Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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MULTI REACTOR SOLUTION POLYMERIZATION
FIELD OF THE INVENTION
This discloses a polymerization process utilizing at least three reactors,
where
two of the reactors are configured in parallel. Ethylene monomer is feed to
each of
the three reactors. Using this process, new multimodal polyethylene
compositions are
obtained while process efficiency improvements are realized.
BACKGROUND OF THE INVENTION
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 ethylene polymerization, or ethylene copolymerization, reactor
temperatures can range from about 80 C to about 300 C while pressures
generally
range from about 3MPag to about 45MPag. The ethylene homopolymer or copolymer
produced remains dissolved in the solvent under reactor conditions. The
residence
time of the solvent in the reactor is relatively short, for example, from
about 1 second
to about 20 minutes. The solution process can be operated under a wide range
of
process conditions that allow the production of a wide variety of ethylene
polymers.
Post reactor, the polymerization reaction is quenched to prevent further
polymerization, by adding a catalyst deactivator, and optionally passivated,
by adding
an acid scavenger. Once deactivated (and optionally passivated), the polymer
solution is passed to a polymer recovery operation (a devolatilization system)
where
the ethylene homopolymer or copolymer is separated from process solvent,
unreacted
residual ethylene and unreacted optional cx-olefin(s).
U.S. Patent No. 5,236,998 describes the use of a three reactor solution
polymerization process. Two reactors are configured in parallel and their
product
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streams are combined on route to a third reactor. The polymerization process
is
catalyzed by a Ziegler-Natta catalyst and allows for the formation of
polyethylene
products comprising three components, one from each reactor. However, the
disclosure fails to disclose or contemplate advantages which may be achieved
by
feeding fresh monomer (and optionally fresh catalyst) to the third reactor.
This is the
subject matter of the present disclosure.
SUMMARY OF THE INVENTION
The present disclosure provides a continuous solution polymerization process
which improves energy efficiency by reducing the amount of energy consumed.
An embodiment of the disclosure is a continuous solution polymerization
process comprising:
injecting ethylene, a process solvent, a first catalyst system, optionally one
or
more a-olefins and optionally hydrogen into each of a first reactor and a
second
reactor configured in parallel to each other to produce a first exit stream
containing a
first polyethylene made in the first reactor and a second exit stream
containing a
second polyethylene made in the second reactor;
passing the first exit stream and the second exit stream into a third reactor
and
injecting into the third reactor, ethylene, and optionally each of:
a process solvent,
one or more a-olefins,
hydrogen and
a second catalyst system,
to produce a third exit stream containing a final polyethylene product;
passing the third exit stream to a devolatilization system to recover the
final
polyethylene product; wherein
the first reactor is operated at lower temperature than the second reactor;
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the first catalyst system is a single site catalyst system; and
if injected into the third reactor, the second catalyst system is a single
site
catalyst system or a Ziegler-Natta catalyst system.
An embodiment of the disclosure is a continuous solution polymerization
process comprising:
injecting ethylene, a process solvent, a first catalyst system, optionally one
or
more a-olefins and optionally hydrogen into each of a first reactor and a
second
reactor configured in parallel to each other to produce a first exit stream
containing a
first polyethylene made in the first reactor and a second exit stream
containing a
second polyethylene made in the second reactor;
passing the first exit stream into a third reactor and injecting into the
third
reactor, ethylene, and optionally each of:
a process solvent,
one or more a-olefins,
hydrogen and
a second catalyst system,
to produce a third exit stream;
combining the second exit stream with the third exit stream to produce a final
product stream containing a final polyethylene product;
passing the final product stream to a devolatilization system to recover the
final
polyethylene product; wherein
the first reactor is operated at lower temperature than the second reactor;
the first catalyst system is a single site catalyst system; and
if injected into the third reactor, the second catalyst system is a single
site
catalyst system or a Ziegler-Natta catalyst system.
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An embodiment of the disclosure is a continuous solution polymerization
process comprising:
injecting ethylene, a process solvent, a first catalyst system, optionally one
or
more a-olefins and optionally hydrogen into each of a first reactor and a
second
reactor configured in parallel to each other to produce a first exit stream
containing a
first polyethylene made in the first reactor and a second exit stream
containing a
second polyethylene made in the second reactor;
passing the second exit stream into a third reactor and injecting into the
third
reactor, ethylene, and optionally each of:
a process solvent,
one or more a-olefins,
hydrogen and
a second catalyst system,
to produce a third exit stream;
combining the first exit stream with the third exit stream to produce a final
product stream containing a final polyethylene product;
passing the final product stream to a devolatilization system to recover the
final
polyethylene product; wherein
the first reactor is operated at lower temperature than the second reactor;
the first catalyst system is a single site catalyst system; and
if injected into the third reactor, the second catalyst system is a single
site
catalyst system or a Ziegler-Natta catalyst system.
In an embodiment of the disclosure, a first catalyst system is a single site
catalyst system comprising:
a) a phosphinimine complex defined by the formula
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(1.-A)aM (PI)b(Q)n
wherein LA is selected from the group consisting of unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; M is a
metal selected from titanium, hafnium and zirconium; PI is a phosphinimine
ligand; and Q is independently selected from the group consisting of a
hydrogen atom, a halogen atom, a Cm hydrocarbyl radical, a C1-18 alkoxy
radical and a C8-18 aryl oxide radical; wherein each of the hydrocarbyl,
alkoxy,
and aryl oxide radicals may be unsubstituted or further substituted by a
halogen
atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C8-18 aryl or aryloxy
radical,
an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl
radicals or a phosphido radical which is unsubstituted or substituted by up to
two C1-8 alkyl radicals; wherein a is 1; b is 1; n is 1 or 2; and (a+b+n) is
equivalent to the valence of the metal M;
b) an alkylaluminoxane co-catalyst;
c) an ionic activator, and;
d) optionally, a hindered phenol.
In an embodiment of the disclosure an alkylaluminoxane co-catalyst is
methylaluminoxane (MAO). =
In an embodiment of the disclosure an ionic activator is trityl tetrakis
(pentafluoro-phenyl) borate.
In an embodiment of the disclosure at least 10 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3.
In an embodiment of the disclosure at least 20 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3.
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In an embodiment of the disclosure at least 30 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3.
In an embodiment of the disclosure a first, second and third reactor operate
at
a temperature from about 80 C to about 300 C and a pressure from about 3 MPag
to
about 45 MPag.
In an embodiment of the disclosure a first reactor operates at a temperature
at
least 25 C lower than the temperature at which a second reactor operates.
In an embodiment of the disclosure a first reactor operates at a temperature
at
least 45 C lower than the temperature at which a second reactor operates.
In an embodiment of the disclosure a first reactor operates at a temperature
of
from about 10 C to about 100 C lower than the temperature at which a second
reactor
operates.
In an embodiment of the disclosure one or more a-olefins is fed exclusively to
the first reactor.
In an embodiment of the disclosure a second catalyst is fed to the third
reactor.
