disclosure, the ethylene copolymer
composition has at least 3 mole percent of one or more than one alpha olefin.
In an embodiment of the disclosure, the ethylene copolymer
composition has from about 1 to about 10 mole percent of one or more than
one alpha-olefin.
In an embodiment of the disclosure, the ethylene copolymer
composition has from about 3 to about 10 mole percent of one or more than
one alpha-olefin.
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In an embodiment of the disclosure, the ethylene copolymer
composition has from about 3 to about 8 mole percent of one or more than
one alpha olefin.
In an embodiment of the disclosure, the ethylene copolymer comprises
ethylene and one or more than one alpha olefin selected from the group
comprising 1-butene, 1-hexene, 1-octene and mixtures thereof.
In an embodiment of the disclosure, the ethylene copolymer comprises
ethylene and one or more than one alpha olefin selected from the group
comprising 1-hexene, 1-octene and mixtures thereof.
In an embodiment of the disclosure, the ethylene copolymer comprises
ethylene and 1-octene.
In an embodiment of the disclosure, the ethylene copolymer comprises
ethylene and at least 1 mole percent 1-octene.
In an embodiment of the disclosure, the ethylene copolymer comprises
ethylene and from 1 to 10 mole percent of 1-octene.
In an embodiment of the disclosure, the ethylene copolymer comprises
ethylene and from 3 to 8 mole percent of 1-octene.
In embodiments of the disclosure, the ethylene copolymer composition
has a density which may be from about 0.855 g/cm3 to about 0.914 g/cm3, or
from about 0.865 g/cm3 to about 0.913 g/cm3, or from about 0.865 g/cm3 to
0.912 g/cm3, or from about 0.875 g/cm3 to about 0.913 g/cm3, or from about
0.875 g/cm3 to about 0.912 g/cm3, or from about 0.865 g/cm3 to about 0.910
g/cm3, or from about 0.865 g/cm3 to about 0.910 g/cm3, or from about 0.875
g/cm3 to about 0.910 g/cm3, or from about 0.885 g/cm3 to about 0.913 g/cm3,
or from about 0.885 g/cm3 to about 0.912 g/cm3, or from about 0.885 g/cm3 to
about 0.910 g/cm3, or from about 0.895 g/cm3 to about 0.913 g/cm3, or from
about 0.895 g/cm3 to about 0.912 g/cm3, or from about 0.895 g/cm3 to about
0.910 g/cm3, or from about 0.895 g/cm3 to about 0.913 g/cm3.
In embodiments of the disclosure the melt index, 12 of the ethylene
copolymer composition may be from about 0.01 dg/min to about 1000 dg/min,
or from about 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min to
about 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or from
about 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about 10
dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about 0.01
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dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1 dg/min, or
from about 0.1 dg/min to about 10 dg/min, or from about 0.1 dg/min to about 5
dg/min, or from about 0.1 dg/min to about 3 dg/min, or from about 0.1 dg/min
to about 2 dg/min, or from about 0.1 dg/min to about 1.5 dg/min, or from about
0.1 dg/min to about 1 dg/min, or from about 0.5 dg/min to about 100 dg/min,
or from about 0.5 dg/min to about 50 dg/min, or from about 0.5 dg/min to
about 25 dg/min, or from about 0.5 dg/min to about 10 dg/min, or from about
0.5 dg/min to about 5 dg/min, or less than about 5 dg/min, or less than about
3 dg/min, or less than about 1.0 dg/min.
In embodiments of the disclosure the high load melt index, 121 of the
ethylene copolymer composition may be from about 10 dg/min to about
10,000 dg/min, or from about 10 dg/min to about 1000 dg/min, or from about
10 dg/min to about 500 dg/min, or from about 10 dg/min to about 250 dg/min,
or from about 10 dg/min to about 150 dg/min, or from about 10 dg/min to
about 100 dg/min.
In embodiments of the disclosure the melt flow ratio 121/12 of the
ethylene copolymer composition may be from about 15 to about 1,000, or
from about 15 to about 100, or from about 15 to about 75, or from about 15 to
about 50, or from about 15 to about 40, or from about 18 to about 50, or from
about 20 to about 75, or from about 20 to about 50, or from about 20 to about
45, or from about 20 to about 40, or from about 20 to about 38, or from about
20 to about 35, or less than about 45, or less than about 40, or less than
about 35, or less than about 30.
In embodiments of the disclosure, the ethylene copolymer composition
has a weight average molecular weight, Mw of from about 40,000 to about
300,000, or from about 40,000 to about 250,000, or from about 50,000 to
about 250,000, or from about 50,000 to about 225,000, or from about 50,000
to about 200,000, or from about 50,000 to about 175,000, or from about
50,000 to about 150,000, or from about 50,000 to about 125,000.
In embodiments of the disclosure, the ethylene copolymer composition
has a lower limit molecular weight distribution, Mw/Mn of 2.0, or 2.1, or 2.2,
or
2.3. In embodiments of the disclosure, the polyethylene composition has an
upper limit molecular weight distribution, Mw/Mn of 6.0, or 5.5, or 5.0, or
4.5, or
4.0, or 3.75, or 3.5.
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In embodiments of the disclosure, the ethylene copolymer composition
has a molecular weight distribution, Mw/Mn of from 2.1 to 6.0, or from 2.1 to
5.5, or from 2.1 to 5.0, or from 2.1 to 4.5, or from 2.1 to 4.0, or from 2.1
to 3.5,
or from 2.1 to 3.0, or from 2.2 to 5.5, or from 2.2 to 5.0, or from 2.2 to
4.5, or
from 2.2 to 4.0, or from 2.2 to 3.5, or from 2.2 to 3Ø
In embodiments of the disclosure, the ethylene copolymer composition
has a Z-average molecular weight distribution, Mz/Mw of 5 4.0, or < 4.0, or 5
3.5, or < 3.5, or 5 3.0, or <3.0, or 5 2.75, or <2.75, or 5 2.50, or < 2.50.
In
embodiments of the disclosure, the polyethylene composition has a Z-average
molecular weight distribution, Mz/Mw of from 1.5 to 4.0, or from 1.75 to 3.5,
or
from 1.75 to 3.0, or from 2.0 to 4.0, or from 2.0 to 3.5, or from 2.0 to 3.0,
or
from 2.0 to 2.75.
In an embodiment of the disclosure, the ethylene copolymer
composition has a unimodal profile in a gel permeation chromatograph
generated according to the method of ASTM D6474-99. The term "unimodal"
is herein defined to mean there will be only one significant peak or maximum
evident in the GPC-curve. A unimodal profile includes a broad unimodal
profile. In contrast, the use of the term "bimodal" is meant to convey that in
addition to a first peak, there will be a secondary peak or shoulder which
represents a higher or lower molecular weight component (i.e. the molecular
weight distribution, can be said to have two maxima in a molecular weight
distribution curve). Alternatively, the term "bimodal" connotes the presence
of two maxima in a molecular weight distribution curve generated according to
the method of ASTM D6474-99. The term "multi-modal" denotes the
presence of two or more, typically more than two, maxima in a molecular
weight distribution curve generated according to the method of ASTM D6474-
99.
In an embodiment of the disclosure, the ethylene copolymer
composition will have a reverse or partially reverse comonomer distribution
profile as measured using GPC-FTIR. If the comonomer incorporation
decreases with molecular weight, as measured using GPC-FTIR, the
distribution is described as "normal". If the comonomer incorporation is
approximately constant with molecular weight, as measured using GPC-FTIR,
the comonomer distribution is described as "flat" or "uniform". The terms
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"reverse comonomer distribution" and "partially reverse comonomer
distribution" mean that in the GPC-FTIR data obtained for a copolymer, there
is one or more higher molecular weight components having a higher
comonomer incorporation than in one or more lower molecular weight
components. The term "reverse(d) comonomer distribution" is used herein to
mean, that across the molecular weight range of an ethylene copolymer,
comonomer contents for the various polymer fractions are not substantially
uniform and the higher molecular weight fractions thereof have proportionally
higher comonomer contents (i.e. if the comonomer incorporation rises with
molecular weight, the distribution is described as "reverse" or "reversed").
Where the comonomer incorporation rises with increasing molecular weight
and then declines, the comonomer distribution is still considered "reverse",
but
may also be described as "partially reverse". A partially reverse comonomer
distribution will exhibit a peak or maximum.
In an embodiment of the disclosure the ethylene copolymer
composition has a reversed comonomer distribution profile as measured
using GPC-FTIR.
In an embodiment of the disclosure the ethylene copolymer
composition has a partially reversed comonomer distribution profile as
measured using GPC-FTIR.
In an embodiment of the disclosure, the ethylene copolymer
composition has a fraction eluting at from 90 to 105 C, having an integrated
area of greater than 3.0 weight percent, in a temperature rising elution
fractionation (TREF) analysis as obtained using a CTREF instrument (a
"CRYSTAF/Temperature Rising Elution Fractionation instrument). In an
embodiment of the disclosure, the ethylene copolymer composition has a
fraction eluting at from 90 to 105 C, having an integrated area of greater
than
3.5 weight percent, in a temperature rising elution fractionation (TREF)
analysis as obtained using a CTREF instrument (a "CRYSTAF/Temperature
Rising Elution Fractionation instrument). In an embodiment of the disclosure,
the ethylene copolymer composition has a fraction eluting at from 90 to
105 C, having an integrated area of greater than 4.0 weight percent, in a
temperature rising elution fractionation (TREF) analysis as obtained using a
CTREF instrument (a "CRYSTAF/Temperature Rising Elution Fractionation
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instrument). In an embodiment of the disclosure, the ethylene copolymer
composition has a fraction eluting at from 90 to 105 C, having an integrated
area of greater than 4.5 weight percent, in a temperature rising elution
fractionation (TREF) analysis as obtained using a CTREF instrument (a
"CRYSTAF/Temperature Rising Elution Fractionation instrument). In an
embodiment of the disclosure, the ethylene copolymer composition has a
fraction eluting at from 90 to 105 C, having an integrated area of greater
than
5.0 weight percent, in a temperature rising elution fractionation (TREF)
analysis as obtained using a CTREF instrument (a "CRYSTAFfTemperature
Rising Elution Fractionation instrument).
In embodiments of the disclosure, the ethylene copolymer composition
has a CDBI50 of from about 50 to 85 weight%, or from about 60 to 85 wt%, or
from about 60 to about 80 wt%, or from about 60 to about 75 wt%, or from
about 50 to about 80 wt%, or from about 50 to about 75 wt%, or from about 55
to about 80 wt%, or from about 55 to about 75 wt%.
In embodiments of the disclosure, the upper limit on the parts per
million (ppm) of hafnium in the ethylene copolymer composition may be about
3.0 ppm, or about 2.5 ppm, or about 2.0 ppm, or about 1.5 ppm, or about 1.0
ppm, or about 0.75 ppm, or about 0.5 ppm. In embodiments of the disclosure,
the lower limit on the parts per million (ppm) of hafnium in the ethylene
copolymer composition may be about 0.0015 ppm, or about 0.0050 ppm, or
about 0.0075 ppm, or about 0.010 ppm, or about 0.015 ppm, or about 0.030
ppm, or about 0.050 ppm, or about 0.075 ppm, or about 0.100 ppm, or about
0.150 ppm, or about 0.175 ppm, or about 0.200 ppm.
In embodiments of the disclosure, the ethylene copolymer composition
has from 0.0015 to 2.5 ppm of hafnium, or from 0.0050 to 2.5 ppm of hafnium,
or from 0.0075 to 2.5 ppm of hafnium, or from 0.010 to 2.5 ppm of hafnium, or
from 0.015 to 2.5 ppm of hafnium, or from 0.050 to 3.0 ppm of hafnium, or
from 0.050 to 2.5 ppm, or from 0.075 to 2.5 ppm of hafnium, or from 0.075 to
2.0 ppm of hafnium, or from 0.075 to 1.5 ppm of hafnium, or from 0.075 to 1.0
ppm of hafnium, or from 0.075 to 0.5 ppm of hafnium, or from 0.100 to 2.0
ppm of hafnium, or from 0.100 to 1.5 ppm of hafnium, or from 0.100 to 1.0
ppm of hafnium, or from 0.100 to 0.75 ppm of hafnium, or from 0.10 to 0.5
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ppm of hafnium, or from 0.15 to 0.5 ppm of hafnium, or from 0.20 to 0.5 ppm
of hafnium.
In embodiments of the disclosure, the ethylene copolymer composition
has at least 0.0015 ppm of hafnium, or at least 0.005 ppm of hafnium, or at
least 0.0075 ppm of hafnium, or at least 0.015 ppm of hafnium, or at least
0.030 ppm of hafnium, or at least 0.050 ppm of hafnium, or at least 0.075 ppm
of hafnium, or at least 0.100 ppm of hafnium, or at least 0.125 ppm of
hafnium, or at least 0.150 ppm of hafnium, or at least 0.175 ppm of hafnium,
or at least 0.200 ppm of hafnium.
In embodiments of the disclosure, the upper limit on the parts per
million (ppm) of titanium in the ethylene copolymer composition may be about
18.0 ppm, or about 16.0 ppm, or about 14.0 ppm, or about 12.0 ppm, or about
10.0 ppm, or about 8.0 ppm. In embodiments of the disclosure, the lower limit
on the parts per million (ppm) of titanium in the ethylene copolymer
composition may be about 0.1 ppm, 0.5 ppm, or about 1.0 ppm, or about 2.0
ppm, or about 3.0 ppm.
In embodiments of the disclosure, the ethylene copolymer composition
has from 0.5 to 20.0 ppm of titanium, or from 0.5 to 18.0 ppm of titanium, or
from 0.5 to 14.0 ppm of titanium, or from 1.0 to 18.0 ppm of titanium, or from
1.0 to 16.0 ppm of titanium, or from 1.0 to 14.0 ppm of titanium, or from 2.0
to
18.0 ppm of titanium, or from 2.0 to 16.0 ppm of titanium, or from 2.0 to
14.0,
or from 3.0 to 18.0 ppm of titanium, or from 3.0 to 16.0 ppm of titanium, or
from 3.0 to 14.0 ppm of titanium.
In an embodiment of the disclosure, the ethylene copolymer
composition has a stress exponent, defined as Logio[16/12]/Logio[6.48/2.16],
which is 5 1.40. In further embodiments of the disclosure the ethylene
copolymer composition has a stress exponent, Logio[16/12]/Logio[6.48/2.16] of
less than 1.38, or less than 1.35, or less than 1.33, or less than 1.30.
In an embodiment of the disclosure, the ethylene copolymer
composition has a dimensionless long chain branching factor, LCBF of
0.001.
The ethylene copolymer composition disclosed herein may be
converted into flexible manufactured articles such as monolayer or multilayer
films. Such films are well known to those experienced in the art; non-limiting
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examples of processes to prepare such films include blown film and cast film
processes.
In the blown film extrusion process an extruder heats, melts, mixes and
conveys a thermoplastic, or a thermoplastic blend. Once molten, the
thermoplastic is forced through an annular die to produce a thermoplastic
tube. In the case of co-extrusion, multiple extruders are employed to produce
a multilayer thermoplastic tube. The temperature of the extrusion process is
primarily determined by the thermoplastic or thermoplastic blend being
processed, for example the melting temperature or glass transition
temperature of the thermoplastic and the desired viscosity of the melt. In the
case of polyolefins, typical extrusion temperatures are from 330 F to 550 F
(166 C to 288 C). Upon exit from the annular die, the thermoplastic tube is
inflated with air, cooled, solidified and pulled through a pair of nip
rollers. Due
to air inflation, the tube increases in diameter forming a bubble of desired
size. Due to the pulling action of the nip rollers the bubble is stretched in
the
machine direction. Thus, the bubble is stretched in two directions: the
transverse direction (TD) where the inflating air increases the diameter of
the
bubble; and the machine direction (MD) where the nip rollers stretch the
bubble. As a result, the physical properties of blown films are typically
anisotropic, i.e. the physical properties differ in the MD and TD directions;
for
example, film tear strength and tensile properties typically differ in the MD
and
TD. In some prior art documents, the terms "cross direction" or "CD" is used;
these terms are equivalent to the terms "transverse direction" or "TD" used in
this disclosure. In the blown film process, air is also blown on the external
bubble circumference to cool the thermoplastic as it exits the annular die.
The
final width of the film is determined by controlling the inflating air or the
internal bubble pressure; in other words, increasing or decreasing bubble
diameter. Film thickness is controlled primarily by increasing or decreasing
the speed of the nip rollers to control the draw-down rate. After exiting the
nip rollers, the bubble or tube is collapsed and may be slit in the machine
direction thus creating sheeting. Each sheet may be wound into a roll of film.
Each roll may be further slit to create film of the desired width. Each roll
of
film is further processed into a variety of consumer products as described
below.
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The cast film process is similar in that a single or multiple extruder(s)
may be used; however the various thermoplastic materials are metered into a
flat die and extruded into a monolayer or multilayer sheet, rather than a
tube.
In the cast film process the extruded sheet is solidified on a chill roll
In the cast film process, films are extruded from a flat die onto a chilled
roll or a nipped roll, optionally, with a vacuum box and/or air-knife. The
cast
films may be monolayer or coextruded multi-layer films obtained by various
extrusion through a single or multiple dies. The resultant films may be the
used as-is or may be laminated to other films or substrates, for example by
thermal, adhesive lamination or direct extrusion onto a substrate. The
resultant films and laminates may be subjected to other forming operations
such as embossing, stretching, thermoforming. Surface treatments such as
corona may be applied and the films may be printed.
In the cast film extrusion process, a thin film is extruded through a slit
onto a chilled, highly polished turning roll, where it is quenched from one
side.
The speed of the roller controls the draw ratio and final film thickness. The
film
is then sent to a second roller for cooling on the other side. Finally it
passes
through a system of rollers and is wound onto a roll.
In an embodiment, two or more thin films are coextruded through two
or more slits onto a chilled, highly polished turning roll, the coextruded
film is
quenched from one side. The speed of the roller controls the draw ratio and
final coextruded film thickness. The coextruded film is then sent to a second
roller for cooling on the other side. Finally, it passes through a system of
rollers and is wound onto a roll.
A cast film may further be laminated, one or more layers, into a
multilayer structure.
Depending on the end-use application, the disclosed ethylene
copolymer composition may be converted into films that span a wide range of
thicknesses. Non-limiting examples include, food packaging films where
thicknesses may range from about 0.5 mil (13 pm) to about 4 mil (102 pm),
and; in heavy duty sack applications film thickness may range from about 2
mil (51pm) to about 10 mil (254 pm).
The ethylene copolymer composition disclosed herein may be used in
monolayer films; where the monolayer may contain more than one ethylene
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copolymer composition and/or additional thermoplastics; non-limiting
examples of thermoplastics include polyethylene polymers and propylene
polymers. The lower limit on the weight percent of the ethylene copolymer
composition in a monolayer film may be about 3 wt%, in other cases about 10
wt% and in still other cases about 30 wt%. The upper limit on the weight
percent of the ethylene copolymer composition in the monolayer film may be
100 wt%, in other cases about 90 wt% and in still other cases about 70 wt%.
The ethylene copolymer composition disclosed herein may also be
used in one or more layers of a multilayer film; non-limiting examples of
multilayer films include three, five, seven, nine, eleven or more layers. The
thickness of a specific layer (containing the ethylene copolymer composition)
within a multilayer film may be about 5%, in other cases about 15% and in
still
other cases about 30% of the total multilayer film thickness. In other
embodiments, the thickness of a specific layer (containing the ethylene
copolymer composition) within a multilayer film may be about 95%, in other
cases about 80% and in still other cases about 65% of the total multilayer
film
thickness. Each individual layer of a multilayer film may contain more than
one ethylene copolymer composition and/or additional thermoplastics.
Additional embodiments include laminations and coatings, wherein
mono or multilayer films containing the disclosed ethylene copolymer
composition are extrusion laminated or adhesively laminated or extrusion
coated. In extrusion lamination or adhesive lamination, two or more
substrates are bonded together with a thermoplastic or an adhesive,
respectively. In extrusion coating, a thermoplastic is applied to the surface
of
a substrate. These processes are well known to those experienced in the art.
Frequently, adhesive lamination or extrusion lamination are used to bond
dissimilar materials, non-limiting examples include the bonding of a paper web
to a thermoplastic web, or the bonding of an aluminum foil containing web to a
thermoplastic web, or the bonding of two thermoplastic webs that are
chemically incompatible, e.g. the bonding of a ethylene copolymer
composition containing web to a polyester or polyamide web. Prior to
lamination, the web containing the disclosed ethylene copolymer
composition(s) may be monolayer or multilayer. Prior to lamination the
individual webs may be surface treated to improve the bonding, a non-limiting
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example of a surface treatment is corona treating. A primary web or film may
be laminated on its upper surface, its lower surface, or both its upper and
lower surfaces with a secondary web. A secondary web and a tertiary web
could be laminated to the primary web; wherein the secondary and tertiary
webs differ in chemical composition. As non-limiting examples, secondary or
tertiary webs may include; polyamide, polyester and polypropylene, or webs
containing barrier resin layers such as EVOH. Such webs may also contain a
vapor deposited barrier layer; for example, a thin silicon oxide (SiOx) or
aluminum oxide (A10) layer. Multilayer webs (or films) may contain three,
five, seven, nine, eleven or more layers.
The ethylene copolymer composition disclosed herein can be used in a
wide range of manufactured articles comprising one or more films or film
layers (monolayer or multilayer). Non-limiting examples of such manufactured
articles include: food packaging films (fresh and frozen foods, liquids and
granular foods), stand-up pouches, retortable packaging and bag-in-box
packaging; barrier films (oxygen, moisture, aroma, oil, etc.) and modified
atmosphere packaging; light and heavy duty shrink films and wraps, collation
shrink film, pallet shrink film, shrink bags, shrink bundling and shrink
shrouds;
light and heavy duty stretch films, hand stretch wrap, machine stretch wrap
and stretch hood films; high clarity films; heavy-duty sacks; household wrap,
overwrap films and sandwich bags; industrial and institutional films, trash
bags, can liners, magazine overwrap, newspaper bags, mail bags, sacks and
envelopes, bubble wrap, carpet film, furniture bags, garment bags, coin bags,
auto panel films; medical applications such as gowns, draping and surgical
garb; construction films and sheeting, asphalt films, insulation bags, masking
film, landscaping film and bags; geomembrane liners for municipal waste
disposal and mining applications; batch inclusion bags; agricultural films,
mulch film and green house films; in-store packaging, self-service bags,
boutique bags, grocery bags, carry-out sacks and t-shirt bags; oriented films,
machine direction and biaxially oriented films and functional film layers in
oriented polypropylene (OPP) films, e.g. sealant and/or toughness layers.
Additional manufactured articles comprising one or more films containing at
least one ethylene copolymer composition include laminates and/or multilayer
films; sealants and tie layers in multilayer films and composites; laminations
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with paper; aluminum foil laminates or laminates containing vacuum deposited
aluminum; polyamide laminates; polyester laminates; extrusion coated
laminates, and; hot-melt adhesive formulations. The manufactured articles
summarized in this paragraph contain at least one film (monolayer or
multilayer) comprising at least one embodiment of the disclosed ethylene
copolymer composition.
Cast films and laminates made from ethylene copolymer compositions
of the present disclosure may be used in a variety of end-uses, such as for
example, for food packaging (dry foods, fresh foods, frozen foods, liquids,
processed foods, powders, granules), for packaging of detergents, toothpaste,
towels, for labels and release liners. The cast films may also be used in
unitization and industrial packaging, notably in stretch films. The cast films
may also be suitable in hygiene and medical applications, for example in
breathable and non-breathable films used in diapers, adult incontinence
products, feminine hygiene products, ostomy bags. The ethylene copolymer
compositions of the present disclosure may also be useful in tapes and
artificial turf applications.
Desired film physical properties (monolayer or multilayer) typically
depend on the application of interest. Non-limiting examples of desirable film
properties include: optical properties (gloss, haze and clarity), dart impact,
Elmendorf tear, modulus (1% and 2% secant modulus), puncture-propagation
tear resistance, tensile properties (yield strength, break strength,
elongation at
break, toughness, etc.) and heat sealing properties (heat seal initiation
temperature and hot tack strength). Specific hot tack and heat sealing
properties are desired in high speed vertical and horizontal form-fill-seal
processes that load and seal a commercial product (liquid, solid, paste, part,
etc.) inside a pouch-like package.
In addition to desired film physical properties, it is desired that the
disclosed ethylene copolymer composition is easy to process on film lines.
Those skilled in the art frequently use the term "processability" to
differentiate
polymers with improved processability, relative to polymers with inferior
processability. A commonly used measure to quantify processability is
extrusion pressure; more specifically, a polymer with improved processability
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has a lower extrusion pressure (on a blown film or a cast film extrusion line)
relative to a polymer with inferior processability.
The films used in the manufactured articles described in this section
may optionally include, depending on its intended use, additives and
adjuvants. Non-limiting examples of additives and adjuvants include, anti-
blocking agents, antioxidants, heat stabilizers, slip agents, processing aids,
anti-static additives, colorants, dyes, filler materials, light stabilizers,
light
absorbers, lubricants, pigments, plasticizers, nucleating agents and
combinations thereof.
In an embodiment of the disclosure, a film or film layer comprises the
ethylene copolymer composition described herein.
In an embodiment of the disclosure, a film or film layer is a monolayer
film and comprises the ethylene copolymer composition described herein.
In an embodiment a film or film layer is a blown film.
In an embodiment a film or film layer is a cast film.
In embodiments of the disclosure, a film or film layer comprises the
ethylene copolymer composition described herein and has a thickness of from
0.5 to 10 mil.
In embodiments of the disclosure, a film or film layer has a thickness of
from 0.5 to 10 mil.
In embodiments of the disclosure, a multilayer film structure has a
thickness of from 0.5 to 10 mil.
In an embodiment of the disclosure, a multilayer film structure
comprises at least one layer comprising the ethylene copolymer composition
described herein, and the multilayer film structure has a thickness of from
0.5
to 10 mil.
An embodiment of the disclosure is a multilayer coextruded blown film
structure.
An embodiment of the disclosure is a multilayer coextruded blown film
structure having a thickness of from 0.5 to 10 mil.
An embodiment of the disclosure is a multilayer coextruded blown film
structure comprising a film layer comprising the ethylene copolymer
composition described herein.
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An embodiment of the disclosure is a multilayer coextruded blown film
structure comprising a film layer comprising the ethylene copolymer
composition described herein, and the multilayer film structure has a
thickness of from 0.5 to 10 mil.
An embodiment of the disclosure is a multilayer coextruded cast film
structure.
An embodiment of the disclosure is a multilayer coextruded cast film
structure having a thickness of from 0.5 to 10 mil.
An embodiment of the disclosure is a multilayer coextruded cast film
structure comprising a film layer comprising the ethylene copolymer
composition described herein.
An embodiment of the disclosure is a multilayer coextruded cast film
structure comprising a film layer comprising the ethylene copolymer
composition described herein, and the multilayer film structure has a
thickness of from 0.5 to 10 mil.
In embodiments of the disclosure, a 1 mil blown film or blown film layer
will have a dart impact strength of 600 g/mil, or 700 g/mil, or 800 g/mil,
or 850 g/mil. In another embodiment of the disclosure, a 1 mil blown
film or
blown film layer will have a dart impact strength of from 600 g/mil to 1200
g/mil. In a further embodiment of the disclosure, a 1 mil blown film or blown
film layer will have dart impact strength of from 700 g/mil to 1100 g/mil. In
a
further embodiment of the disclosure, a 1 mil blown film or blown film layer
will
have dart impact strength of from 800 g/mil to 1200 g/mil. In yet another
embodiment of the disclosure, a 1 mil blown film or blown film layer will have
dart impact strength of from 800 g/mil to 1100 g/mil. In still yet another
embodiment of the disclosure, a 1 mil blown film or blown film layer will have
dart impact strength of from 850 g/mil to 1050 g/mil.
In embodiments of the disclosure, a 1 mil blown film or blown film layer
will have a haze of 5 10%, or 5 8%, 5 6%, or 5. 5%. In embodiments of the
disclosure, a 1 mil film or blown film layer will have a haze of from 2% to
10%,
or from 2% to 8%, or from 3% to 6%.
In embodiments of the disclosure, a 1 mil blown film or blown film layer
will have an ASTM puncture resistance value of 80 J/mm, or > 90 J/mm, or
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> 95 J/mm, or > 100 J/mm. In embodiments of the disclosure, a 1 mil blown
film or blown film layer will have ASTM puncture value of from 80 J/mm to 140
J/mm, or from 90 J/mm to 130 J/mm, or from 100 J/mm to 125 J/mm.
In embodiments of the disclosure, a 2 mil blown film or blown film layer
will have a seal initiation temperature (SIT) of 5 100 C, or 95 C, or 5 90 C,
Or 5 85 C, or < 100 C, or < 95 C, or < 90 C, or < 85 C. In an embodiment of
the disclosure, a 2 mil blown film or blown film layer will have a seal
initiation
temperature (SIT) of from 75 C to 105 C. In an embodiment of the disclosure,
a 2 mil blown film or blown film layer will have a seal initiation temperature
(SIT) of from 80 C to 100 C. In an embodiment of the disclosure, a 2 mil
blown film or blown film layer will have a seal initiation temperature (SIT)
of
from 80 C to 95 C.
In embodiments of the disclosure, a 2 mil blown film or blown film layer
will have a hot tack onset temperature (HTOT) of 5 100 C, or 5 95 C, or 5
90 C, or 5 88 C, or 5 85 C, or < 100 C, or < 95 C, or < 90 C, or < 88 C, or <
85 C. In an embodiment of the disclosure, a 2 mil or blown film layer blown
film will have a hot tack onset temperature (HTOT) of from 55 C to 100 C. In
an embodiment of the disclosure, a 2 mil blown film or blown film layer will
have a hot tack onset temperature (HTOT) of from 60 C to 88 C. In an
embodiment of the disclosure, a 2 mil blown film or blown film layer will have
a
hot tack onset temperature (HTOT) of from 60 C to 85 C.
In an embodiment of the disclosure, a 2 mil blown film or blown film
layer will have a hot tack window (HTW) of 40 C. In an embodiment of the
disclosure, a 2 mil blown film or blown film layer will have a hot tack window
(HTW) of 45 C. In an embodiment of the disclosure, a 2 mil or blown film
layer blown film will have a hot tack window (HTW) of ?. 50 C. In an
embodiment of the disclosure, a 2 mil blown film or blown film layer will have
a
hot tack window (HTW) of 55 C. In an embodiment of the disclosure, a 2
mil blown film or blown film layer will have a hot tack window (HTW) of from
40 to 75 C. In an embodiment of the disclosure, a 2 mil blown film or blown
film layer will have a hot tack window (HTW) of from 40 to 70 C. In an
embodiment of the disclosure, a 2 blown mil film or blown film layer will have
a
hot tack window (HTW) of from 45 to 75 C. In an embodiment of the
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disclosure, a 2 mil blown film or blown film layer will have a hot tack window
(HTW) of from 45 to 70 C. In an embodiment of the disclosure, a 2 mil blown
film or blown film layer will have a hot tack window (HTW) of from 45 to 65 C.
An embodiment of the disclosure is a multilayer film structure
comprising at least one film layer comprising the ethylene copolymer
composition described herein.
An embodiment of the disclosure is a multilayer film structure
comprising at least one film layer comprising the ethylene copolymer
composition described herein where the multilayer film structure has at least
3
layers, or at least 5 layers, or at least 7 layers, or at least 9 layers.
An embodiment of the disclosure is a multilayer film structure
comprising at least one film layer comprising the ethylene copolymer
composition described herein where the multilayer film structure has 9 layers.
An embodiment of the disclosure is a multilayer film structure
comprising at least one sealant layer comprising the ethylene copolymer
composition described herein.
An embodiment of the disclosure is a multilayer film structure
comprising a sealant layer comprising the ethylene copolymer composition
described herein.