In an embodiment of the disclosure a first reactor and a second reactor are
continuously stirred tank reactors.
In an embodiment of the disclosure a first reactor and a second reactor are
loop reactors.
In an embodiment of the disclosure a first reactor and a second reactor are
independently a continuously stirred tank reactor or a loop reactor.
In an embodiment of the disclosure a third reactor is a tubular reactor.
In an embodiment of the disclosure a second catalyst system is a single site
catalyst system comprising:
a) a phosphinimine complex defined by the formula
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(LA)aM (PI)b(Q)n
wherein LA is selected from the group consisting of unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; M is a
metal selected from titanium, hafnium and zirconium; PI is a phosphinimine
ligand; and Q is independently selected from the group consisting of a
hydrogen atom, a halogen atom, a Ci-io hydrocarbyl radical, a Ci-io alkoxy
radical and a C5-10 aryl oxide radical; wherein each of the hydrocarbyl,
alkoxy,
and aryl oxide radicals may be unsubstituted or further substituted by a
halogen
atom, a C1-18 alkyl radical, a C1-5 alkoxy radical, a C6-10 aryl or aryloxy
radical,
an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl
radicals or a phosphido radical which is unsubstituted or substituted by up to
two C1-5 alkyl radicals; wherein a is 1; b is 1; n is 1 or 2; and (a+b+n) is
equivalent to the valence of the metal M;
b) an alkylaluminoxane co-catalyst;
c) an ionic activator, and;
d) optionally, a hindered phenol.
In an embodiment of the disclosure a second catalyst system is a Ziegler-Natta
.. catalyst system.
In an embodiment of the disclosure a process solvent is one or more C5 to C12
alkanes.
In an embodiment of the disclosure one or more a-olefins are selected from C3
to Cio a-olefins.
In an embodiment of the disclosure one or more a-olefins are selected from 1-
hexene or 1-octene or a mixture of 1-hexene and 1-octene.
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In an embodiment of the disclosure a first exit stream and a second exit
stream
are combined upstream at a third reactor.
Brief Description of Figures
Figures 1-3 are presented for the purpose of illustrating selected embodiments
of this disclosure; it being understood, that the embodiments in this
disclosure are not
limited to the precise arrangement of, or the number of, vessels shown.
Figure 1. Figure 1 illustrates a continuous solution polymerization process
where a first and second polymerization reactor are configured in parallel to
one
another and are upstream of a third reactor which receives a combined effluent
from
both the first and the second reactors.
Figure 2. Figure 2 illustrates a continuous solution polymerization process
where a first and second, polymerization reactor are configured in parallel to
one
another and a third reactor receives effluent from the first reactor.
Figure 3. Figure 3 illustrates a continuous solution polymerization process
where a first and second polymerization reactor are configured in parallel and
a third
reactor receives effluent from the second reactor.
Figure 4A shows the gel permeation chromatographs with Fourier transform
infra-red (GPC-FTIR) detection obtained for polyethylene product compositions
made
according to the present disclosure. The comonomer content, shown as the
number
of short chain branches per 1000 carbons (y-axis), is given relative to the
copolymer
molecular weight (x-axis). The upwardly sloping 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 iri the Figure, the number of short chain branches
increases at
higher molecular weights, and hence the comonomer incorporation is said to be
"reversed" or "partially reversed" with a peak or maximum present for
Inventive
Examples 2, 4 and 5.
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Figure 4B shows the gel permeation chromatographs with Fourier transform
infra-red (GPC-FTIR) detection obtained for comparative polyethylene product
compositions.
Figure 5A shows the temperature rising elution fractionation (TREF) analysis
and profile of polyethylene product compositions made according to the present
disclosure.
Figure 5B shows the temperature rising elution fractionation (TREF) analysis
and profile of comparative polyethylene product compositions.
Figure 6A shows the differential scanning calorimetry analysis (DSC) and
profile of polyethylene product compositions made according to the present
disclosure.
Figure 6B shows the differential scanning calorimetry analysis (DSC) and
profile of comparative polyethylene product compositions.
Figure 7A shows the hot tack profiles for the films made using the
polyethylene
product compositions made according to the present invention.
Figure 7B shows the hot tack profiles for the films made using the comparative
polyethylene product compositions.
Figure 8A shows the cold seal profiles for the films made using the
polyethylene product compositions made according to the present invention.
Figure 8B shows the cold seal profiles for the films made using the
comparative
polyethylene product compositions.
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
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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 amounts of the components
actually used
will conform to the maximum of 100 percent.
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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.
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The term "heterogeneous 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.
The term "homogeneous 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, phopshinimine catalysts, and
constrained geometry catalysts all of which are well known in the art.
Typically, homogeneous polyethylenes have narrow molecular weight
distributions, for example gel permeation chromatography (GPC) Mw/Mn values of
less
than 2.8, although exceptions may arise; Mw and Mn refer to weight and number
average molecular weights, respectively. In contrast, the Mw/Mn of
heterogeneous
ethylene polymers are typically greater than the Mw/Mn of homogeneous ethylene
polymers. In general, homogeneous ethylene polymers also have a narrow
comonomer distribution, i.e. each macromolecule within the molecular weight
distribution has a similar comonomer content. Frequently, the composition
distribution
breadth index "CDBI" is used to quantify how the comonomer is distributed
within an
ethylene polymer, as well as to differentiate ethylene polymers produced with
different
catalysts or processes. The "CDBI50" 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 CDBI50 of an ethylene interpolymer can be
calculated from TREF curves (Temperature Rising Elution Fractionation); the
TREF
method is described in Wild, et al., J. Polym. Sc., Part B, Polym. Phys., Vol.
20 (3),
pages 441-455. Typically the CDBI50 of homogeneous ethylene polymers are
greater
than about 70%. In contrast, the CDBI50 of a-olefin containing heterogeneous
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ethylene polymers are generally lower than the CD8150 of homogeneous ethylene
polymers.
It is well known to those skilled in the art, that homogeneous ethylene
polymers
are frequently further subdivided into "linear homogeneous ethylene polymers"
and
"substantially linear homogeneous 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 "homogeneous
polyethylene" 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 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,
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=
branched and cyclic hydrocarbons containing at least one carbon-carbon double
bond
that is deficient by one hydrogen radical.
As used herein, the term "aryl" group includes phenyl, naphthyl, pyridyl and
other radicals whose molecules have an aromatic ring structure; non-limiting
examples include naphthylene, phenanthrene and anthracene. An "arylalkyl"
group is
an alkyl group having an aryl group pendant there from; non-limiting examples
include
benzyl, phenethyl and tolylmethyl; an "alkylaryl" is an aryl group having one
or more
alkyl groups pendant there from; non-limiting examples include tolyl, xylyl,
mesityl and
cumyl.
As used herein, the phrase "heteroatom" includes any atom other than carbon
and hydrogen that can be bound to carbon. A "heteroatom-containing group" is a
hydrocarbon radical that contains a heteroatom and may contain one or more of
the
same or different heteroatoms. In one embodiment, a heteroatom-containing
group is
a hydrocarbyl group containing from 1 to 3 atoms selected from the group
consisting
of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and
sulfur.