An embodiment of the disclosure is a multilayer film structure
comprising a sealant layer comprising the ethylene copolymer composition
described herein and where the multilayer film structure has at least 3
layers.
An embodiment of the disclosure is a multilayer film structure
comprising a sealant layer comprising the ethylene copolymer composition
described herein and where the multilayer film structure has at least 5
layers.
An embodiment of the disclosure is a multilayer film structure
comprising a sealant layer comprising the ethylene copolymer composition
described herein and where the multilayer film structure has at least 7
layers.
An embodiment of the disclosure is a multilayer film structure
comprising a sealant layer comprising the ethylene copolymer composition
described herein and where the multilayer film structure has at least 9
layers.
An embodiment of the disclosure is a multilayer film structure
comprising a sealant layer comprising the ethylene copolymer composition
described herein and where the multilayer film structure has 9 layers.
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In embodiments of the disclosure, a 2 mil cast film or cast film layer will
have a seal initiation temperature (SIT) of 5 100 C, or 5 95 C, or 5 90 C, or
<
100 C, or < 95 C, or < 90 C. In an embodiment of the disclosure, a 2 mil cast
film or cast film layer will have a seal initiation temperature (SIT) of from
75 C
to 105 C. In an embodiment of the disclosure, a 2 mil cast film or cast film
layer will have a seal initiation temperature (SIT) of from 80 C to 100 C. In
an
embodiment of the disclosure, a 2 mil cast film or cast film layer will have a
seal initiation temperature (SIT) of from 80 C to 95 C.
In embodiments of the disclosure, a 2 mil cast film structure will have a
seal initiation temperature (SIT) of 5 100 C, or 5 95 C, or 5 90 C, or < 100
C,
or < 95 C, or < 90 C. In an embodiment of the disclosure, a 2 mil cast film
structure will have a seal initiation temperature (SIT) of from 75 C to 105 C.
In an embodiment of the disclosure, a 2 mil cast film structure will have a
seal
initiation temperature (SIT) of from 80 C to 100 C. In an embodiment of the
disclosure, a 2 mil cast film structure will have a seal initiation
temperature
(SIT) of from 80 C to 95 C.
In embodiments of the disclosure, a 2 mil cast film or cast film layer will
have a hot tack onset temperature (HTOT) of 5 100 C, or 5 95 C, or 5 90 C,
or 5 88 C, or 5. 85 C, or < 100 C, or < 95 C, or < 90 C, or < 88 C, or < 85 C.
In an embodiment of the disclosure, a 2 mil cast film or cast film layer will
have a hot tack onset temperature (HTOT) of from 65 C to 100 C. In an
embodiment of the disclosure, a 2 mil cast film or cast film layer will have a
hot tack onset temperature (HTOT) of from 70 C to 95 C. In an embodiment
of the disclosure, a 2 mil cast film or cast film layer will have a hot tack
onset
temperature (HTOT) of from 75 C to 95 C.
In embodiments of the disclosure, a 2 mil cast film structure will have a
hot tack onset temperature (HTOT) of 5 100 C, or 5 95 C, or 5 90 C, or 5
88 C, or 5 85 C, or < 100 C, or < 95 C, or < 90 C, or < 88 C, or < 85 C. In an
embodiment of the disclosure, a 2 mil cast film structure will have a hot tack
onset temperature (HTOT) of from 65 C to 100 C. In an embodiment of the
disclosure, a 2 mil cast film structure will have a hot tack onset temperature
(HTOT) of from 70 C to 95 C. In an embodiment of the disclosure, a 2 mil
cast film structure will have a hot tack onset temperature (HTOT) of from 75 C
to 95 C.
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In an embodiment of the disclosure, a 2 mil cast film or cast film layer
will have a hot tack window (HTW) of 15 C. In an embodiment of the
disclosure, a 2 mil cast film or cast film layer will have a hot tack window
(HTW) of 17.5 C. In an embodiment of the disclosure, a 2 mil cast film or
cast film layer will have a hot tack window (HTW) of 20 C. In an
embodiment of the disclosure, a 2 mil cast film or cast film layer will have a
hot tack window (HTW) of from 15 to 40 C. In an embodiment of the
disclosure, a 2 mil cast film or cast film layer will have a hot tack window
(HTW) of from 17.5 to 40 C. In an embodiment of the disclosure, a 2 mil cast
film or cast film layer will have a hot tack window (HTW) of from 20 to 40 C.
In an embodiment of the disclosure, a 2 mil cast film or cast film layer will
have a hot tack window (HTW) of from 20 to 35 C.
In an embodiment of the disclosure, a 2 mil cast film structure will have
a hot tack window (HTW) of ?. 15 C. In an embodiment of the disclosure, a 2
mil cast film structure will have a hot tack window (HTW) of 17.5 C. In an
embodiment of the disclosure, a 2 mil cast film structure will have a hot tack
window (HTW) of 20 C. In an embodiment of the disclosure, a 2 mil cast
film structure will have a hot tack window (HTW) of from 15 to 40 C. In an
embodiment of the disclosure, a 2 mil cast film structure will have a hot tack
window (HTW) of from 17.5 to 40 C. In an embodiment of the disclosure, a 2
mil cast film structure will have a hot tack window (HTW) of from 20 to 40 C.
In an embodiment of the disclosure, a 2 mil cast film structure will have a
hot
tack window (HTW) of from 20 to 35 C.
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.
EXAMPLES
General Testing Procedures
Prior to testing, each polymer specimen was conditioned for at least 24
hours at 23 2 C and 50 10% relative humidity and subsequent testing was
conducted at 23 2 C and 50 10% relative humidity. Herein, the term
"ASTM conditions" refers to a laboratory that is maintained at 23 2 C and 50
10% relative humidity; and specimens to be tested were conditioned for at
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least 24 hours in this laboratory prior to testing. ASTM refers to the
American
Society for Testing and Materials.
Density
Ethylene copolymer composition densities were determined using
ASTM D792-13 (November 1,2013).
Melt Index
Ethylene copolymer composition 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.
Conventional Size Exclusion Chromatography (SEC)
Ethylene copolymer composition samples (polymer) solutions (1 to 3
mg/mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene
(TCB) and rotating on a wheel for 4 hours at 150 C in an oven. An antioxidant
(2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture in order to
stabilize the polymer against oxidative degradation. The BHT concentration
was 250 ppm. Polymer solutions were chromatographed at 140 C on a PL
220 high-temperature chromatography unit equipped with four Shodex
columns (H1803, H1804, H1805 and H1806) using TCB as the mobile phase
with a flow rate of 1.0 mL/minute, with a differential refractive index (DR1)
as
the concentration detector. BHT was added to the mobile phase at a
concentration of 250 ppm to protect GPC columns from oxidative degradation.
The sample injection volume was 200 pL. The GPC columns were calibrated
with narrow distribution polystyrene standards. The polystyrene molecular
weights were converted to polyethylene molecular weights using the Mark-
Houwink equation, as described in the ASTM standard test method D6474-12
(December 2012). The GPC raw data were processed with the Cirrus GPC
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software, to produce molar mass averages (Mn, Mw, Mz) and molar mass
distribution (e.g. Polydispersity, Mw/Mn). In the polyethylene art, a commonly
used term that is equivalent to SEC is GPC, i.e. Gel Permeation
Chromatography.
Triple Detection Size Exclusion Chromatography (3D-SEC)
Ethylene copolymer composition samples (polymer) solutions (1 to 3
mg/mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene
(TCB) and rotating on a wheel for 4 hours at 150 C in an oven. An antioxidant
(2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture in order to
stabilize the polymer against oxidative degradation. The BHT concentration
was 250 ppm. Sample solutions were chromatographed at 140 C on a PL
220 high-temperature chromatography unit equipped with a differential
refractive index (DRI) detector, a dual-angle light scattering detector (15
and
90 degree) and a differential viscometer. The SEC columns used were either
four Shodex columns (H1803, HT804, H1805 and HT806), or four PL Mixed
ALS or BLS columns. TCB was the mobile phase with a flow rate of 1.0
mL/minute, BHT was added to the mobile phase at a concentration of 250
ppm to protect SEC columns from oxidative degradation. The sample injection
volume was 200 pL. The SEC raw data were processed with the Cirrus GPC
software, to produce absolute molar masses and intrinsic viscosity ([ri]). The
term "absolute" molar mass was used to distinguish 3D-SEC determined
absolute molar masses from the molar masses determined by conventional
SEC. The viscosity average molar mass (Mv) determined by 3D-SEC was
used in the calculations to determine the Long Chain Branching Factor
(LCBF).
GPC-FTIR
Ethylene copolymer composition (polymer) solutions (2 to 4 mg/mL)
were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and
rotating on a wheel for 4 hours at 150 C in an oven. The antioxidant 2,6-di-
tert-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize
the polymer against oxidative degradation. The BHT concentration was 250
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ppm. Sample solutions were chromatographed at 140 C on a Waters GPC
150C chromatography unit equipped with four Shodex columns (H1803,
H1804, HT805 and HT806) using TCB as the mobile phase with a flow rate of
1.0 mL/minute, with a FTIR spectrometer and a heated FTIR flow through cell
coupled with the chromatography unit through a heated transfer line as the
detection system. BHT was added to the mobile phase at a concentration of
250 ppm to protect SEC columns from oxidative degradation. The sample
injection volume was 300 pL. The raw FTIR spectra were processed with
OPUS FTIR software and the polymer concentration and methyl content were
calculated in real time with the Chemometric Software (PLS technique)
associated with the OPUS. Then the polymer concentration and methyl
content were acquired and baseline-corrected with the Cirrus GPC software.
The SEC columns were calibrated with narrow distribution polystyrene
standards. The polystyrene molecular weights were converted to polyethylene
molecular weights using the Mark-Houwink equation, as described in the
ASTM standard test method D6474. The comonomer content was calculated
based on the polymer concentration and methyl content predicted by the PLS
technique as described in Paul J. DesLauriers, Polymer 43, pages 159-170
(2002); herein incorporated by reference.
The GPC-FTIR method measures total methyl content, which includes
the methyl groups located at the ends of each macromolecular chain, i.e.
methyl end groups. Thus, the raw GPC-FTIR data must be corrected by
subtracting the contribution from methyl end groups. To be more clear, the
raw GPC-FTIR data overestimates the amount of short chain branching (SCB)
and this overestimation increases as molecular weight (M) decreases. In this
disclosure, raw GPC-FTIR data was corrected using the 2-methyl correction.
At a given molecular weight (M), the number of methyl end groups (NE) was
calculated using the following equation; NE = 28000/M, and NE (M dependent)
was subtracted from the raw GPC-FTIR data to produce the SCB/1000C (2-
Methyl Corrected) GPC-FTIR data.
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CRYSTAF/TREF (CTEF)
The "Composition Distribution Breadth Index", hereinafter CDBI, of the
ethylene copolymer compositions (and Comparative Examples) was
measured using a CRYSTAF/TREF 200+ unit equipped with an IR detector,
hereinafter the CTREF. The acronym "TREF" refers to Temperature Rising
Elution Fractionation. The CTREF was supplied by PolymerChAR S.A.
(Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia,
Spain). The CTREF was operated in the TREF mode, which generates the
chemical composition of the polymer sample as a function of elution
temperature, the Co/Ho ratio (Copolymer/Homopolymer ratio) and the CDBI
(the Composition Distribution Breadth Index), i.e. CDBI50 and CDBI25. A
polymer sample (80 to 100 mg) was placed into the reactor vessel of the
CTREF. The reactor vessel was filled with 35 ml of 1,2,4-trichlorobenzene
(TCB) and the polymer was dissolved by heating the solution to 150 C for 2
hours. An aliquot (1.5 mL) of the solution was then loaded into the CTREF
column which was packed with stainless steel beads. The column, loaded
with sample, was allowed to stabilize at 110 C for 45 minutes. The polymer
was then crystallized from solution, within the column, by dropping the
temperature to 30 C at a cooling rate of 0.09 C/minute. The column was then
equilibrated for 30 minutes at 30 C. The crystallized polymer was then eluted
from the column with TCB flowing through the column at 0.75 mUminute,
while the column was slowly heated from 30 C to 120 C at a heating rate of
0.25 C/minute. The raw CTREF data were processed using Polymer ChAR
software, an Excel spreadsheet and CTREF software developed in-house.
CDBI50 was defined as the percent of polymer whose composition is within
50% of the median comonomer composition; CDBI50 was calculated from the
composition distribution cure and the normalized cumulative integral of the
composition distribution curve, as described in United States Patent
5,376,439. Those skilled in the art will understand that a calibration curve
is
required to convert a CTREF elution temperature to comonomer content, i.e.
the amount of comonomer in the ethylene/a-olefin polymer fraction that elutes
at a specific temperature. The generation of such calibration curves are
described in the prior art, e.g. Wild, et al., J. Polym. Sci., Part B, Polym.
Phys.,
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Vol. 20 (3), pages 441-455: hereby fully incorporated by reference. CDBI25 as
calculated in a similar manner; CDBI25 is defined as the percent of polymer
whose composition is with 25% of the median comonomer composition. At
the end of each sample run, the CTREF column was cleaned for 30 minutes;
specifically, with the CTREF column temperature at 160 C, TCB flowed (0.5
mL/minute) through the column for 30 minutes.
CTREF peak elution temperatures were used to determine the amount
of branching (SCB1 (#C6/1000C)) and density of the first ethylene copolymer
using the following equations: SCB1 (#C6/1000C) = 74.29¨ 0.7598 (TPcTREF),
where TPCTREF is the peak elution temperature of the first ethylene copolymer
in the CTREF chromatogram, and SCB1 (#C6/1000C) = 9341.8(p1)2¨ 17766
(p1) + 8446.8, where p1 was the density of the first ethylene copolymer. The
SCB2 (#C6/1000C) and density of the second ethylene copolymer was
determined using blending rules, given the overall SCB of the ethylene
copolymer composition, SCB-overall composition (measured as #C6/1000C,
where #C6 is the number of hexyl branches or as a proxy for hexyl branches,
the #CH3/1000C from FTIR, where #CH3 is the number of methyl groups) and
the overall density of the ethylene copolymer composition. See Figure 3,
which shows the relative position of the TPCTREF of the first ethylene
copolymer
for Inventive Example 1.
The CTREF procedures described above are also used to determine
the modality of a TREF profile, the temperatures or temperatures ranges
where elution intensity maxima (elution peaks) occur, and the weight percent
(wt%) of the ethylene copolymer composition which elutes at a temperature of
from 90 C to 105 C (i.e. the intergrated area of the fraction, in weight
percent,
of the ehtylene copolymer composition which elutes at from 90 C to 105 C in
a CTREF analysis).
Neutron Activation (Elemental Analysis)
Neutron Activation Analysis, hereinafter N.A.A., was used to determine
catalyst metal residues in ethylene copolymer compositions as follows. A
radiation vial (composed of ultrapure polyethylene, 7 mL internal volume) was
filled with an ethylene copolymer composition sample and the sample weight
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was recorded. Using a pneumatic transfer system the sample was placed
inside a SLOWPOKE TM 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 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
copolymer composition 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).
Unsaturation
The quantity of unsaturated groups, i.e. double bonds, in an ethylene
copolymer composition was determined according to ASTM D3124-98
(vinylidene unsaturation, published March 2011) and ASTM D6248-98 (vinyl
and trans unsaturation, published July 2012). An ethylene copolymer
composition 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.
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Comonomer Content: Fourier Transform Infrared (FTIR) Spectroscopy
The quantity of comonomer in an ethylene copolymer composition was
determined by FTIR and reported as the Short Chain Branching (SCB)
content having dimensions of CH3#/1000C (number of methyl branches per
1000 carbon atoms). This test was completed according to ASTM D6645-01
(2001), employing a compression molded polymer plaque and a Thermo-
Nicolet 750 Magna-IR Spectrophotometer. The polymer plaque was prepared
using a compression molding device (Wabash-Genesis Series press)
according to ASTM D4703-16 (April 2016).
13C Nuclear Magnetic Resonance (NMR)
Between 0.21 and 0.30 g of polymer sample was weighed into 10mm
NMR tubes. The sample was then dissolved with deuterated ortho-
dichlorobenzene (ODCB-d4) and heated to 125 C; a heat gun was used to
assist the mixing process. 13C NMR spectra (24000 scans per spectra) were
collected on a Bruker AVANCE III HD 400 MHz NMR spectrometer fitted with
a 10 mm PABBO probehead maintained at 125 C. Chemical shifts were
referenced to the polymer backbone resonance, which was assigned a value
of 30.0 ppm. 13C spectra were processed using exponential multiplication
with a line broadening (LB) factor of 1.0 Hz. They were also processed using
Gaussian multiplication with LB = -0.5 Hz and GB = 0.2 to enhance resolution.
Differential Scanning Calorimetry (DSC)
Primary melting peak ( C), melting peak temperatures ( C), heat of
fusion (J/g) and crystallinity (%) was determined using differential scanning
calorimetry (DSC) as follows: the instrument was first calibrated with indium;
after the calibration, a polymer specimen is equilibrated at 0 C and then the
temperature was increased to 200 C at a heating rate of 10 C/min; the melt
was then kept isothermally at 200 C for five minutes; the melt was then cooled
to 0 C at a cooling rate of 10 C/min and kept at 0 C for five minutes; the
specimen was then heated to 200 C at a heating rate of 10 C/min. The DSC
Tm, heat of fusion and crystallinity are reported from the 2nd heating cycle.
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Dynamic Mechanical Analysis (DMA)
Oscillatory shear measurements under small strain amplitudes were
carried out to obtain linear viscoelastic functions at 190 C under N2
atmosphere, at a strain amplitude of 10% and over a frequency range of 0.02-
126 rad/s at 5 points per decade. Frequency sweep experiments were
performed with a TA Instruments DHR3 stress-controlled rheometer using
cone-plate geometry with a cone angle of 5 , a truncation of 137 pm and a
diameter of 25 mm. In this experiment a sinusoidal strain wave was applied
and the stress response was analyzed in terms of linear viscoelastic
functions. The zero shear rate viscosity (no) based on the DMA frequency
sweep results was predicted by Ellis model (see R.B. Bird et al. "Dynamics of
Polymer Liquids. Volume 1: Fluid Mechanics" Wiley-Interscience Publications
(1987) p.228) or Carreau-Yasuda model (see K. Yasuda (1979) PhD Thesis,
IT Cambridge). In this disclosure, the LCBF (Long Chain Branching Factor)
was determined using the DMA determined flo.
Melt Strength
The melt strength is measured on Rosand RH-7 capillary rheometer
(barrel diameter = 15mm) with a flat die of 2-mm Diameter, LID ratio 10:1 at
190 C. Pressure Transducer: 10,000 psi (68.95 MPa). Piston Speed: 5.33
mm/min. Haul-off Angle: 52 . Haul-off incremental speed: 50 ¨ 80 m/min2 or
65 15 m/min2. A polymer melt is extruded through a capillary die under a
constant rate and then the polymer strand is drawn at an increasing haul-off
speed until it ruptures. The maximum steady value of the force in the plateau
region of a force versus time curve is defined as the melt strength for the
polymer.
Film Dart Impact
Film dart impact strength was determined using ASTM D1709-09
Method A (May 1, 2009). In this disclosure the dart impact test employed a
1.5 inch (38 mm) diameter hemispherical headed dart.
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Film Puncture
Film "puncture", the energy (J/mm) required to break the film was
determined using ASTM D5748-95 (originally adopted in 1995, reapproved in
2012).
Film Lubricated Puncture
The "lubricated puncture" test was performed as follows: the energy
(J/mm) to puncture a film sample was determined using a 0.75-inch (1.9-cm)
diameter pear-shaped fluorocarbon coated probe travelling at 10-inch per
minute (25.4-cm/minute). ASTM conditions were employed. Prior to testing
the specimens, the probe head was manually lubricated with Muko
Lubricating Jelly to reduce friction. Muko Lubricating Jelly is a water-
soluble
personal lubricant available from Cardinal Health Inc., 1000 Tesma Way,
Vaughan, ON L4K 5R8 Canada. The probe was mounted in an lnstron Model
5 SL Universal Testing Machine and a 1000-N load cell as used. Film
samples (1.0 mil (25 Jim) thick, 5.5 inch (14 cm) wide and 6 inch (15 cm)
long)
were mounted in the Instron and punctured.
Film Tensile
The following film tensile properties were determined using ASTM
D882-12 (August 1,2012): tensile break strength (MPa), elongation at break
(%), tensile yield strength (MPa), tensile elongation at yield (%) and film
toughness or total energy to break (ft=lb/in3). Tensile properties were
measured in the both the machine direction (MD) and the transverse direction
(TD) of the blown films.
Film Secant Modulus
The secant modulus is a measure of film stiffness. The secant modulus
is the slope of a line drawn between two points on the stress-strain curve,
i.e.
the secant line. The first point on the stress-strain curve is the origin,
i.e. the
point that corresponds to the origin (the point of zero percent strain and
zero
stress), and; the second point on the stress-strain curve is the point that
corresponds to a strain of 1%; given these two points the 1% secant modulus
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is calculated and is expressed in terms of force per unit area (MPa). The 2%
secant modulus is calculated similarly. This method is used to calculated film
modulus because the stress-strain relationship of polyethylene does not follow
Hook's law; i.e. the stress-strain behavior of polyethylene is non-linear due
to
its viscoelastic nature. Secant moduli were measured using a conventional
Instron tensile tester equipped with a 200 lbf load cell. Strips of monolayer
film samples were cut for testing with following dimensions: 14 inch long, 1
inch wide and 1 mil thick; ensuring that there were no nicks or cuts on the
edges of the samples. Film samples were cut in both the machine direction
(MD) and the transverse direction (TD) and tested. ASTM conditions were
used to condition the samples. The thickness of each film was accurately
measured with a hand-held micrometer and entered along with the sample
name into the Instron software. Samples were loaded in the Instron with a
grip separation of 10 inch and pulled at a rate of 1 inch/min generating the
Is strain-strain curve. The 1% and 2% secant modulus were calculated using
the lnstron software.
Film Puncture-Propagation Tear
Puncture-propagation tear resistance of blown film was determined
using ASTM D2582-09 (May 1, 2009). This test measures the resistance of a
blown film to snagging, or more precisely, to dynamic puncture and
propagation of that puncture resulting in a tear. Puncture-propagation tear
resistance was measured in the machine direction (MD) and the transverse
direction (TD) of the blown films.
Film Elmendorf Tear
Film tear performance was determined by ASTM D1922-09 (May 1,
2009); an equivalent term for tear is "Elmendorf tear". Film tear was
measured in both the machine direction (MD) and the transverse direction
(TD) of the blown films.
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Film Opticals
Film optical properties were measured as follows: Haze, ASTM D1003-
13 (November 15, 2013), and; Gloss ASTM D2457-13 (April 1,2013).
Film Dynatup Impact
Instrumented impact testing was carried out on a machine called a
Dynatup Impact Tester purchased from Illinois Test Works Inc., Santa
Barbara, CA, USA; those skilled in the art frequently call this test the
Dynatup
impact test. Testing was completed according to the following procedure.
Test samples are prepared by cutting about 5 inch (12.7 cm) wide and about
6 inch (15.2 cm) long strips from a roll of blown film; film was about 1 mil
thick.
Prior to testing, the thickness of each sample was accurately measured with a
handheld micrometer and recorded. ASTM conditions were employed. Test
samples were mounted in the 9250 Dynatup Impact drop tower/test machine
using the pneumatic clamp. Dynatup tup #1, 0.5 inch (1.3 cm) diameter, was
attached to the crosshead using the Allen bolt supplied. Prior to testing, the
crosshead is raised to a height such that the film impact velocity is 10.9
0.1
ft/s. A weight was added to the crosshead such that: 1) the crosshead
slowdown, or tup slowdown, was no more than 20% from the beginning of the
test to the point of peak load and 2) the tup must penetrate through the
specimen. If the tup does not penetrate through the film, additional weight is
added to the crosshead to increase the striking velocity. During each test the
Dynatup Impulse Data Acquisition System Software collected the
experimental data (load (lb) versus time). At least 5 film samples are tested
and the software reports the following average values: "Dynatup Maximum
(Max) Load (1b)", the highest load measured during the impact test; "Dynatup
Total Energy (ft=lb)", the area under the load curve from the start of the
test to
the end of the test (puncture of the sample), and; "Dynatup Total Energy at
Max Load (ft.lb)", the area under the load curve from the start of the test to
the
maximum load point.
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Film Hexane Extractables
Hexane extractables was determined according to the Code of Federal
Registration 21 CFR 177.1520 Para (c) 3.1 and 3.2; wherein the quantity of
hexane extractable material in a film is determined gravimetrically.
Elaborating, 2.5 grams of 3.5 mil (89 um) monolayer film was placed in a
stainless steel basket, the film and basket were weighed (W), while in the
basket the film was: extracted with n-hexane at 49.5 C for two hours; dried at
80 C in a vacuum oven for 2 hours; cooled in a desiccator for 30 minutes,
and; weighed (wf). The percent loss in weight is the percent hexane
extractables w( C6): wC6 = 100 x (wi-w1')/w1.
Film Hot Tack
In this disclosure, the "Hot Tack Test" was performed as follows, using
ASTM conditions. Hot tack data was generated using a J&B Hot Tack Tester
which is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630
Maamechelen, Belgium. In the hot tack test, the strength of a polyolefin to
polyolefin seal is measured immediately after heat sealing two film samples
together (the two film samples were cut from the same roll of 2.0 mil (51-um)
thick film), i.e. when the polyolefin macromolecules that comprise the film
are
in a semi-molten state. This test simulates the heat sealing of polyethylene
films on high speed automatic packaging machines, e.g., vertical or horizontal
form, fill and seal equipment. The following parameters were used in the J&B
Hot Tack Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5
second; film sealing pressure, 0.27 N/mm2; delay time, 0.5 second; film peel
speed, 7.9 in/second (200 mm/second); testing temperature range, 131 F to
293 F (55 C to 145 C); temperature increments, 9 F (5 C); and five film
samples were tested at each temperature increment to calculate average
values at each temperature. In this way, a hot tack profile of pulling force
vs
sealing temperature is generated. The following data can be calculated from
this hot tack profile: the "Hot Tack Onset Temperature @ 1.0 N ( C)" or the
"HTOT", is the temperature at which a hot tack force of 1N was observed (an
average of five film samples); the "Max Hot tack Strength (N)", is the
maximum hot tack force observed (an average of five film samples) over the
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testing temperature range; the "Temperature ¨ Max. Hot tack ( C)", is the
temperature at which the maximum hot tack force was observed. Finally, the
hot-tack (strength) window (the "hot tack window" or the "HTVV") is defined as
the range of temperature, in C spanned by the hot tack curve at a given seal
strength, for example 2.5 Newtons. A person skilled in the art will realize
that
a hot tack window can be determined for differently defined seal strengths.
Generally speaking, for a given seal strength, the larger the hot tack window,
the greater the temperature window over which a high sealing force can be
maintained or achieved.
Film Heat Seal Strength
In this disclosure, the "Heat Seal Strength Test" (also known as "the
cold seal test") was performed as follows. ASTM conditions were employed.
Heat seal data was generated using a conventional lnstron Tensile Tester. In
this test, two film samples are sealed over a range of temperatures (the two
film samples were cut from the same roll of 2.0 mil (51-iim) thick film). The
following parameters were used in the Heat Seal Strength (or cold seal) Test:
film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film
sealing pressure, 40 psi (0.28 N/mm2); temperature range, 212 F to 302 F
(100 C to 150 C) and temperature increment, 9 F (5 C). After aging for at
least 24 hours at ASTM conditions, seal strength was determined using the
following tensile parameters: pull (crosshead) speed, 12 inch/min (2.54
cm/min); direction of pull, 90 to seal, and; 5 samples of film were tested at
each temperature increment. The Seal Initiation Temperature, hereafter
"SIT", is defined as the temperature required to form a commercially viable
seal; a commercially viable seal has a seal strength of 2.0 lb per inch of
seal
(8.8 N per 25.4 mm of seal).
Long Chain Branching Factor (LCBF)
The LCBF (dimensionless) was determined for the ethylene copolymer
composition using the method described in U.S. Pat. Appl. Pub. No.
2018/0305531 which is incorporated herein by reference.
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Ethylene Copolymer Compositions
Ethylene copolymer compositions were each made using a mixed dual
catalyst system in an "in-series" dual reactor solution polymerization
process.
As a result, ethylene copolymer compositions each comprised a first ethylene
copolymer made with a single site catalyst and a second ethylene copolymer
made with a multi-site catalyst. An "in series" dual reactor, solution phase
polymerization process, including one employing a mixed dual catalyst has
been described in U.S. Pat. Appl. Pub. No. 2018/0305531. Basically, in an
"in-series" dual reactor system the exit stream from a first polymerization
reactor (R1) flows directly into a second polymerization reactor (R2).
The R1 pressure was from about 14 MPa to about 18 MPa; while R2 was
operated at a lower pressure to facilitate continuous flow from R1 to R2. Both
R1 and R2 were continuously stirred reactors (CSTR's) and 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 and in the removal of product.
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), and the volume of the second CSTR reactor (R2) was 5.8
gallons (22 L). Monomer (ethylene) and comonomer (1-octene) were purified
prior to addition to the reactor using conventional feed preparation systems
(such as contact with various absorption media to remove impurities such as
water, oxygen and polar contaminants). The reactor feeds were pumped to
the reactors at the ratios shown in Table 1. Average residence times for the
reactors are calculated by dividing average flow rates by reactor volume and
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 single site catalyst (SSC) components were used to
prepare the first ethylene copolymer in a first reactor (R1) configured in
series
to a second reactor (R2): diphenylmethylene(cyclopentadienyl)(2,7-di-t-
butylfuorenyl)hafnium dimethide [(2,7-tBu2F1u)Ph2C(Cp)HfMe21;
methylaluminoxane (MMA0-07); trityl tetrakis(pentafluoro-phenyl)borate (trityl
borate), and 2,6-di-tert-butyl-4-ethylphenol (BFIEB). Methylaluminoxane
(MMA0-07) and 2,6-di-tert-butyl-4-ethylphenol are premixed in-line and then
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combined with diphenylmethylene(cyclopentadienyl)(2,7-di-t-
butylfuorenyl)hafnium dimethide and trityl tetrakis(pentafluoro-phenyl)borate
just before entering the polymerization reactor (R1). The efficiency of the
single site catalyst formulation was optimized by adjusting the mole ratios of
the catalyst components and the R1 catalyst inlet temperature.
The following Ziegler-Natta (ZN) catalyst components were used to
prepare the second ethylene copolymer in a second reactor (R2) configured in
series to a first reactor (R1): butyl ethyl magnesium; tertiary butyl
chloride;
titanium tetrachloride; diethyl aluminum ethoxide; and triethyl aluminum.
Methylpentane was used as the catalyst component solvent and the in-line
Ziegler-Natta catalyst formulation was prepared using the following steps and
then injected into the second reactor (R2). In step one, a solution of
triethylaluminum and butyl ethyl magnesium (Mg:Al = 20, mol:mol) was
combined with a solution of tertiary butyl chloride and allowed to react for
about 30 seconds to produce a MgCl2 support. 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 prior to injection into second reactor
(R2). The in-line Ziegler-Natta catalyst was activated in the reactor by
injecting a solution of diethyl aluminum ethoxide into R2. The quantity of
titanium tetrachloride added to the reactor is shown in Table 1. The
efficiency
of the in-line Ziegler-Natta catalyst formulation was optimized by adjusting
the
mole ratios of the catalyst components.
Polymerization in the continuous solution polymerization process was
terminated by adding a catalyst deactivator to the second reactor exit stream.