Non-limiting examples of heteroatom-containing groups include radicals of
imines,
amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics,
oxazolines,
thioethers, and the like. The term "heterocyclic" refers to ring systems
having a
carbon backbone that comprise from 1 to 3 atoms selected from the group
consisting
of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and
sulfur.
As used herein the term "unsubstituted" means that hydrogen radicals are
bounded to the molecular group that follows the term unsubstituted. The term
"substituted" means that the group following this term possesses one or more
moieties
that have replaced one or more hydrogen radicals in any position within the
group;
non-limiting examples of moieties include halogen radicals (F, Cl, Br),
hydroxyl
groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups,
alkoxy
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groups, phenyl groups, naphthyl groups, Ci to C30 alkyl groups, C2 to C30
alkenyl
groups, and combinations thereof. Non-limiting examples of substituted alkyls
and
= aryls include: acyl radicals, alkylamino radicals, alkoxy radicals,
aryloxy radicals,
alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals,
aryloxycarbonyl
radicals, carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy
radicals,
acylamino radicals, arylamino radicals and combinations thereof.
Herein the term "R1" refers to a first reactor in a continuous solution
polymerization process; it being understood that R1 is distinctly different
from the
symbol R1; the latter is used in chemical formula, e.g. representing a
hydrocarbyl
group. Similarly, the term "R2" refers to a second reactor, and; the term "R3"
refers to
a third reactor.
As used herein, the term "oligomers" refers to an ethylene polymer of low
molecular weight, e.g., an ethylene polymer with a weight average molecular
weight
(Mw) of about 2000 to 3000 daltons. Other commonly used terms for oligomers
include "wax" or "grease". As used herein, the term "light-end impurities"
refers to
chemical compounds with relatively low boiling points that may be present in
the
various vessels and process streams within a continuous solution
polymerization
process; non-limiting examples include, methane, ethane, propane, butane,
nitrogen,
CO2, chloroethane, HCI, etc.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Catalyst systems that are efficient in polymerizing olefins are well known in
the
art. In the embodiments disclosed herein, at least one catalyst system is
employed in
a continuous solution polymerization process.
In embodiment of the disclosure a first catalyst system is a single site
catalyst
system and comprises at least one single-site catalyst that produces a
homogeneous
ethylene polymer.
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The catalyst components which make up the single site catalyst system are not
particularly limited, i.e. a wide variety of catalyst components can be used.
In one non-limiting embodiment of the disclosure, a single site catalyst
system
comprises the following three or four components: a phosphinimine metal
complex; an
alkylaluminoxane co-catalyst; an ionic activator and optionally a hindered
phenol.
In an embodiment of the disclosure, and as shown in Table 1, the term
"component (a)" refers to a phosphinimine metal complex, the term "component
(b)"
refers to an alkylaluminoxane co-catalyst, the term "component (c)" refers to
an ionic
activator, and; the term "component (d)" refers to an optional hindered
phenol.
In an embodiment of the disclosure, non-limiting examples of component (a)
are represented by formula:
(LA)aM(PI)b(Q)n
wherein (LA) represents is cyclopentadienyl type ligand; M represents a metal
atom; PI
represents a phosphinimine ligand; Q represents an activatable ligand; a is 0
or 1; b is
1 or 2; (a+b) = 2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of
the metal
M.
As used herein, the term "cyclopentadienyl-type" ligand is meant to include
ligands which contain at least one five-carbon ring which is bonded to the
metal via
eta-5 (or in some cases eta-3) bonding. Thus, the term "cyclopentadienyl-type"
includes, for example, unsubstituted cyclopentadienyl, singly or multiply
substituted
cyclopentadienyl, unsubstituted indenyl, singly or multiply substituted
indenyl,
unsubstituted fluorenyl and singly or multiply substituted fluorenyl.
Hydrogenated
versions of indenyl and fluorenyl ligands are also contemplated for use in the
current
disclosure, so long as the five-carbon ring which bonds to the metal via eta-5
(or in
some cases eta-3) bonding remains intact. Substituents for a cyclopentadienyl
ligand,
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an indenyl ligand (or hydrogenated version thereof) and a fluorenyl ligand (or
hydrogenated version thereof) may be selected from the group consisting of a
C1-30
hydrocarbyl radical (which hydrocarbyl radical may be unsubstituted or further
substituted by for example a halide and/or a hydrocarbyl group; for example a
suitable
substituted C1-30 hydrocarbyl radical is a pentafluorobenzyl group such as
¨CH2C6F5);
a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical (each
of which
may be further substituted by for example a halide and/or a hydrocarbyl
group); an
amido radical which is unsubstituted or substituted by up to two C1-8 alkyl
radicals; a
phosphido radical which is unsubstituted or substituted by up to two C1-8
alkyl radicals;
a silyl radical of the formula -Si(R')3 wherein each R is independently
selected from
the group consisting of hydrogen, a Ci-a alkyl or alkoxy radical, C6-10 aryl
or aryloxy
radicals; and a germanyl radical of the formula -Ge(R')3 wherein R' is as
defined
directly above.
Non-limiting examples of metal M in the phosphinimine metal complex include
Group 4 metals, titanium, zirconium and hafnium.
The phosphinimine ligand, PI, is defined by formula:
(RP)3 P = N -
wherein the RP groups are independently selected from: a hydrogen atom; a
halogen
atom; C1-20 hydrocarbyl radicals which are unsubstituted or substituted with
one or
more halogen atom(s); a C1-8 alkoxy radical; a C6-10 aryl radical; a C6-10
aryloxy radical;
an amido radical; a silyl radical of formula -Si(Rs)3, wherein the Rs groups
are
independently selected from, a hydrogen atom, a C1-8 alkyl or alkoxy radical,
a C6-10
aryl radical, a C6-10 aryloxy radical, or a germanyl radical of formula -
Ge(RG)3, wherein
the RG groups are defined as RS is defined in this paragraph.
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
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metal center M by suitable acidic or electrophilic catalyst activator
compounds (also
known as "co-catalyst" compounds) respectively, examples of which are
described
below. The activatable ligand 0 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.
In embodiments of the present disclosure, the activatable ligand, 0 is
independently selected from the group consisting of a hydrogen atom; a halogen
atom, a Ci-lo hydrocarbyl radical; a Ci-io 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 Ci-
e alkyl; a
C1-8 alkoxy; a C6-10 aryl or aryloxy; an amido or a phosphido radical, but
where 0 is not
a cyclopentadienyl. Two Q ligands may also be joined to one another and form
for
example, a substituted or unsubstituted diene ligand (i.e. 1,3-butadiene); or
a
delocalized heteroatom containing group such as an acetate or acetamidinate
group.
In a convenient embodiment of the disclosure, each X is independently selected
from
the group consisting of a halide atom, a C1-4 alkyl radical and a benzyl
radical.