The catalyst deactivator used was octanoic acid (caprylic acid), commercially
available from P&G Chemicals, Cincinnati, OH, U.S.A. The catalyst
deactivator was added such that the moles of fatty acid added were 50% of
the total molar amount of hafnium, titanium and aluminum added to the
polymerization process; to be clear, the moles of octanoic acid added = 0.5 x
(moles hafnium + moles titanium + moles aluminum).
A two-stage devolatilization process was employed to recover the
ethylene copolymer composition 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
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(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 10-fold higher than
the molar amount of tertiary butyl chloride and titanium tetrachloride added
to
the solution process.
Prior to pelletization the ethylene copolymer composition was stabilized
by adding 500 ppm of lrganox 1076 (a primary antioxidant) and 500 ppm of
Irgafos 168 (a secondary antioxidant), based on weight of the ethylene
copolymer composition. Antioxidants were dissolved in process solvent and
added between the first and second V/L separators.
Table 1 shows the reactor conditions used to make each of the
inventive ethylene copolymer compositions. Table 1 includes process
parameters, such as the ethylene and 1-octene splits between the reactors
(R1 and R2), the reactor temperatures, the ethylene conversions, etc.
The properties of the inventive ethylene copolymer compositions
(Inventive Examples 1-6) as well as those for several comparative resins
(Comparative Examples 1-7) are shown in Table 2. Comparative Example 1
is ELITE AT6202, a resin commercially available from the Dow Chemical
Company. ELITE A16202 has a density of about 0.908 g/cm3 and a melt
index 12 of about 0.83 dg/min. Comparative Example 2 is Affinity PL 1840G,
a resin commercially available from the Dow Chemical Company. Affinity PL
1840G has a density of 0.909 9/cm3 and a melt index 12 of 0.88 dg/min.
Comparative Example 3 is Queo 1001, a resin commercially available from
Borealis AG. Queo 1001 has a density of 0.909 g/cm3 and a melt index (2 of
1.11 dg/min. Comparative Example 4 is EXCEED 1012HA, a resin
commercially available from ExxonMobil. EXCEED 1012HA has a density of
about 0.912 g/cm3 and a melt index 12 of about 0.98 dg/min. Comparative
Example 5 is EXCEED 3812, a resin commercially available from
ExxonMobil. EXCEED 3812 has a density of about 0.911 g/cm3 and a melt
index 12 of about 3.78 dg/min. Comparative Example 6 is a resin made
according to U.S. Pat. Appl. Pub. No. 2016/0108221. Comparative Example
6 is an ethylene/1-octene copolymer, has a density of about 0.914 g/cm3, a
melt index 12 of about 0.86 dg/min, and is made in a multi reactor solution
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process in which a first reactor and a second reactor are configured in series
with one another. Comparative Example 7 is SURPASS FPs317-A, a resin
commercially available from the NOVA Chemicals Corporation. SURPASS
FPs317-A has a density of 0.917 g/cm3 and a melt index 12 of 3.83 dg/min.
Details of the inventive ethylene copolymer composition components:
the first ethylene copolymer and the second ethylene copolymer, are provided
in Table 3. The ethylene copolymer composition component properties
shown in Table 3 were determined using a combination of CTREF analytical
methods and calculations from a Polymerization Process Model (e.g. for the
determination of SCB1, SCB2, dl and d2, wt1 and wt2, Mw1, Mw2, Mn1,
Mn2, 121 and 122).
Polymerization Process Model
For multicomponent (or bimodal resins) polyethylene polymers, the Mw,
Mn, and Mw/Mn were calculated herein, by using a reactor model simulation
using the input conditions which were employed for actual pilot scale run
conditions (for references on relevant reactor modeling methods, see
"Copolymerization" by A. Hamielec, J. MacGregor, and A. Penlidis in
Comprehensive Polymer Science and Supplements, volume 3, Chapter 2,
page 17, Elsevier, 1996 and "Copolymerization of Olefins in a Series of
Continuous Stirred-Tank Slurry-Reactors using Heterogeneous Ziegler-Natta
and Metallocene Catalysts. I. General Dynamic Mathematical Model" by
J.B.P Soares and A.E Hamielec in Polymer Reaction Engineering, 4(2&3),
p153, 1996.)
The model takes for input the flow of several reactive species (e.g.
catalyst, monomer such as ethylene, comonomer such as 1-octene,
hydrogen, and solvent) going to each reactor, the temperature (in each
reactor), and the conversion of monomer (in each reactor), and calculates the
polymer properties (of the polymer made in each reactor, i.e., the first and
second ethylene copolymers) using a terminal kinetic model for continuously
stirred tank reactors (CSTRs) connected in series. The "terminal kinetic
model" assumes that the kinetics depend upon the monomer unit within the
polymer chain on which the active catalyst site is located (see
"Copolymerization" by A. Hamielec, J. MacGregor, and A. Penlidis in
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Comprehensive Polymer Science and Supplements, Volume 3, Chapter 2,
page 17, Elsevier, 1996). In the model, the copolymer chains are assumed to
be of reasonably large molecular weight to ensure that the statistics of
monomer/comonomer unit insertion at the active catalyst center is valid and
that monomers/comonomers consumed in routes other than propagation are
negligible. This is known as the "long chain" approximation.
The terminal kinetic model for polymerization includes reaction rate
equations for activation, initiation, propagation, chain transfer, and
deactivation pathways. This model solves the steady-state conservation
equations (e.g., the total mass balance and heat balance) for the reactive
fluid
which comprises the reactive species identified above.
The total mass balance for a generic CSTR with a given number of
inlets and outlets is given by:
(1) 0 = Eirhi
where rhi represents the mass flow rate of individual streams with index i
indicating the inlet and outlet streams.
Equation (1) can be further expanded to show the individual species
and reactions:
Einlinf. Rj
(2) 0=
PmixV /Pmix
where Mi is the average molar weight of the fluid inlet or outlet (/), xi.; is
the
mass fraction of species j in stream i, pmix is the molar density of the
reactor
mixture, V is the reactor volume, R1 is the reaction rate for species], which
has units of km01/m3s.
The total heat balance is solved for an adiabatic reactor and is given
by:
(3)
where, riti is the mass flow rate of stream i (inlet or outlet), Al-li is the
difference in enthalpy of stream i versus a reference state , qRx is the heat
released by reaction(s), V is the reactor volume, W is the work input (i.e.,
agitator), 0 is the heat input/loss.
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The catalyst concentration input to each reactor is adjusted to match
the experimentally determined ethylene conversion and reactor temperature
values in order solve the equations of the kinetic model (e.g., propagation
rates, heat balance and mass balance).
The H2 concentration input to each reactor may be likewise adjusted so
that the calculated molecular weight distribution of a polymer made over both
reactors (and, hence, the molecular weight of polymer made in each reactor)
matches that which is observed experimentally.
The weight fraction, wt1 and wt2 of material made in each reactor, R1
and R2, is determined from knowing the mass flow of monomer and
comonomer into each reactor along with knowing the conversions for
monomer and comonomer in each reactor calculated based on kinetic
reactions.
The degree of polymerization (dpn) for a polymerization reaction is
given by the ratio of the rate of chain propagation reactions over the rate of
chain transfer/termination reactions:
(4) dpn =
kp1iCfm1l+kp1241[m2]+kp2102[7n2] RP
=
ktmii +ktmi2[7n2]0i+ktm2i [m242+ktn.(191+kts202+ktlli +ktH2 Rt
where kp12 is the propagation rate constant for adding monomer 2 to a
growing polymer chain ending with monomer 1, [mi] is the molar
concentration of monomer 1 (ethylene) in the reactor, [m2] is the molar
concentration of monomer 2 (1-octene) in the reactor, ktmi2 the termination
rate constant for chain transfer to monomer 2 for a growing chain ending with
monomer 1, kts1 is rate constant for the spontaneous chain termination for a
chain ending with monomer 1, kun is the rate constant for the chain
termination by hydrogen for a chain ending with monomer 1. (/), and 02and
the fraction of catalyst sites occupied by a chain ending with monomer 1 or
monomer 2 respectively.
The number average molecular weight (Mn) for a polymer follows from
the degree of polymerization and the molecular weight of a monomer unit.
From the number average molecular weight of polymer in a given reactor, and
76
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assuming a Flory-Schulz distribution for a single site catalyst, the molecular
weight distribution is determined for the polymer using the following
relationships.
(5) w(n) = n12 e-tn
where n is the number of monomer units in a polymer chain, w(n) is the
weight fraction of polymer chains having a chain length n, and r is calculated
using the equation:
1 Rt
= =
dpn Rp
where dpn is the degree of polymerization, Rp is the rate of propagation
and Rt is the rate of termination.
The Flory-Schulz distribution can be transformed into the common log
scaled GPC trace by applying:
dW n2 (_-1-1
(6) = ln(10)¨e dPn
dlo g (M) dpn2
where dW
dlog(MW) is the differential weight fraction of polymer with a chain length
n (n = MW /28 where 28 is the molecular weight of the polymer segment
corresponding to a C2H4 unit) and dpn is the degree of polymerization.
Assuming a Flory-Schultz model, different moments of molecular
weight distribution can be calculated using the following:
= ni W(n)dn
0
thus,
tio = 1,
= dpn, and
112 = 2 dpn2 ;
SO,
Mn = MWmonomer¨ = MWmonomer dPn
112
Mw = MWmonomer 2 MWmonomer dPn
where m
- -Wmonomer is the molecular weight of the polymer segment
corresponding to a C2F14 unit of monomer.
77
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Alternatively, when a Ziegler-Natta catalyst is employed, the molecular
weight distribution of the polymer made in a given reactor by a Ziegler-Natta
catalyst, can be modeled as above but using the sum of four such single site
catalyst sites, each of which is assumed to have a Flory-Schultz distribution.
When considering the kinetics of the process model for a Zielger-Natta
catalyst, the total amount of the Ziegler-Natta catalyst components fed to a
reactor are known, and it is assumed that there is the same weight fraction of
each of the four active catalyst sites modeled, but where each site has its
own
kinetics.
Finally, when a single site catalyst produces long chain branching, the
molecular weight distribution is determined for the polymer using the
following
relationships (see "Polyolefins with Long Chain Branches Made with Single-
Site Coordination Catalysts: A Review of Mathematical Modeling Techniques
for Polymer Microstructure" by J.B.P Soares in Macromolecular Materials and
Engineering, volume 289, Issue 1, Pages 70-87, Wiley-VCH, 2004 and
"Polyolefin Reaction Engineering" by J.B.P Soares and T.F.L. McKenna
Wiley-VCH, 2012).
(1 - a) T-Be-TBn ( BnArci)
w (n) = ___________________________________ 2 __
(1 + a) 1 + a )
where n is the number of monomer units in a polymer chain, w (n) is the
weight fraction of polymer chains having a chain length n, and TB and a are
calculated using equations below:
T 1 Rt + RuB
8 dpg Rp
RLCB
a = ¨Rp
where dee, is degree of polymerization, Rp is the rate propagation, Rt is the
rate of termination and RLCB is the rate of long chain branching formation
calculated using equation below:
RLCB = kpl3 01 [M-31
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where kp13 is the propagation rate constant for adding monomer 3
(macromonomer which is formed in the reactor) to a growing polymer chain
ending with monomer 1, [m3] is the molar concentration of macromonomer in
the reactor.
The weight distribution can be transformed into the common log scaled
GPC trace by applying:
dW
(7)
dlog(M)= 111(10) (1¨a) (1+a) v TB_ _________ 1¨e¨TBn (2 TE2211-1
a 1 1+a
where dW
dlog(MW) is the differential weight fraction of polymer with a chain length
n (n = MW/28 where 28 is the molecular weight of the polymer segment
corresponding to a C2H4 unit).
From the weight distribution, different moments of molecular weight
distribution can be calculated using the following:
R 1 + a
Mn = Mwmonomer
¨ a
1 + a
Mw = 2 Mwmonomer dri't (1 ¨ a)2
where dpg is degree of polymerization, and a is calculated as above.
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0
01
0
Iµ)
LA.) TABLE 1
0
Reactor Operating Conditions
0 Example No. Inventive 1 Inventive 2
Inventive 3 Inventive 4 Inventive 5 Inventive 6
Total Solution Rate (TSR)
551.1 525.0 549.9 550.0 500.0 500.0
(kg/h)
Ethylene Concentration
12.4 12.3 12.6 12.6 13.8 13.8
(wt% overall)
Ethylene Split Between
45.0 45.0 45.0 45.0 45.0 45.0
Reactors (R1/(R1+R2)
1-octene/ethylene
0.930 1.051 0.780 0.670 0.919 0.638
(wt%) (total)
1-Octene Split Between
0.20 0.20 0.20 0.28 0.25 0.33
Reactors (R1/(R1 + R2))
Polymer Production Rate
60.5 57.2 61.3 61.3 63.1 63.0
in kg/h (by near infra-red)
Reactor 1 (R1)
Total Solution Rate in R1
323.7 315.9 331.7 331.8 279.7 284.9
(kg/h)
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0
W
0
Ul
0
,1 Ethylene concentration
n) 9.50 9.20 9.40
9.40 11.10 10.90
w
(wt%) in R1
n)
0
1-. 1-Octene/ethylene in fresh
to
1 0.38 0.43 0.32
0.39 0.43 0.41
0 feed (g/g)
,1
1
n)
to Primary Feed Inlet
30.0 30.0 30.0
30.0 30.0 30.0
Temperature in R1 ( C)
R1 Control temperature
137.8 135.0 136.1
135.9 154.0 154.0
( C)
Ethylene conversion, by
80.04 80.16 79.86
80.09 80.00 80.00
near infra-red, in R1 ( /0)
Hydrogen Feed (ppm) 5.96 4.97 6.30
6.30 0.00 0.03
Single Site Catalyst (ppm)
0.33 0.40 0.32
0.32 0.30 0.29
to R1
SSC - Al/Hf (mol/mol) 30.3 30.1 30.1
30.1 30.1 30.1
SSC - BHEB/AI (mol/mol) 0.40 0.41 0.56
0.42 0.44 0.41
SSC - B/Hf (mol/mol) 1.21 1.20 1.20
1.20 1.21 1.20
R1 Diluent Temperature
29.3 35.1 38.2
32.3 30.4 31.0
( C)
_ _
Reactor 2 (R2)
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0
W
0
01
0
,1 Total Solution Rate in R2
n)
W 227.4 209.2 218.2
218.2 220.3 215.1
K) (kg/h)
0
1-.
to Ethylene fresh feed to R2
I 16.53 16.98 17.46
17.46 17.23 17.64
0
,1 concentration (wt%)
1
n)
to 1-Octene/ethylene in fresh
1.52 1.72 1.28 1.00 1.32 0.82
feed (g/g)
. _.