Particularly suitable activatable ligands 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 component (b), is
an alkylaluminoxane co-catalyst. Although the exact structure of this co-
catalyst is
uncertain, subject matter experts generally agree that it is an oligomeric
species that
contain repeating units of the general formula:
(R)2A10-(Al(R)-0)n-Al(R)2
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where the R groups may be the same or different linear, branched or cyclic
hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about
50. A
non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO)
wherein
each R group is a methyl radical.
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 catalyst activator 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 activator is
often used
in combination with activatable ligands such as halogens.
In an embodiment of the disclosure, component (c) of the single site catalyst
system is an ionic activator. In general, ionic activators are comprised of a
cation and
a bulky anion; wherein the latter is substantially non-coordinating. Non-
limiting
examples of ionic activators are boron ionic activators that are four
coordinate with
four ligands bonded to the boron atom. Non-limiting examples of boron ionic
activators include the following formulas 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 sily1 radical of formula -Si(R9)3, where each R9 is independently
selected from
hydrogen atoms and C1-4 alkyl radicals, and
[(R9)tZHNB(R7)4]-
=
19
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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(perfluorophenyl)boron with anilinium and trityl
(or
triphenylmethylium). Additional non-limiting examples of ionic activators
include:
triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron,
tri(n-
butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,
trimethylammoniurn 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,
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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.
The optional fourth catalyst component of the single site catalyst system is a
= hindered phenol, component (d). 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, (a) through (d) are optimized as described
further
below.
In an embodiment of the disclosure a second catalyst system is a single site
catalyst system as described above or a Ziegler-Natta catalyst as described
below.
= Ziegler-Natta catalyst systems are well known to those skilled in the
art.
In this disclosure, a second catalyst system 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
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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 polyethylene. 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 (component (e)) is reacted with a solution of a chloride compound
(component (f)) to form a magnesium chloride support suspended in solution.
Non-
limiting examples of magnesium compounds include Mg(R1)2; wherein the R1
groups
22
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may be the same or different, linear, branched or cyclic hydrocarbyl radicals
containing 1 to 10 carbon atoms. Non-limiting examples of chloride compounds
include R2CI; wherein R2 represents a hydrogen atom, or a linear, branched or
cyclic
hydrocarbyl radical containing 1 to 10 carbon atoms. In the first step, the
solution of
magnesium compound may also contain an aluminum alkyl (component (g)). 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
carbon atoms. In the second step a solution of the metal compound (component
(h)) is added to the solution of magnesium chloride and the metal compound is
10 supported on the magnesium chloride. Non-limiting examples of suitable
metal
compounds include M(X)nor MO(X)n; where M represents a metal selected from
Group 4 through Group 8 of the Periodic Table, or mixtures of metals selected
from
Group 4 through Group 8; 0 represents oxygen, and; X represents chloride or
bromide; n is an integer from 3 to 6 that satisfies the oxidation state of the
metal.
.. Additional non-limiting examples of suitable metal compounds include Group
4 to
Group 8 metal alkyls, metal alkoxides (which may be prepared by reacting a
metal
alkyl with an alcohol) and mixed-ligand metal compounds that contain a mixture
of
halide, alkyl and alkoxide ligands. In the third step a solution of an alkyl
aluminum co-
catalyst (component (i)) 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(OR9)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
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CA 2964563 2017-04-19
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 05 to 012 alkanes
or
mixtures thereof.
To produce an active Ziegler-Natta catalyst system the quantity and mole
ratios
of the components, (e) through (i) are optimized as described further below.
Embodiments of the solution polymerization process of the present disclosure
are shown in Figures 1-3.
Referring to Figure 1, 2 and 3 process solvent is injected into two parallel
reactors, reactor 1 "R1" and reactor 2 "R2" via streams A and B and into the
third
reactor, reactor 3 "R3" via stream C. Ethylene is injected into reactors 1, 2
and 3 via
streams D, E and F respectively. Optional a-olefin is injected into reactors
1, 2 and 3
via streams G, H, and I respectively. As shown in Figures 1-3, the process
solvent,
ethylene and optional a-olefin feed streams are combined to form reactor feed
streams J, K and L that feed reactors 1, 2 and 3, respectively. Optional
hydrogen is
injected into reactors 1, 2 and 3 via streams M, N and 0 respectively.
A single site catalyst system (the first catalyst system) is injected into
reactors 1
and 2 via streams P and Q respectively. When an a-olefin is injected into
reactors 1
and/or 2, a first and/or second ethylene copolymer are produced in reactors 1
and 2,
respectively. If an a-olefin is not added, then ethylene homopolymers are
formed.
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In an embodiment of the disclosure, an a-olefin is injected into reactor 1 but
not
into reactor 2, so that a first polyethylene made in reactor 1 is an ethylene
copolymer
and a second polyethylene made in reactor 2 is an ethylene homopolymer.
Catalyst streams R and S contain an ionic activator dissolved in a catalyst
component solvent. Catalyst streams T and U contain an organometallic complex,
such as a phosphinimine complex, dissolved in a catalyst component solvent.
Catalyst streams V and W contain an alkylaluminoxane co-catalyst dissolved in
a
catalyst component solvent. Optional catalyst streams X and Y contain a
hindered
phenol dissolved in a catalyst component solvent. Catalyst component solvents
for
the various catalyst components may be the same or different.
Optionally a second catalyst system is injected into reactor 3. The second
catalyst system may be a single site catalyst or a Ziegler-Natta catalyst.
In an embodiment a single site catalyst is injected into reactor 3. Hence in
an
embodiment of the disclosure, catalyst stream Z contains an ionic activator
dissolved
in a catalyst component solvent; catalyst stream AA contains an organometallic
complex, such as a phosphinimine complex, dissolved in a catalyst component
solvent; catalyst stream BB contains an alkylaluminoxane co-catalyst dissolved
in a
catalyst component solvent; and optional catalyst stream CC contains a
hindered
phenol dissolved in a catalyst component solvent. Catalyst component solvents
for
.. the various catalyst components may be the same or different.
In an embodiment a Ziegler-Natta catalyst is injected into reactor 3. The
Ziegler-Natta catalyst may be prepared in line as discussed above and fed to
reactor 3
(not shown in the Figures), or the Zielger-Natta catalyst may be prepared in
batch
mode, stored in a holding tank and activated before entering reactor 3, or on
route to
reactor 3 as discussed above (not shown in the Figures).
HACIMCBS pec \ 201 6028Canada.docx
In an embodiment of the continuous solution polymerization process shown in
Figure 1, reactor 1 produces exit stream 1' and reactor 2 produces exit stream
2'. Exit
streams 1' and 2' are then combined on route to Reactor 3. A third ethylene
copolymer is produced in reactor 3. Reactor 3 produces an exit stream 3'
containing a
final polyethylene product.
In an embodiment of the continuous solution polymerization process shown in
Figure 1, reactor 3 produces exit stream 3' containing a final polyethylene
product.
Downstream of reactor 3, a catalyst deactivator is added via catalyst
deactivator tank
T2 forming deactivated stream which is then fed via a pressure let down
device, 100
to a devolatilization system. The devolatilization system comprises a
vapour/liquid
("V/L") separator 103 (or alternatively a liquid/liquid separator, not shown),
downstream of a heat exchanger, 101 and a second pressure let-down device 102.
Two streams are formed in V/L separator 103 (or alternatively a liquid/liquid
separator); bottom stream 104 containing an ethylene polymer rich solution and
gaseous overhead stream 115. Optionally, bottom stream 104 enters a second V/L
separator 105 (or alternatively a liquid/liquid separator, not shown) and two
streams
are formed; bottom stream 106 and gaseous overhead stream 117. Optionally,
bottom stream 106 enters a third V/L separator 107 (or alternatively a
liquid/liquid
separator, not shown) and two streams are formed; product stream 108 and
gaseous
overhead stream 109.
Product stream 108 proceeds to polymer recovery. Gaseous overhead
streams 115, 117 and 109 are sent to a distillation column where solvent,
ethylene
and optional a-olefin are separated and recycled to the solution
polymerization
process.
Another embodiment of the continuous solution polymerization process is
shown in Figure 2. All feed and exit streams are labelled analogously to that
26
Date Recue/Date Received 2023-08-09
discussed above with respect to Figure 1. In an embodiment of the continuous
solution polymerization process shown in Figure 2, reactor 1 produces exit
stream 1'
which flows into reactor 3. Reactor 3 then produces an exit stream 3'. Reactor
2
produces an exit stream 2' which is combined with the exit stream 3' to
produce a final
product stream containing a final polyethylene product. The final product
stream is
deactivated by adding catalyst deactivator from catalyst deactivator tank T2
forming a
deactivated stream. The deactivated stream is then fed via a pressure let down
device, 100 to a devolatilization system. The devolatilization system
comprises a
vapour/liquid ("V/L") separator 103 (or alternatively a liquid/liquid
separator, not
shown), a downstream heat exchanger, 101 and a second pressure let-down device
102. Two streams are formed in V/L separator 103 (or alternatively a
liquid/liquid
separator); bottom stream 104 containing an ethylene polymer rich solution and
gaseous overhead stream 115. Optionally, bottom stream 104 enters a second V/L
separator 105 (or alternatively a liquid/liquid separator, not shown) and two
streams
are formed; bottom stream 106 and gaseous overhead stream 117. Optionally,
bottom stream 106 enters a third V/L separator 107 (or alternatively a
liquid/liquid
separator, not shown) and two streams are formed; product stream 108 and
gaseous
overhead stream 109. Product stream 108 proceeds to polymer recovery. Gaseous
overhead streams 115, 117 and 109 are sent to a distillation column where
solvent,
ethylene and optional a-olefin are separated and recycled to the solution
polymerization process.
Another embodiment of the continuous solution polymerization process is
shown in Figure 3. All feed and exit streams are labelled analogously to that
discussed above with respect to Figure 1. In an embodiment of the continuous
solution polymerization process shown in Figure 3, reactor 2 produces exit
stream 2'
which flows into reactor 3. Reactor 3 then produces an exit stream 3'. Reactor
1
27
Date Recue/Date Received 2023-08-09
produces an exit stream 1' which is combined with the exit stream 3' to
produce a final
product stream containing a final polyethylene product. The final product
stream is
deactivated by adding catalyst deactivator from catalyst deactivator tank T2
forming a
deactivated stream. The deactivated stream is then fed via a pressure let down
.. device, 100 to a devolatilization system. The devolatilization system
comprises a
vapour/liquid ("V/L") separator 103 (or alternatively a liquid/liquid
separator, not
shown), a downstream heat exchanger, 101 and a second pressure let-down device
102. Two streams are formed in V/L separator 103 (or alternatively a
liquid/liquid
separator); bottom stream 104 containing an ethylene polymer rich solution and
gaseous overhead stream 115. Optionally, bottom stream 104 enters a second V/L
separator 105 (or alternatively a liquid/liquid separator, not shown) and two
streams
are formed; bottom stream 106 and gaseous overhead stream 117. Optionally,
bottom stream 106 enters a third V/L separator 107 (or alternatively a
liquid/liquid
separator, not shown) and two streams are formed; product stream 108 and
gaseous
overhead stream 109. Product stream 108 proceeds to polymer recovery. Gaseous
overhead streams 115, 117 and 109 are sent to a distillation column where
solvent,
ethylene and optional a-olefin are separated and recycled to the solution
polymerization process.
With reference to Figures 1-3, catalyst deactivator tank T2 may contain neat
(100%) catalyst deactivator, a solution of catalyst deactivator in a solvent,
or a slurry
of catalyst deactivator in a solvent. Non-limiting examples of suitable
solvents include
linear or branched C5 to C12 alkanes. In this disclosure, how the catalyst
deactivator is
added is not particularly important. Once added, the catalyst deactivator
substantially
stops the polymerization reaction by changing active catalyst species to
inactive
forms. Suitable deactivators are well known in the art, non-limiting examples
include:
amines (e.g. U.S. Pat. No. 4,803,259 to Zboril et al.); alkali or alkaline
earth metal
28
Date Recue/Date Received 2023-08-09
CA 2964563 2017-04-19
salts of carboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.);
water (e.g.
U.S. Pat. No. 4,731,438 to Bernier et al.); hydrotalcites, alcohols and
carboxylic acids
(e.g. U.S. Pat. No. 4,379,882 to Miyata); or a combination thereof (U.S. Pat
No.
6,180,730 to Sibtain et al.).
In an embodiment of the disclosure, a pass ivating agent may be added to the
final product stream downstream of the heat exchange 101, but upstream of the
pressure let-down device 102 (not shown in Figures 1-3). Without wishing to be
bound by any single theory, passification helps to reduce chloride levels in
the final
polyethylene product. The addition of passivators may be particularly useful
when a
Ziegler-Natta catalyst system is fed to reactor 3. The passivator may be added
in a
solvent, or as a slurry of passivator in a solvent. Non-limiting examples of
suitable
solvents include linear or branched C5 to C12 alkanes. In this disclosure, how
a
passivator is added is not particularly important. Suitable passivators are
well known
in the art, non-limiting examples include alkali or alkaline earth metal salts
of
carboxylic acids or hydrotalcites. The quantity of passivator added can vary
over a
wide range.
In an embodiment of the continuous solution polymerization process the first
and second reactors are continuously stirred tanks reactors (CSTRs).
In an embodiment of the continuous solution polymerization process the third
reactor is a tubular reactor.
In an embodiment of the continuous solution polymerization process described
herein ethylene is added to each of reactors 1, 2 and 3.
In an embodiment of the continuous solution polymerization process described
herein a single site catalyst system is added to each of the first and second
reactors,
but not to the third reactor.