Primary Feed
40.0 40.0 40.1 40.0 40.0 40.1
Temperature in R2 ( C)
R2 Control Temperature
182.0 179.9 182.2 181.9 202.1 202.0
( C)
Ethylene conversion, by
81.95 82.03 82.07 81.99 86.57 86.50
near infra-red, in R2 (%)
Hydrogen Feed (ppm) 0.51 0.52 0.49
0.49 8.56 9.35
Multi-Site Catalyst (Ti
0.35 0.35 0.35 0.35 0.35 0.35
ppm) to R2
,
ZN - tertbutylchloride/Mg
1.52 1.52 1.52 1.52 1.52 1.52
(mol/mol)
ZN - diethyl aluminum
1.35 1.35 1.35 1.35 1.35 1.35
ethoxide/Ti (mol/mol)
82
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0
W
0
Ul
0
,1 ZN - Mg/Ti (mol/mol) 7.2 7.2 7.2
7.2 7.2 7.2
n)
LA)
R2 Diluent Temperature
n) 32.8 37.2 40.0
35.2 33.8 34.3
0
1-. ( C)
to
1
0
,1
1
n)
to
TABLE 2
Polymer Properties
Example No. Inventive 1 Inventive 2
Inventive 3 Inventive 4 Inventive 5 Inventive 6
Density (g/cm3) 0.9082 0.9061 0.9128 '
0.9123 0.9067 0.9133
Melt Index 12 (g/10
0.85 0.82 0.84
0.76 3.66 3.56
min)
Melt Index 121 (g/10
21.5 21.5 19.9
18.7 90 89
min)
Melt Flow Ratio
25.4 25.4 23.6
23.7 24.8 24.6
(121/12)
Stress Exponent 1.29 1.29 1.25
1.27 1.25 1.29
Mn 41842 35726 37552
41197 31813 29624
Mw 105477 101423 108775
115423 73637 74869
Mz 212739 213447 229055
283932 134410 148528
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0
W
0
01
0
,1
n) Polydispersity
u.) 2.52 2.92 2.9 2.8
2.31 2.53
n) Index (Mw/Mn)
0
1-.
to CTREF - High
1
0
,1 Temperature 95.7 95.9 95.8
95.8 95.4 95.6
1
n)
to Elution Peak ( C)
CTREF - CDBI5o 70.1 69.8 69.6 '
64.8 71.2 67.4
CTREF - weight '
percent (wt%)
8.9 9.5 10.6
11.8 5.5 8.5
eluting at from
90 C to 105 C
CTREF - TPCTREF 61.1 58.4 68.1 '
62.4 61.3 62.1
Heat of Fusion
101.4 96.6 113.9
114.1 96 113.3
(J/g)
Crystallinity (%) 35 33.3 39.3
39.4 33.1 39.1
_
Branch
21.5 23.5 17.9
18.5 24.1 19.2
Freq/1000C
Comonomer 1-octene 1-octene 1-octene 1-
octene 1-octene 1-octene
Comonomer
4.3 4.7 3.6 3.7
4.8 3.8
Content (mole%)
84
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0
01
0
Comonomer
15.3 16.5 12.9
13.3 16.9 13.8
Content (wt%)
Ti (ppm) 4.82 - 5.34 6.81
5.15 12.0 9.32
Hf (ppm) 0.316 0.410 0.324
0.323 0.219 0.243
Melt Strength -
4.06 4.17 3.98 4.27 1.18 1.17
190 C (cN)
LCBF 0.00091 0.000877 0.00117
0.00143 <0.001 0.000266
Internal
0.006 0.007 0.005 0.005 0.008 0.007
Unsaturation/100C
Side Chain
0.001 0.001 0 0 0.006 0.006
Unsaturation/100C
Terminal
0.025 0.023 0.026 0.027 0.032 0.036
Unsaturation/100C
TABLE 2 Continued
Polymer Properties
Example No. Comp. 1 Comp. 2 Comp. 3
Comp. 4 Comp. 5 Comp. 6 Comp. 7
Density (g/cm3) 0.9081 0.9091 0.9093
0.9116 0.9113 0.9141 0.9173
\\chclients\ipgroup\Cliff\CBSpec\CIPOOnlineFilings\2018081Canada.docx
0
W
0
IA
0
,I Melt Index 12 (g/10
n) 0.83 0.88 1.11 0.98
3.78 0.86 3.83
w
n) min)
0
1-. Melt Index 121 (g/10
to
1 25.8 30.4 41.2 16.4
63 6.2 93
0
,I min)
1
n)
to Melt Flow Ratio
29.9 34.7 36.2 16.7 16.7 19.5 22.7
(121/12)
Stress Exponent 1.34 1.48 1.48 1.13
1.12 22 1.2
Mn 43351 42720 38112 48526
42934 43435 29105
Mw 94385 81470 82272 101890
74382 108418 72510
Mz 175746 136620 149535 ' 167833 .
114940 231322 146082
Polydispersity
2.18 1.91 2.16 2.1 1.73 2.5 2.49
Index (Mw/Mn)
_ =
CTREF - High
Temperature 78.1 75.9 88.4 92.5
92.6 95.9 94.5
Elution Peak ( C)
CTREF - CDB15o 86.5 83.9 - 86.7 71.6
74.9 62 81.3
CTREF - weight
percent (wt%) 0.1 0 0 3.9
1.5 14.5 4.6
eluting at from
86
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0
01
0
90 C to 105 C
Heat of Fusion
106.2 105.3 113.4 111.37 121.4 122.5
(J/g)
Crystallinity (%) 36.61 36.3 39.1
38.4 41.8 42.25
Branch
16.1 17.7 18.6 15.9
18.9 16.9 14.7
Freq/1000C
Comonomer ID 1-hexene 1-octene 1-octene 1-hexene
1-hexene 1-octene 1-octene
Comonomer
3.2 3.5 3.7 3.2
3.8 3.4 2.9
Content (mole%)
Comonomer
9.1 12.8 13.4 9
10.6 12.3 10.8
Content (wt%)
Ti (ppm)
8.06 0.227
Hf (ppm)
NA NA
Melt Strength -
3.89
190 C (cN) 3.99 3.71 2.27
0.72 4.36 0.71
LCBF <0.001
<0.001
Internal
0.003 0.004 0.013 0.001
0.001 0.007 0.021
Unsaturation/100C
87
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0
W
0
01
0
,1 Side Chain
n) 0.002 0.001 0.011 0.001
0.003 0.004 0.003
w Unsaturation/100C
K)
0 Terminal -
to 0.006 0.008 0.01 0.009
0.007 0.028 0.007
,
o Unsaturation/100C
,1
1
n)
to
TABLE 3
Polyethylene Composition Component Properties
Example No. Inv. 1 Inv. 2 Inv. 3
Inv. 4 Inv. 5 Inv. 6
The First Ethylene
Copolymer
_ _
Single Site Single Site Single
Site Single Site Single Site Single Site
Catalyst Type 1
Catalyst Catalyst Catalyst
Catalyst Catalyst Catalyst
_
weight fraction, wt1
0.43 0.43 0.43
0.45 0.41 0.43
(wt%)
_
121 (g/10min) 0.25e 0.18 e 0.24e
0.28e 1.23e 1.02 e
p1 (g/cm3) 0.8968 c 0.8945 c 0.9018 c
0.8974 c 0.8967 c 0.8971 c
¨
Mn1 67039 72857 67588
65038 44565 46667
Mwl 138736 150845 ¨ 139807
134283 91859 ' 96339
Mw1/Mn1 2.07 2.07 - 2.07
2.06 2.06 2.06
88
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0
W
0
01
0
,1 short chain branches
n)
w
n) per 1000 carbons 27.49a 29.92a 22.70a
26.95a 27.64a 27.26a
o
i-. (SCB1)
to
1
0
,1 The Second Ethylene
1
n)
to Copolymer
_
Ziegler-Natta Ziegler-Natta Ziegler-Natta Ziegler-Natta Ziegler-Natta Ziegler-
Natta
Catalyst Type 2
Catalyst Catalyst Catalyst Catalyst Catalyst
Catalyst
_
weight fraction, wt2
0.57 0.57 0.57 0.55 0.59 0.57
(wt%)
_.
122 (g/10min) 1.72e 1.56e 1.62e
1.47e 8.65e 6.93e
p2 (g/cm3) 0.9169d 0.9150d 0.9212d
0.9243 d 0.9138d 0=9254d
Mn2 25640 26102 25909 - 26267
19384 20076
Mw2 ' 87053 89323 88458
90604 57146 60546
Mw2/Mn2 3.40 3.42 3.41
3.45 2.95 3.02
short chain branches
per 1000 carbons 1691b 18=56b 1422b
11=70b 21=60b 13.20 b
(SCB2)
a SCB1, the number of hexyl branches per thousand backbone carbon atoms of the
first ethylene copolymer = 74.29-0.7598
(TPc-rREF); where TPCTREF is the peak elution temperature of the first
ethylene copolymer in the CTREF chromatogram.
89
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0
01
0 b SCB2, the number of hexyl branches per thousand backbone carbon
atoms of the second ethylene copolymer is determined by
considering the linear branch frequency rule and the respective weight
fractions of the first and second ethylene copolymer
0
components; SCB2 = (SCB overall - wtl* SCB1)/(wt2).
0 c p1 =
k al ¨ (a12- 4*ao*(a2-(SCB1C6/1000C))) .5))/(2*ao); where ao = 9341.81, al = -
17765.91 and az = 8446.849
d p2 = (pf
Wtl*p1)/(Wt2);- where p 1 , p2 and pf are the densities of the first ethylene
copolymer, the second ethylene copolymer and the
overall (ethylene copolymer composition) density respectively, and wt1 and wt2
represent the respective weight fractions of the first
and second ethylene copolymer components.
e Melt Index (12, dg/min): Log 12 = 7.8998042-3.9089344log(Mw/1000)-
0.27994391*Mn/Mw; where Mw is weight average molecular
weight of the respective component and Mn is number average molecular weight
of the respective component (i.e. the first or the
second ethylene copolymer) as determined by polymerization process modeling
(See Polymerization Process Model section).
\\chclients\ipgroup\Cliff\CBSpec\CIPOOnlineFilings\2018081Canada.docx
The data in Table 2, clearly shows that in contrast to Comparative
Examples 1-5, the Inventive Example ethylene copolymer compositions have
more than 4 weight percent of material eluting at from 90 to 100 C in a TREF
analysis. The Inventive Example ethylene copolymer compositions also have
more than 0.100 ppm of hafnium as well as more than 1 ppm of titanium
present, whereas both Comparative Examples 6 and 7 which are made with a
different catalyst system (one which does not employ a hafnium based
polymerization catalyst) are expected to have zero ppm of hafnium present.
Blown Film (Monolaver)
Inventive ethylene copolymer compositions, Inventive Examples 1-4,
having a melt index, 12 of 1 g/10min or less, as well as comparative resins,
Comparative Examples 1, 2, 3, 4 and 6 having a melt index, 12 of 1.11 g/10min
or less, were blown into monolayer film using a Gloucester Blown Film Line,
with a Gloucester extruder, 2.5-inch (6.45 cm) barrel diameter, 24/1 LID
(barrel Length/barrel Diameter) equipped with: a barrier screw; a low pressure
4 inch (10.16 cm) diameter die with a 35 mil (0.089 cm) die gap, and; a
Western Polymer Air ring. The die was coated with polymer processing aid
(PPA) by spiking the line with a high concentration of PPA masterbatch to
avoid melt fracture. The extruder was equipped with the following screen
pack: 20/40/60/80/20 mesh. Blown films, of about 1.0 mil (25.4 pm) thick and
2.0 mil (50.8 pm) thick, at 2.5:1 Blow Up Ratio (BUR), were produced at a
constant output rate of 100 lb/hr (45.4 kg/hr) by adjusting extruder screw
speed, and; the frost line height was maintained at 16-18 inch (40.64-45.72
cm) by adjusting the cooling air. The monolayer 1-mil film produced with a
blow-up ratio (BUR) of 2.5 were used for obtaining the physical properties of
the films. The monolayer 2-mil film (BUR = 2.5) was used for obtaining the
cold-seal and hot tack profiles. Blown film processing conditions are provided
in Table 4. Data for film blown from the ethylene copolymer compositions of
the present disclosure is provided in Table 5, along with data for films made
from various comparative resins. The film properties of the ethylene
copolymer compositions of the present disclosure provided in Table 5, along
with data for films made from various comparative resins are measured on 1-
mil film (BUR = 2.5) except for hot tack and cold seal properties. The hot
tack
91
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test profiles for film blown from ethylene copolymer compositions of the
present disclosure, along with those made from various comparative resins
are given in Figure 4.
92
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0
W
0
01
0
,1
i.) TABLE 4
W
i.) Blown Film Process Conditions
0
1-.
to Example No. Inventive 1 Inventive 2
Inventive 3 Inventive 4
1
0
,I Blow Up Ratio 2.5:1 2.5:1
2.5:1 2.5:1
1
n)
to Layflat 15.7 15.7
15.7 15.7
Thickness (mil) 1 1
1 1
Output (lb/hr) 100 100
100 100
Melt Temperature ( F) 430 430
432 431
Frost Line Height
(inches) 18 18
18 18
. _
Cooling Setting (Blower)
( c) 7 7
7 7
Magnehelic (in-H20) ' 7.0 7.3
7.0 7.3
Nip Pressure (psi) 30 30
30 30
Nip Roll Speed (ft/min) 133 133
133 132
Die Mill Gap (mils) 35 35
35 35
Extruder Current:
(Amps) 41 41
42 42
Extruder Voltage: (Volts) 197 195
201 199
93
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0
W
0
01
0 Extruder Pressure (psi) 4502 4527
4537 4585
,1
K)
LA.) Screw Speed (rpm) 41 40
42 42
n)
0
1-. Specific Output
to
1
0 (Ib/hr.rpm) X 10 24.4 25.0
23.8 23.8
,1
1
n) Power (kW) 8.1 8.0
8.4 8.4
to
Specific Energy
(VV/lb/hr) 80.8 80.0
84.4 83.6
TABLE 4 Continued
Blown Film Process Conditions
Example No. Comp. 1 1 Comp. 2
Comp. 3 Comp. 4 Comp. 6
Blow Up Ratio 2.5:1 . 2.5:1
2.5:1 2.5:1 2.5:1
,
Layflat 15.7 15.7
15.7 15.7 15.7
Thickness (mil) 1 1 1
1 1
Output (lb/hr) 100 100 100
100 100
Melt Temperature ( F) 431 431 431
433 432
Frost Line Height
18 18 16
16 18
(inches)
94
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0
W
0
Ul
0
,1 Cooling Setting (Blower)
n) 8 8 9
8 7
w
( C)
n)
0
1-. Magnehelic (in-H20) 9.8 9.8
13.3 11.3 7.0
_
to
1 _ -
0 Nip Pressure (psi) 30 30 30
30 30
,1
1
n)
to Nip Roll Speed (ft/min) 133 133 132
130 133
_ -
Die Mill Gap (mils) 35 35 35
35 35
-
Extruder Current:
39 35 32
45 44
(Amps)
Extruder Voltage: (Volts) 199 195 181
183 219
Extruder Pressure (psi) 4002 3662
3404 4567 4905
Screw Speed (rpm) 42 41 39
37 46
_
Specific Output
,
23.8 24.4
25.6 27.0 21.7
(Ib/hr.rpm) X 10
Power (kW) 8.1 6.2 5.8
8.2 9.6
-
_
Specific Energy
81.3 61.9
57.9 82.4 96.4
(VV/Ib/hr)
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0
01
0 TABLE 5
LA) Blown Film Properties
0
Example No. Inventive 1 Inventive 2
Inventive 3 Inventive 4
Film Physical Properties
Thickness Profile Ave 1.03 1.05
1.06 1.07
Film Toughness
Dart Impact (g/mil) 999 892
939 909
Slow Puncture - Lube/Tef
111 119
106 108
(J/mm)
Film Tear Resistance
Tear - MD (g/mil) 229 217
220 270
Tear - TD (g/mil) 486 457
522 538
Film Stiffness
1% Sec Modulus - MD
136 204
266 164
(Mpa)
1% Sec Modulus - TD
177 152
167 167
(Mpa)
2% Sec Modulus - MD
126 179.5
235 151
(Mpa)
96
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0
01
0
2% Sec Modulus - TD
158 136 153 154
(Mpa)
0
Film Tensile Strength
o =
Tensile Break Str - MD
48.8 65.5 59.3 47.3
(Mpa)
1
Tensile Break Str - TD
35.9 35.8 45.9 45.3
(Mpa)
Elongation at Break - MD
518 546 544 507
(%)
Elongation at Break - TD
684 647 718 708
(%)
Tensile Yield Str - MD
7.6 8 10.7 8.9
(Mpa)
Tensile Yield Str - TD
7.7 6.9 8.8 8.7
(Mpa)
Tensile Elong at Yield -
11 9
9 10
MD (%)
Tensile Elong at Yield -
10 10 10 10
TD (%)
97
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Ul
0
Film Optics
Gloss at 450 78 77
78 73
Haze (%) 3A 3.6
3.5 4.5
Cold Seal Properties ¨2
mil film
S.I.T. @ 8.8N Seal
84.5 83.9 93.8 93.2
Strength ( C)
Max Force (N) 19.0 20.5
23.5 25.1
Temp. @ Max Force ( C) 120 125
130 125
Hot Tack Properties ¨2
mil film
Hot Tack Onset
Temperature @ 1.0N ( C) 71.5 61.5
83.8 83.9
- 2 mil film
Maximum Hot Tack
4.5 4.3
5.0 4.6
Strength (N) - 2 mil film
Hot Tack Window at 2.5
51.1 48.9 59.5 57.6
N, HT1N ( C)
98
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01
0
TABLE 5 Continued
Blown Film Properties
0
Example No. Comp. 1 Comp. 2 Comp. 3
Comp. 4 Comp. 6
Film Physical Properties
Thickness Profile Ave 1.06 -
1.05 1.02 1.03 1.05
Film Toughness
Dart Impact (g/mil) 685 708
1052 789
Slow Puncture - Lube/Tef
106 120 100 84 95
(J/mm)
Film Tear Resistance
Tear-MD (g/mil) 164 149
250 247
Tear - TD (g/mil) 459 - 380
565 575
Film Stiffness
1% Sec Modulus - MD
141 126 102 162.7 166
(MPa)
1% Sec Modulus - TD
165 170 102 183.1 180
(MPa)
2% Sec Modulus - MD
133 116 98 149.6 154
(MPa)
99
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0
W
0
01
0
,1 2% Sec Modulus - TD
n) 154 151 95
167.8 165
u..)