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In an embodiment of the continuous solution polymerization process described
herein a single site catalyst system is added to each of the first, second and
third
reactors.
In an embodiment of the continuous solution polymerization process described
.. herein a single site catalyst system comprises a phosphinimine complex.
Referring to the embodiments shown in Figures 1, 2 and 3; an active single
site
catalyst system is produced by optimizing the proportion of each of the four
single site
catalyst components, (a) through (d) as defined above. The term "active" means
the
single site catalyst system is very efficient in converting olefins to
polyolefins; in
practice the optimization objective is to maximize the following ratio:
(pounds of
ethylene interpolymer product produced)/(pounds of catalyst consumed). The
quantity
of the phosphinimine complex, component (a), added to reactors 1 and 2 is
expressed
as the parts per million (ppm) of component (a) in the total mass of the
solutions in
reactors 1 and 2; which may be referred to hereafter as "R1(a) (ppm)" or
"R2(a)
.. (ppm)". The upper limit on R1 (a) (ppm) or R2(a) (ppm) may be about 5, in
some
cases about 3 and is other cases about 2. The lower limit in R1 (a) (ppm) and
R2(a)
(ppm) may be about 0.02, in some cases about 0.05 and in other cases about
0.1.
The proportion of catalyst component (c), the ionic activator, added to R1 and
R2 is optimized by controlling the (ionic activator)/(phosphinimine complex)
molar ratio
in R1 and R2 solution; hereafter "R1(c)/(a)" and "R2(c)/(a)". The upper limit
on R1 and
R2 (c)/(a) may be about 10, in some cases about 5 and in other cases about 2.
The
lower limit on R1(c)/(a) and R2 (c)/(a) may be about 0.1, in some cases about
0.5 and
in other cases about 1Ø
The proportion of catalyst component (b), the alkylaluminoxane is optimized by
controlling the (Al from alkylaluminoxane)/(phosphinimine complex) molar ratio
in R1
and R2 solution; hereafter "R1(b)/(a)" and "R2(b)/(a)". The alkylaluminoxane
co-
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catalyst is generally added in a molar excess relative to the bulky ligand-
metal
complex. The upper limit on R1(b)/(a) and R2(b)/(a) may be about 1000, in some
cases about 500 and is other cases about 200. The lower limit on R1(b)/(a) and
R2(b)/(a) may be about 1, in some cases about 10 and in other cases about 30.
The addition of catalyst component (d), the hindered phenol, to R1 and R2 is
optional in the embodiments shown in Figures 1-3. If added, the proportion of
component (d) is optimized by controlling the (hindered phenol)/(Al from
alkylaluminoxane) molar ratio in R1 and R2; hereafter "R1(d)/(b)" and
"R2(d)/(b)" .
The upper limit on R1 (d)/(b) and R2 (d)/(b) may be about 10, in some cases
about 5
and in other cases about 2. The lower limit on R1 (d)/(b) and R2 (d)/(b) may
be 0.0, in
some cases about 0.1 and in other cases about 0.2.
If a single site catalyst is feed to reactor 3, then the phosphinimine complex
(a),
the ionic activator (c), the alkylaluminoxane (b) and optional, hindered
phenol (d), are
optimized as already described for reactors 1 and 2. Namely, the following are
controlled.
The quantity of phosphinimine complex, component (a) added to reactor 3 as
expressed as the parts per million (ppm) of component (a) in the total mass of
the
solutions in reactor 3, which may be referred to hereafter as "R3(a) (ppm)";
the upper
limit on R3(a) (ppm) may be about 5, in some cases about 3 and is other cases
about
2. The lower limit in R3 (a) (ppm) and R2(a) (ppm) may be about 0.02, in some
cases
about 0.05 and in other cases about 0.1.
The proportion of catalyst component (c), the ionic activator, added to R3 is
optimized by controlling the (ionic activator)/(phosphinimine complex) molar
ratio in
R3; hereafter "R3(c)/(a)". The upper limit on R3(c)/(a) may be about 10, in
some
cases about 5 and in other cases about 2. The lower limit on R3(c)/(a) may be
about
0.1, in some cases about 0.5 and in other cases about 1Ø
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The proportion of catalyst component (b), the alkylaluminoxane is optimized by
controlling the (Al from alkylaluminoxane)/(phosphinimine complex) molar ratio
in R3
solution; hereafter "R3(b)/(a)". The alkylaluminoxane co-catalyst is generally
added in
a molar excess relative to the bulky ligand-metal complex. The upper limit on
R3(b)/(a) may be about 1000, in some cases about 500 and is other cases about
200.
The lower limit on R3(b)I(a) may be about 1, in some cases about 10 and in
other
cases about 30.
The addition of catalyst component (d), the hindered phenol, to R3 is optional
in
the embodiments shown in Figures 1-3. If added, the proportion of component
(d) is
optimized by controlling the (hindered phenol)/(AI from alkylaluminoxane)
molar ratio
in R3; hereafter "R3(d)/(b)". The upper limit on R3(d)/(b) may be about 10, in
some
cases about 5 and in other cases about 2. The lower limit on R3(d)/(b) may be
0.0, in
some cases about 0.1 and in other cases about 0.2.
Any combination of the single site catalyst component streams in Figures 1-3
may, or may not, be heated or cooled. The upper limit on catalyst component
stream
temperatures may be about 70 C; in other cases about 60 C and in still other
cases
about 50 C. The lower limit on catalyst component stream temperatures may be
about 0 C; in other cases about 20 C and in still other cases about 40 C.
For more information on the optimization of a single site catalyst for use
with a
continuous polymerization process see U.S. Pat. Appl. No. 2016/0108221A1.
Referring to the embodiments shown in Figures 1, 2 and 3; a Ziegler-Natta
catalyst system is produced by optimizing the proportion of each of the five
Ziegler-
Natta catalyst components, (e) through (i) as defined above.
An efficient in-line Ziegler-Natta catalyst system may be found by optimizing
the
following molar ratios: (aluminum alkyl)/(magnesium compound) or (g)/(e);
(chloride
compound)/(magnesium compound) or (f)/(e); (alkyl aluminum co-catalyst)/(metal
32
Date Recue/Date Received 2023-08-09
compound) or (i)/(h), and; (aluminum alkyl)/(metal compound) or (g)I(h); as
well as the
time these compounds have to react and equilibrate. The upper limit on the
(aluminum alkyl)/(magnesium compound) molar ratio may be about 70, in some
cases
about 50 and is other cases about 30. The lower limit on the (aluminum
.. alkyl)/(magnesium compound) molar ratio may be about 3.0, in some cases
about 5.0
and in other cases about 10. The upper limit on the (chloride
compound)/(magnesium compound) molar ratio may be about 4, in some cases about
3.5 and is other cases about 3Ø The lower limit on the (chloride
compound)/(magnesium compound) molar ratio may be about 1.0, in some cases
.. about 1.5 and in other cases about 1.9. The upper limit on the (alkyl
aluminum co-
catalyst)/(metal compound) molar ratio may be about 10, in some cases about
7.5 and
is other cases about 6Ø The lower limit on the (alkyl aluminum co-
catalyst)/(metal
compound) molar ratio may be 0, in some cases about 1.0 and in other cases
about
2Ø
For more information on the optimization of an in-line Ziegler-Natta catalyst
system and the use of a batch Ziegler-Natta catalyst system for use with a
continuous
polymerization process see U.S. Pat. Appl. No. 2016/0108221A1.
In the continuous solution processes embodiments shown in Figures 1, 2 and 3
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,
33
Date Recue/Date Received 2023-08-09
CA 2964563 2017-04-19
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.
It is well known to individuals experienced in the art that reactor feed
streams
(solvent, monomer, a-olefin, hydrogen, catalyst system etc.) must be
essentially free
of catalyst deactivating poisons; non-limiting examples of poisons include
trace
amounts of oxygenates such as water, fatty acids, alcohols, ketones and
aldehydes.
Such poisons are removed from reactor feed streams using standard purification
practices; non-limiting examples include molecular sieve beds, alumina beds
and
oxygen removal catalysts for the purification of solvents, ethylene and a-
olefins, etc.
Referring to the first and second reactors in Figures 1, 2 and 3 any
combination
of the reactor 1 or 2 feed streams may be heated or cooled. The upper limit on
reactor feed stream temperatures may be about 90 C; in other cases about 80 C
and
in still other cases about 70 C. The lower limit on reactor feed stream
temperatures
may be about -20 C; in other cases about 0 C, in other cases about 10 C and in
still
other cases about 20 C. Any combination of the streams feeding reactor 3 may
be
heated or cooled. In some cases, reactor 3 reactor feed streams are tempered,
i.e.
the reactor 3 feed streams are heated to at least above ambient temperature.
The
upper temperature limit on the reactor 3 feed streams in some cases are about
200 C,
in other cases about 170 C and in still other cases about 140 C; the lower
34
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temperature limit on the tubular reactor feed streams in some cases are about
40 C,
in other cases about 60 C, in other cases about 90 C and in still other cases
about
120 C; with the proviso that the temperature of the reactor 3 feed streams are
lower
than the temperature of the process stream that enters reactor 3.
In the embodiments shown in Figures 1-3 the operating temperatures of the
solution polymerization reactors, reactors 1, 2 and 3 can vary over a wide
range. For
example, the upper limit on reactor temperatures in some cases may be about
300 C,
in other cases about 280 C and in still other cases about 260 C; and the lower
limit in
some cases may be about 80 C, in other cases about 100 C and in still other
cases
about 125 C.
In an embodiment of the disclosure, the first reactor is operated at a lower
temperature than the second reactor.
The maximum temperature difference between these two reactors, T2 ¨ T1,
where "T2" is the R2 operation temperature and "T" is the R1 operation
temperature,
in some cases is about 120 C, in other cases about 100 C and in still other
cases
about 80 C; the minimum T2¨ T1 temp in some cases is about 1 C, in other cases
about 5 C and in still other cases about 10 C.
In an embodiment of the disclosure, the first reactor operates at a
temperature,
T1 which is at least 25 C lower than the temperature at which the second
reactor
operates, T2.
In an embodiment of the disclosure, the first reactor operates at a
temperature,
T1 which is at least 35 C lower than the temperature at which the second
reactor
operates, T2.
In an embodiment of the disclosure, the first reactor operates at a
temperature,
T1 which is at least 45 C lower than the temperature at which the second
reactor
operates, 12.
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In an embodiment of the disclosure, the first reactor operates at a
temperature,
T1 which is at least 55 C lower than the temperature at which the second
reactor
operates, T2.
In an embodiment of the disclosure, the first reactor operates at a
temperature,
T1 of from 10 to 100 C lower than the temperature at which the second reactor
operates, T2.
In an embodiment of the disclosure, the first reactor operates at a
temperature
T1 of from about 125 C to about 155 C and the second reactor operates at a
temperature T2 of from about 185 C to about 205 C.
In an embodiment of the present disclosure, the third reactor operates at a
temperature T3 which is higher than the temperature at which the first reactor
operates, T1.
In an embodiment of the present disclosure, the third reactor operates at a
temperature T3 which is higher than the temperature at which the first and
second
reactors operate, T1 and T2 respectively.
In an embodiment of the present disclosure, the third reactor operates at a
temperature T3 which is higher than the weighted average of the operating
temperatures at which the first and second reactors operate.
In an embodiment of the present disclosure, the third reactor operates at a
temperature T3 which is higher than the inlet temperature of the third
reactor.
In an embodiment of the present disclosure, and with reference to Figure 1,
the
third reactor operates at a temperature T3 which is higher than the
temperature of the
combined reactor 1 and 2 exit streams 1' and 2' respectively.
In an embodiment of the present disclosure, and with reference to Figure 1,
the
third reactor operates at a temperature T3 which is higher than the weighted
average
temperature of the combined reactor 1 and 2 exit streams 1' and 2'
respectively.
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In embodiments of the disclosure, the third reactor may be operated at, at
least
about 100 C higher than reactor 1; in other cases at least about 60 C higher
than
reactor 1, in still other cases at least about 30 C higher than reactor 1.
In embodiments of the disclosure, the third reactor may be operated at, at
least
about 60 C higher than reactor 2; in other cases at least about 30 C higher
than
reactor 2, in still other cases at least about 10 C higher than reactor 2, in
alternative
cases 0 C higher, i.e. the same temperature as reactor 2.
In an embodiment of the disclosure, the first reactor operates at a
temperature
= of from about 115 C to about 155 C and the second reactor operates at a
temperature
of from about 190 C to about 205 C.
The temperature within reactor 3 may increase along its length. The maximum
temperature difference between the inlet and outlet of R3 in some cases is
about
100 C, in other cases about 60 C and in still other cases about 40 C. The
minimum
= temperature difference between the inlet and outlet of R3 is in some
cases may be
0 C, in other cases about 3 C and in still other cases about 10 C. In some
cases R3
is operated an adiabatic fashion and in other cases R3 is heated.
The pressure in the polymerization reactors should be high enough to maintain
the polymerization solution as a single phase solution and to provide the
upstream
pressure to force the polymer solution from the reactors through a heat
exchanger and
on to polymer recovery operations. Referring to the embodiments shown in
Figures 1,
2 and 3, the operating pressure of the solution polymerization reactors can
vary over a
wide range. For example, the upper limit on reactor pressure in some cases may
be
about 45 MPag, in other cases about 30 MPag and in still other cases about 20
MPag;
and the lower limit in some cases may be about 3 MPag, in other some cases
about 5
MPag and in still other cases about 7 MPag.
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In an embodiment of the disclosure, one or more of the solution polymerization
reactors can be operated at a pressure which is low enough for the one phase
polymer solution to phase separate into a two phase liquid/liquid polymer
solution.