(Mpa)
K) .
0
I-. Film Tensile Strength
to
1
o Tensile Break Str - MD
,1
1 - 57.8
53.2 61.7 52.7
n) (Mpa)
to
Tensile Break Str - TD -
49.8
48.1 58 767
(Mpa)
Elongation at Break - MD
553 - 543 599 557
(%)
Elongation at Break - TD
- 759 762 762 10
(%)
Tensile Yield Str - MD -
7.2 7.4 8.8 8.9
(Mpa)
Tensile Yield Str - TD -
7,5 7.3 9.2 9.1
(Mpa)
Tensile Elong at Yield -
- 11 15 10 10
MD (%)
Tensile Elong at Yield -
- 10 38 10 10
TD (c/o)
100
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Ul
0
Film Optics
Gloss at 450 69 69
82 80
Haze (%) - 10 4.5 4.1
3.4 3.6
0 Cold Seal Properties -2
mil film
S.I.T. @ 8.8N Seal
106.6 94.7 93.0 88.5 94.3
Strength ( C)
Max Force (N) 25.2 24.7 23.4
19.1 23.1
Temp. @ Max Force ( C) 140 120 130
145 145
Hot Tack Properties - 2
mil film
Hot Tack Onset
Temperature @ 1.0N ( C) 100.2 92.3 96.8
83.9 87.1
- 2 mil film
Maximum Hot Tack
4.6 4.4 3.9
5.0 4.9
Strength (N) - 2 mil film
Hot Tack Window at 2.5
39.4 27.1 11.7 37.5 32.2
N, HTW ( C)
101
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The data provided in Table 5 together with the data in Figure 4
demonstrate that the inventive ethylene copolymer compositions (Inventive
Examples 1-4) can be made into blown film having a good balance of
properties, including good dart impact, good puncture resistance, and good
sealing properties. For example, and with reference to Figure 4, the blown
films made from the inventive ethylene copolymer compositions (Inventive
Examples 1-4) have good hot tack and cold seal performance.
Without wishing to be bound by theory, in the hot tack (or cold seal)
profile (seal temperature vs. seal force), good hot tack (or cold seal)
performance is indicated by an early (or low) hot tack (or cold seal) onset
temperature, then a relatively high sealing force over a wide range of hot
tack
seal temperatures. See for example the shape of the curves in Figure 4 for
Inventive Examples 1-4, relative to Comparative Examples 1-4 and 6. The
shape of the hot tack curves for Inventive Examples 1 and 2, are particularly
good and have an early hot tack seal onset temperature combined by a high
sealing force over a wide range of hot tack seal temperatures. In an effort to
provide a more quantitatively measurement of this improved hot tack sealing
performance, a new parameter, the "the hot-tack (strength) window" (the "hot
tack window" or the "HTW") has been defined herein. In the present instance,
the HTW is simply the range of temperature, in C spanned by the hot tack
curve at a seal strength of 2.5 Newtons. The larger the hot tack window, the
greater the temperature window over which a high sealing force can be
maintained or achieved.
As shown in Table 5 and in Figure 4, the Inventive Examples 1, 2, 3
and 4 each have a HTW (at 2.5 N) of significantly greater than 40 C, whereas
each of the Comparative Examples, 1-4, and 6 have a HTW (at 2.5N) of less
than 40 C. The Inventive Examples 1-4 also have a relatively low hot tack
onset temperature (HTOT), of below about 85 C.
Good cold seal properties are evidenced by data given in Table 5 for
the Inventive Examples 1, 2, 3 and 4. From the data provided in Table 5, a
person skilled in the art will recognize that the Inventive Examples 1, 2, 3
and
4 each have a relatively low cold seal initiation temperature (SIT), of below
about 94 C.
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In addition to the good sealing properties, the data in Table 5 shows
that the Inventive Examples 1, 2, 3 and 4 have a superior combination of high
dart impact values, low haze values and high puncture resistance values
relative to the Comparative Examples 1-4 and 6.
Cast Film
Inventive ethylene copolymer compositions, Inventive Examples 5 and
6, which have a melt index, 12 of between 3 and 4 g/10min, as well as
comparative resins, Comparative Examples 5 and 7, which have a melt index,
12 of between 3 and 4 g/10 min, were used to make coextruded cast film on a
Gloucester cast film line. The coextruded films had a three layer A/B/A
structure with A being the skin layer and B being the core layer, and where
each layer was the same polymer. The extruder barrel and adapter
temperatures are set to 380 F and the die temperature is set to 400 F. The
extruder was equipped with the following screen pack: 20/40/60/80/20 mesh.
The casting roll and the cooling rolls are set at temperatures 90 F and 80 F,
respectively. Cast films, of about 0.8 mil (20.3 pm) thick, 2.0 mil (50.8 pm)
thick, and 3.5 mil (88.9 pm) thick were produced by adjusting winder
parameters as listed in Table 6. The cast film processing conditions are
provided in Table 6. Data for a three layer cast film having a thickness of
0.8
mil and made from the ethylene copolymer compositions of the present
disclosure (Inventive Examples 5 and 6) is provided in Table 7, along with
data for a three layer cast film having a thickness of 0.8 mil and made from
various comparative resins (Comparative Examples 5 and 7). Table 7 also
includes cold seal and hot tack properties for three layer cast films having a
thickness of 2 mil and made from the ethylene copolymer compositions of the
present disclosure (Inventive Examples 5 and 6) along with cold seal and hot
tack properties for a three layer cast film having a thickness of 2 mil and
made
from various comparative resins (Comparative Examples 5 and 7). The hot
tack test profiles for a three layer cast film having a thickness of 2 mil and
made from Inventive Examples 5 or 6, as well as Comparative Examples 5 or
7 are shown in Figure 5.
103
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0
W
0
01
0
,1 TABLE 6
n)
w
n) Cast
Film Process Conditions
0
1-.
to Example No. Inventive 5 Inventive 5 Inventive 5
Inventive 6 Inventive 6 Inventive 6
1
0 _ ,1 Core resin Inventive 5 Inventive 5
Inventive 5 Inventive 6 Inventive 6 _ Inventive 6
1 .
n) -
to Skin resin Inventive 5 Inventive 5 Inventive 5
Inventive 6 Inventive 6 Inventive 6
Core % 80 80 80 _ 80
80 80
. .
Skin % 20 20 20 20
20 20
_
Coex structure A/B/A A/B/A A/B/A
A/B/A A/B/A A/B/A
-
Extruders/Die
_
Die Gap (in) 0.025 0.025 0.025
0.025 0.025 0.025
Output (lbs/hr) - 462 462 462 452
452 452
Melt Temperature
500-550 500-550 500-550 500-550
500-550 500-550
Range ( F)
_.
Film thickness (mil) - 0.8 2 3.5 0.8 2
3.5
Vacuum box
Primary chamber
(rpm) 660 660 660 660
660 660
Pre-sweep chamber
(rpm) 1440 1440 1440
1440 1440 1440
104
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0
W
0
Ul r
0 Winder .
,1
n)
LA) Line speed (fpm) 800 310 180
800 310 180
n)
0 Swarp speed (fpm) 808 311 ' 179
807 311 - 178
to
1
0 Layon speed (fpm) 817 312 179 '
816 313 178
,1
1 _
n) Tension adj. pot 2.58 2.58 2.58
2.58 2.58 2.58
to
-
Taper adj. pot 1.50 1.50 1.50 1.50
1.50 1.50
Swarp tension pot 2.40 2.40 2.40 2.40 -
2.40 2.40
Layon draw adj.pot 1.80 1.80 1.80 1.80
1.80 1.80
_
Layon tession pot 0.89 0.89 0.89 0.89 0.89
- 0.89
Web width (in) 18 18 18 18
18 18
_ Roll width (in) - 26 26 26
24 25 24
TABLE 6 Continued
Cast Film Process Conditions
Example No. Comp. 5 Comp. 5 Comp. 5 Comp. 7
Comp. 7 Comp. 7
_
Core resin Comp. 5 Comp. 5 Comp. 5 Comp. 7 Comp. 7
Comp. 7
Skin resin Comp. 5 Comp. 5 Comp. 5 Comp. 7 Comp. 7
Comp. 7
Core % 80 80 80 80 80
80
105
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0
W
0
Ul
0
,1 Skin % 20 20 20
20 20 20
n)
w
n) Coex structure A/B/A A/B/A A/B/A
A/B/A A/B/A A/B/A
0
1-.
to Extruders/Die
1
0 _
,I Die Gap (in) 0.025 0.025 0.025
0.025 0.025 0.025
1
_
n)
to Output (lbs/hr) 458 458 458
458 458 458
Melt Temperature
500-550 500-550 500-550
500-550 500-550 500-550
Range ( F)
Film thickness (mil) 0.8 2 3.5
0.8 2 3.5
Vacuum box
Primary chamber (rpm) 660 660 - 660
660 660 660
Pre-sweep chamber
(rpm) 1440 1440 1440
1440 1440 1440
_
Winder
_
Line speed (fpm) 800 310 178
800 310 180
Swarp speed (fpm) 808 311 180 .
807 311 179
Layon speed (fpm) ' 816 312 180
816 312 180
Tension adj. pot 2.58 ' 2.58 - 2.58
2.58 2.58 2.58
Taper adj. pot 1.50 1.50 1.50 '
1.50 1.50 1.50
_
Swarp tension pot 2.40 2.40 2.40
2.40 2.40 2.40
106
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0
W
0
Ul
0 Layon draw adj.pot 1.80 1.80 1.80 1.80
1.80 1.80
,1
i.)
u.) Layon tession pot 0.89 0.89 0.89 -
0.89 0.89 0.89
i.)
0 Web width (in) 18 18 18 18
18 18
1-.
to .
' Roll width (in) 24 25 25 24
25 26
0
,1
1
K)
l0
TABLE 7
Three Laver Coextruded Cast Film Properties
Example No. Inv. 5 Inv. 6
Comp. 5 Comp. 7
Film Thickness (mil) 0.8/2 0.8/2
0.8/2 0.8/2
Dart Impact (g/mil) 580 569 '
610 396
_
Slow Puncture - Lube/Tef
117 88 105 80
(J/mm)
Tear-MD (g/mil) 334 384
303 383
Tear - TD (g/mil) 673 626
520 536
1% Sec Modulus-MD (Mpa) 74 100
83 125
1% Sec Modulus - TD (Mpa) 69 124
82 202
2% Sec Modulus-MD (Mpa) ' 72 99
81 118
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0
W
0
01
0
,1
n) 2% Sec Modulus - TD (Mpa) 68 119
83 151
w
n) Tensile Break Strength - MD 43.2 50
43.1 51.6
0
1-.
to Tensile Break Strength - TD 40.2 41.8
38.8 44
1
0
,1 Elongation at Break-MD 484 516
481 535
1
n)
to Elongation at Break - TD 719 732
701 730
Tensile Yield Str - MD 7.4 7.8 '
7.6 8.2
Tensile Yield Str - TD 7.4 7.7
7.5 7.8
Tensile Elong at Yield - MD
10 10 11
( /0)
Tensile Elong at Yield - TD
10 10
10 10
(o/o)
Film Opticals
Gloss at 45 ( ) 87 88
84 89
Haze (%) 0.8 1.2
2.6 1.5
Cold Seal Properties ¨ 2
mil film
S.I.T. @ 8.8N Seal Strength
84.8 89.1
93.1 101.5
( C)
Max Force (N) 18.3 19.6
20.4 19.2
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0
Ul
0 Temp. @ Max Force ( C) 115 125
130 135
Hot Tack Properties ¨2 mil
0
film
0 Hot Tack Onset Temperature
79.1 90.3
90.3 101.8
@ 1.0N ( C) - 2 mil film
Maximum Hot Tack Strength
3.5 4.1
4.4 4.1
(N) -2 mil film
Hot Tack Window at 2.5 N,
21.6 33.3
22.7 26.0
HTVV ( C)
109
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The data provided in Table 7 together with the data in Figure 5
demonstrate that the Inventive ethylene copolymer compositions (Inventive
Examples 5 and 6) can be made into a cast film structure having good sealing
properties. For example, and with reference to Table 7 and Figure 5, the
three layer cast films made from the Inventive ethylene copolymer
compositions (Inventive Examples 5 and 6) have good hot tack and cold seal
performance. As shown in Table 7 and in Figure 5, the Inventive Example 5
provided for superior (i.e. lower) hot tack onset temperature (HTOT) and
superior (i.e. lower) seal initiation temperature (SIT) than either of the
Comparative Examples 5 and 7: Inventive Example 5 gave a HTOT of less
than about 80 C, while Comparative Examples 5 and 7 gave HTOT values of
90.3 C and 101.8 C respectively; Inventive Example 5 gave a SIT of less than
about 90 C, while Comparative Examples 5 and 7 gave SIT values of 93.1 C
and 101.5 C respectively. Also shown in Table 7 and in Figure 5, is that the
Inventive Example 6 provided a larger hot tack widow (HTVV at 2.5 N) of over
30 C when used in the cast film structure, while Comparative Examples 5 and
7 provided a hot tack window (HTVV at 2.5N) of less than 30 C when used in
the cast film structure. Inventive Example 6 gave a SIT of just less than
about
90 C, while Comparative Examples 5 and 7 gave SIT values of 93.1 C and
101.5 C respectively.
Blown Film (Multilaver)
Multilayer blown film was produced on a 9-layer line commercially
available from Brampton Engineering (Brampton ON, Canada). The structure
of the 9-layer films produced is shown in Table 8. Layer 1 contained either an
inventive ethylene copolymer composition made according to the present
disclosure or a comparative resin as a sealant layer. More specifically, layer
1
contained either 89.5 wt% of Inventive Example 1 or Inventive Example 2 or
Comparative Example 6, 4.0 wt% of an antiblock masterbatch, 2.5 wt% of a
slip masterbatch and 4.0 wt% of a processing aid masterbatch, such that layer
1 contained 6250 ppm of antiblock (silica (diatomaceous earth)), 1500 ppm of
slip (eurcamide) and 1500 ppm of processing aid (fluoropolymer compound).
Note that the additive masterbatch carrier resins were a LLDPE which had a
melt index, 12 of about 2.0 g/10min, and a density of about 0.918 g/cc. Layer
1
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was the insider layer, i.e. inside the bubble as the multilayer film was
produced on the blown film line. The total thickness of the 9 layer film was
held constant at 3.5-mil; the thickness of layer 1 was 0.525 mil (13.3 m),
i.e.
15% of 3.5 mil (see Table 8). Layers 2, 5, and 8 contained SURPASS
HPs167-AB a high density polyethylene resin available from NOVA Chemicals
Corporation having a density of about 0.967 g/cc and a melt index, 12 of about
1.20 dg/min. Layers 3, 4, 6 and 7 contained SCLAIR FP120-C an
ethylene/l-octene copolymer resin available from NOVA Chemicals
Corporation having a density of about 0.920 g/cc and a melt index, 12 of about
1 dg/min. Layer 9 contained as a sealant resin, SCLAIR 19C a high density
polyethylene resin available from NOVA Chemicals Corporation having a
density of about 0.958 g/cc and a melt index 12 of about 0.95 dg/min. More
specifically, layer 9 contained 97.0 wt% of the sealant resin, 3.0 wt% of an
antiblock masterbatch such that layer 9 contained 6250 ppm of antiblock
(silica (diatomaceous earth)). The multilayer die technology consisted of a
pancake die, FLEX-STACK Co-extrusion die (SCD), with flow paths machined
onto both sides of a plate, the die tooling diameter was 6.3-inches, in this
disclosure a die gap of 85-mil was used consistently, film was produced at a
Blow-Up-Ratio (BUR) of 2.5 and the output rate of the line was held constant
at 250 lb/hr. The specifications of the nine extruders was as follows: screws
1.5-in diameter, 30/1 length to diameter ratio, 7-polyethylene screws with
single flights and Madddox mixers, 2-Nylon screws, extruders were air cooled,
equipped with 20-H.P. motors and all extruders were equipped with
gravimetric blenders. The nip and collapsing frame included a Decatex
horizontal oscillating haul-off and pearl cooling slats just below the nips.
The
line was equipped with a turret winder and oscillating slitter knives.
The sealing properties of the nine layer blown films (having a thickness
of 3.5 mil) made as described above are provided in Table 9. The hot tack
test profiles of the nine layer blown films are shown in Figure 6.
111
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Table 8
Multilaver Blown Film Structure
wt. % of Materials and
Weight% in Each Layer
Layer the 9- Material A Material B
Number layer
Material wt. % Material wt. ok
structure
Additive
Layer 9 5 19C 97 3.0
Masterbatches
Layer 8 10 HPs167-AB 100
Layer 7 12 FP120-C 100
Layer 6 13 FP120-C 100
Layer 5 10 HPs167-AB 100
Layer 4 13 FP120-C 100
Layer 3 12 FP120-C 100
Layer 2 10 HPs167-AB 100
Inv. 1 or Inv. 2 Additive
Layer 1 15 89.5 10.5
or Comp. 6 Masterbatches
Table 9
Sealing Properties of 3.5 Mil, Multilaver Blown Film Structure
Hot Tack
Maxim Hot Hot Tack S.I.T. @ 8.8N
Example No. Onset
Tack Strength Window at 5 Seal Strength
Used in Layer 1 Temperature
(N) N, HTW ( C) ( C)
@ 1.0N ( C)
Inventive 1 76.1 9.4 64.8 85.7
Inventive 2 80.7 9.1 61.9 90.0
Comp. 6 92.8 7.5 49.6 101.1
The data provided in Table 9 together with the data in Figure 6
demonstrate that when the inventive ethylene copolymer compositions are
used as a sealant layer (layer 1) in a multilayer blown film structure, the
structure has improved sealing properties. When used as the sealant layer,
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Inventive Examples 1 and 2 provided for superior (i.e. lower) hot tack onset
temperature (HTOT) and superior (i.e. lower) seal initiation temperature (SIT)
than Comparative Example 6: Inventive Examples 1 and 2 gave a HTOT of
less than about 81 C, while Comparative Example 6 gave HTOT value of
92.8; Inventive Examples 1 and 2 gave SIT values of about 90 C or less,
while Comparative Example 6 gave an SIT value of 101.1 C. Also shown in
Table 9 and in Figure 6, is that when used in the sealant layer 1 of the
multilayer film structure, the Inventive Examples 1 and 2 provided for a
larger
hot tack widow (HTW at 5 N), of over 60 C, while Comparative Example 6
provided a hot tack window value of less about 50 C. The Inventive
Examples 1 and 2 also lead to a higher maximum hot tack strength at greater
than about 9 N, while Comparative Example 6 gave a maximum hot tack
strength of 7.5 N.
Without wishing to be bound by theory, the superior hot tack properties
afforded by the inventive ethylene copolymer compositions are desired in high
speed vertical and horizontal form-fill-seal processes where a product
(liquid,
solid, paste, part, etc.) is loaded and sealed inside a pouch-like package.
Generally, the packaging industry prefers ethylene copolymer compositions
(e.g. for use as sealant resins) that have broad hot tack windows, as such
products may consistently produce leak-proof packages as various
parameters are changed on the packaging equipment. Further, it is desirable
that the Hot Tack Onset temperature (HTOT ( C)) occurs at the lowest
possible temperature. Also desirable is a high hot tack seal strength at high
temperatures, such that the seal strength remains sufficient at a range of
elevated temperatures. In contrast, the use of a resin with poor hot tack
properties can limit the packaging line production rate. Finally, in addition
to
the forgoing, it is desirable to have lower seal initiation temperature (SIT)
for
end use applications.
Non-limiting embodiments of the present disclosure include the
following:
Embodiment A. An ethylene copolymer composition comprising:
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(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.7 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
wherein the ethylene copolymer composition has at least 0.0015 parts
per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
Embodiment B. The ethylene copolymer composition according to
Embodiment A having a molecular weight distribution of from 2.2 to 5Ø
Embodiment C. The ethylene copolymer composition according to
Embodiment A or B having a melt flow ratio, 121/12 of from 20 to 50.
Embodiment D. The ethylene copolymer composition according to
Embodiment A, B, or C wherein the first ethylene copolymer has from 10 to 50
short chain branches per thousand carbon atoms (SCB1).
Embodiment E. The ethylene copolymer composition according to
Embodiment A, B, C or D wherein the second ethylene copolymer has from 3
to 25 short chain branches per thousand carbon atoms (SCB2).
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Embodiment F. The ethylene copolymer composition according to
Embodiment A, B, C, D or E wherein the first ethylene copolymer is present in
from 30 to 55 weight percent.
Embodiment G. The ethylene copolymer composition according to
Embodiment A, B, C, D, E or F wherein the second ethylene copolymer is
present in from 70 to 45 weight percent.
Embodiment H. The ethylene copolymer composition according to
Embodiment A, B, C, or D wherein the first ethylene copolymer is present in
from 30 to 55 weight percent; the second ethylene copolymer is present in
from 70 to 45 weight percent; and the third ethylene copolymer is present in 0
weight percent.
Embodiment I. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G or H having a composition distribution
breadth index, CDBI50 of from 50 to 75 weight percent.
Embodiment J. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, or I having a dimensionless long chain
branching factor, LCBF 0.001.
Embodiment K. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I or J having at least 3 mole percent of
one or more than one alpha-olefin.
Embodiment L. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I or J having from 3 to 10 mole percent of
one or more than one alpha-olefin.
Embodiment M. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I or J having from 3 to 8 mole percent of
one or more than one alpha-olefin.
Embodiment N. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L or M wherein said one or more
than one alpha-olefin is selected from the group comprising 1-hexene, 1-
octene and mixtures thereof.
Embodiment 0. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L or M wherein said one or more
than one alpha-olefin is 1-octene.
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Embodiment P. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N or 0 wherein the first
ethylene copolymer is a made with a single site catalyst.
Embodiment Q. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0 or P wherein the
second ethylene copolymer is a made with a Ziegler-Natta catalyst system.
Embodiment R. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, 1, J, K, L, M, N, 0, P or Q wherein the
third ethylene copolymer is a made with a Ziegler-Natta catalyst system.
Embodiment S. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P or Q wherein the
third ethylene copolymer is a made with a with a single site catalyst.
Embodiment T. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, or S wherein
the first ethylene copolymer is a made with a single site catalyst system
comprising a metallocene catalyst having the formula (I):
Ri
R4
1-11 Q
R2R5/ R3
%44111
Ilk
(I)
wherein G is a group 14 element selected from carbon, silicon, germanium, tin
or lead; Ri is a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy
radical or a C6_10 aryl oxide radical; R2 and R3 are independently selected
from
a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical or a C6-
10
aryl oxide radical; R4 and R5 are independently selected from a hydrogen
atom, an unsubstituted C1-20 hydrocarbyl radical, a substituted C1-20
hydrocarbyl radical, a C1-20 alkoxy radical or a C6-10 aryl oxide radical; and
Q is
independently an activatable leaving group ligand.
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Embodiment U. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S or T
wherein
the first ethylene copolymer has a composition distribution breadth index,
CDBI50 of at least 75 weight percent.
Embodiment V. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S, T or U
wherein the second ethylene copolymer has a composition distribution
breadth index, CDBI50 of less than 75 weight percent.
Embodiment W. The ethylene copolymer composition of Embodiment
A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S, T, U or V wherein the
first
ethylene copolymer is a homogeneously branched ethylene copolymer.
Embodiment X. The ethylene copolymer composition of Embodiment
A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S, T, U, V or W wherein
the
second ethylene copolymer is a heterogeneously branched ethylene
copolymer.
Embodiment Y. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S, T, U, V, W
or X wherein the second ethylene copolymer has a Mw/Mn of from 2.5 to 5Ø
Embodiment Z. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S, T, U, V,
W,
X or Y having from 0.050 parts per million (ppm) to 2.5 ppm of hafnium.
Embodiment AA. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S, T, U, V,
W,
X, Y or Z having from 0.50 ppm to 14.0 parts per million (ppm) of titanium.
Embodiment BB. The ethylene copolymer composition according to
Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, Q, R, S, T, U, V,
W,
X, Y, Z or AA wherein the third ethylene copolymer is present in from 5 to 30
weight percent.
Embodiment CC. The ethylene copolymer composition according to
Embodiment A or BB wherein the third ethylene copolymer has a density of
from 0.865 to 0.945 g/cm3; a molecular weight distribution, Mw/Mn of from 2.0
to 6.0; and a melt index, 12 of from 0.3 to 200 g/10min.
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Embodiment DD. A film layer comprising an ethylene copolymer
composition, the ethylene copolymer composition comprising:
(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.7 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
wherein the ethylene copolymer composition has at least 0.0015 parts
per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
Embodiment EE. The film layer according to Embodiment DD wherein
the film layer is a blown film.
Embodiment FF. The film layer according to Embodiment DD or EE
having a hot tack window (HTVV) of at least 45 C when measured at a film
thickness of about 2 mil.
Embodiment GG. The film layer according to Embodiment DD, EE, or
FF having a seal initiation temperature (SIT) of less than 95 C when
measured at a film thickness of about 2 mil.
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Embodiment HH. The film layer according to Embodiment DD, EE, FF
or GG having a hot tack onset temperature (HTOT) of less than 88 C when
measured at a film thickness of about 2 mil.
Embodiment II. The film layer according to Embodiment DD, EE, FF,
GG or HH having a dart impact strength of at least 800 g/mil when measured
at a film thickness of about 1 mil.
Embodiment JJ. The film layer according to Embodiment DD, EE, FF,
GG, HH or II having a slow puncture resistance value of at least 100 J/mm
when measured at a film thickness of about 1 mil.
Embodiment KK. The film layer according to Embodiment DD, EE, FF,
GG, HH, 11 or JJ having a haze value of less than 6% when measured at a film
thickness of about 1 mil.
Embodiment LL. The film layer according to Embodiment DD wherein
the film layer is a cast film.
Embodiment MM. A multilayer film structure comprising at least one
film layer comprising an ethylene copolymer composition, the ethylene
copolymer composition comprising:
(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.7 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
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wherein the ethylene copolymer composition has at least 0.0015 parts
per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
Embodiment NN. The multilayer film structure according to
Embodiment MM wherein the at least one film layer is a blown film.
Embodiment 00. The multilayer film structure according to
Embodiment NN wherein the at least one film layer has a hot tack window
(HTW) of at least 45 C when measured at a film thickness of about 2 mil.
Embodiment PP. The multilayer film structure according to
Embodiment NN or 00 wherein the at least one film layer has a seal initiation
temperature (SIT) of less than 95 C when measured at a film thickness of
about 2 mil.
Embodiment QQ. The multilayer film structure according to
Embodiment NN, 00 or PP wherein the at least one film layer has a hot tack
onset temperature (HTOT) of less than 88 C when measured at a film
thickness of about 2 mil.
Embodiment RR. The multilayer film structure according to
Embodiment NN, 00, PP or QQ wherein the at least one film layer has a dart
impact strength of at least 800 g/mil when measured at a film thickness of
about 1 mil.
Embodiment SS. The multilayer film structure according to
Embodiment NN, 00, PP, QQ or RR wherein the at least one film layer has a
slow puncture resistance value of at least 100 J/mm when measured at a film
thickness of about 1 mil.
Embodiment TT. The multilayer film structure according to
Embodiment NN, 00, PP, QQ, RR or SS wherein the at least one film layer
has a haze value of less than 6% when measured at a film thickness of about
1 mil.
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Embodiment UU. The multilayer film structure according to
Embodiment MM, NN, 00, PP, QQ, RR, SS or TT wherein the film structure
has at least three film layers.
Embodiment VV. The multilayer film structure according to
Embodiment MM, NN, 00, PP, QQ, RR, SS or TT wherein the film structure
has at least five film layers.
Embodiment WW. The multilayer film structure according to
Embodiment MM, NN, 00, PP, QQ, RR, SS or IT wherein the film structure
has at least seven film layers.
Embodiment XX. The multilayer film structure according to
Embodiment MM, NN, 00, PP, QQ, RR, SS or TT wherein the film structure
has at least nine film layers.
Embodiment YY. The multilayer film structure according to
Embodiment MM, NN, 00, PP, QQ, RR, SS or TT wherein the film structure
has 9 layers.
Embodiment ZZ. The multilayer film structure according to
Embodiment MM, NN, 00, PP, QQ, RR, SS, IT, UU, W, WW, XX or YY
where the at least one film layer is at least one sealant layer in the
multilayer
film structure.
Embodiment AAA. The multilayer film structure according to
Embodiment MM wherein the at least one film layer is a cast film.
Embodiment BBB. The multilayer film structure according to
Embodiment AAA having a seal initiation temperature (SIT) of less than 90 C
when measured at a film thickness of about 2 mil.
Embodiment CCC. A multilayer film structure comprising a sealant
layer, the sealant layer comprising an ethylene copolymer composition, the
ethylene copolymer composition comprising:
(i) from 20 to 80 weight percent of a first ethylene copolymer having a
density of from 0.855 to 0.913 g/cm3; a molecular weight distribution, Mw/Mn
of
from 1.7 to 2.3; and a melt index, 12 of from 0.1 to 20 g/10min;
(ii) from 80 to 20 weight percent of a second ethylene copolymer
having a density of from 0.875 to 0.936 g/cm3; a molecular weight
distribution,
Mw/Mn of from 2.3 to 6.0; and a melt index, 12 of from 0.3 to 100 g/10min; and
(iii) from 0 to 40 weight percent of a third ethylene copolymer;
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wherein the number of short chain branches per thousand carbon
atoms in the first ethylene copolymer (SCB1) is greater than the number of
short chain branches per thousand carbon atoms in the second ethylene
copolymer (SCB2);
wherein the density of the second ethylene copolymer is equal to or
greater than the density of the first ethylene copolymer;
wherein the ethylene copolymer composition has a density of from
0.865 to 0.913 g/cm3; a melt index, 12 of from 0.5 to 10 g/10min; and a
fraction
eluting at from 90 to 105 C, having an integrated area of greater than 4
weight
percent, in a CTREF analysis;
wherein the ethylene copolymer composition has at least 0.0015 parts
per million (ppm) of hafnium;
wherein the weight percent of the first, second or third ethylene
copolymer is defined as the weight of the first, second or the third ethylene
copolymer divided by the weight of the sum of (i) the first ethylene
copolymer,
(ii) the second ethylene copolymer and (iii) the third ethylene copolymer,
multiplied by 100%.
Embodiment DDD. The multilayer film structure according to
Embodiment CCC wherein the film structure has at least three film layers.
Embodiment EEE. The multilayer film structure according to
Embodiment CCC wherein the film structure has at least five film layers.
Embodiment FFF. The multilayer film structure according to
Embodiment CCC wherein the film structure has at least seven film layers.
Embodiment GGG. The multilayer film structure according to
Embodiment CCC wherein the film structure has at least nine film layers.
Embodiment HHH. The multilayer film structure according to
Embodiment CCC wherein the film structure has 9 layers.
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