The polyethylene product produced in the continuous solution polymerization
process may be recovered using conventional devolatilization systems that are
well
known to persons skilled in the art, non-limiting examples include flash
devolatilization
systems and devolatilizing extruders.
Referring to the embodiments shown in Figures 1-3, prior to entering the first
V/L separator, 103 the deactivated solution may have a maximum temperature in
some cases of about 300 C, in other cases about 290 C and in still other cases
about
280 C; the minimum temperature may be in some cases about 150 C, in other
cases
= about 200 C and in still other cases about 220 C. Immediately prior to
entering the
first V/L separator the deactived solution in some cases may have a maximum
pressure of about 40 MPag, in other cases about 25 MPag and in still cases
about 15
MPag; the minimum pressure in some cases may be about 1.5 MPag, in other cases
about 5 MPag and in still' other cases about 6 MPag.
= The first V/L separator 103 may be operated over a relatively broad range
of
temperatures and pressures. For example, the maximum operating temperature of
the first V/L separator in some cases may be about 300 C, in other cases about
285 C and in still other cases about 270 C; the minimum operating temperature
in
some cases may be about 100 C, in other cases about 140 C and in still other
cases
170 C. The maximum operating pressure of the first V/L separator in some cases
may be about 20 MPag, in other cases about 10 MPag and in still other cases
about 5
MPag; the minimum operating pressure in some cases may be about 1 MPag, in
other
cases about 2 MPag and in still other cases about 3 MPag.
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The second V/L separator,105 may be operated over a relatively broad range
of temperatures and pressures. For example, the maximum operating temperature
of
the second V/L separator in some cases may be about 300 C, in other cases
about
250 C and in still other cases about 200 C; the minimum operating temperature
in
some cases may be about 100 C, in other cases about 125 C and in still other
cases
about 150 C. The maximum operating pressure of the second V/L separator in
some
cases may be about 1000 kPag, in other cases about 900 kPag and in still other
cases about 800kPag; the minimum operating pressure in some cases may be about
kPag, in other cases about 20 kPag and in still other cases about 30 kPag.
10 The third V/L separator, 107 may be operated over a relatively broad
range of
temperatures and pressures. For example, the maximum operating temperature of
the third V/L separator in some cases may be about 300 C, in other cases about
250 C, and in still other cases about 200 C; the minimum operating temperature
in
some cases may be about 100 C, in other cases about 125 C and in still other
cases
about 150 C. The maximum operating pressure of the third V/L separator in some
cases may be about 500 kPag, in other cases about 150 kPag and in still other
cases
about 100 kPag; the minimum operating pressure in some cases may be about 1
kPag, in other cases about 10 kPag and in still other cases 25 about kPag.
In an embodiment of the present disclosure, one or more V/L separator may be
.. operated at vacuum pressure.
Embodiments of the continuous solution polymerization process shown in
Figures 1-3 show three V/L separators. However, continuous solution
polymerization
embodiments may include configurations comprising at least one V/L separator.
In another embodiment of the disclosure, a two phase liquid/liquid polymer
solution may be present or induced to be present downstream of the final
polymerization reactor. Such a two phase liquid/liquid polymer solution may be
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separated into a polymer lean phase and a polymer rich phase downstream of the
final polymerization reactor. A liquid/liquid ("UL") phase separator may be
operated
over a relatively broad range of temperatures and pressures. One or more L/L
phase
separators may be used.
Any reactor shape or design may be used for reactors 1 and 2 in Figures 1-3;
non-limiting examples include unstirred or stirred spherical, cylindrical or
tank-like
vessels, as well as tubular reactors or recirculating loop reactors. At
commercial scale
the maximum volume of reactors 1 and 2 in some cases may be about 20,000
gallons
(about 75,710 L), in other cases about 10,000 gallons (about 37,850 L) and in
still
other cases about 5,000 gallons (about 18,930 L). At commercial scale the
minimum
volume of reactors 1 and 2 in some cases may be about 100 gallons (about 379
L), in
other cases about 500 gallons (about 1,893 L) and in still other cases about
1,000
gallons (about 3,785 L). At pilot plant scales reactor volumes are typically
much
smaller, for example the volume of reactors 1 and 2 at pilot scale could be
less than
about 10 gallons (less than about 37 L).
In this disclosure the volume of reactor R2 may be expressed as a percent of
the volume of reactor R1..
In embodiments of the disclosure the upper limit on the volume of R2 in some
cases may be about 600% of R1, in other cases about 400% of R1 and in still
other
cases about 200% of R1. For clarity, if the volume of R1 is 5,000 gallons and
R2 is
200% the volume of R1, then R2 has a volume of 10,000 gallons.
In embodiments of the disclosure the lower limit on the volume of R2 in some
cases may be about 50% of R1, in other cases about 100% of R1 and in still
other
cases about 150% of R1. In the case of continuously stirred tank reactors the
stirring
rate can vary over a wide range; in some cases from about 10 rpm to about 2000
rpm,
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in other cases from about 100 to about 1500 rpm and in still other cases from
about
200 to about 1300 rpm.
In an embodiment of this disclosure, reactor 3 is a tubular reactor, and the
volume of R3, may be expressed as a percent of the volume of reactor R2. The
upper
limit on the volume of R3 in some cases may be about 500% of R2, in other
cases
about 300% of R2 and in still other cases about 100% of R2. The lower limit on
the
volume of R3 in some cases may be about 3% of R2, in other cases about 10% of
R2
and in still other cases about 50% of R2.
The "average reactor residence time", a commonly used parameter in the
.. chemical engineering art, is defined by the first moment of the reactor
residence time
distribution; the reactor residence time distribution is a probability
distribution function
that describes the amount of time that a fluid element spends inside the
reactor. The
average reactor residence time can vary widely depending on process flow rates
and
reactor mixing, design and capacity.
In embodiments of the disclosure, the upper limit on the average reactor
residence time of the solution in reactors 1 and 2 is about 720 seconds, or
about 600
seconds, or about 480 seconds, or about 360 seconds, or about 240 seconds, or
about 180 seconds.
In embodiments of the disclosure, the lower limit on the average reactor
residence time of the solution in reactors 1 and 2 is about 10 seconds, or
about 20
seconds, or about 30 seconds, or about 40 seconds, or about 60 seconds.
In embodiments of the disclosure, the upper limit on the average reactor
residence time of the solution in reactor 3 is about 600 seconds, or about 360
seconds, or about 180 seconds.
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In embodiments of the disclosure, the lower limit on the average reactor
residence time of the solution in reactor 3 is about 1 second, or about 5
seconds, or
about 10 seconds.
Optionally, additional reactors (e.g. CSTRs, loops or tubes, etc.) could be
added to the continuous solution polymerization process embodiments shown in
Figures 1-3.
In operating the continuous solution polymerization process embodiments
shown in Figures 1-3 the total amount of ethylene supplied to the process can
be
portioned or split between the three reactors R1, R2 and R3.
This operational variable is referred to as the Ethylene Split (ES), i.e.
"ESR1",
"ESR2" and "ESR3" refer to the weight percent of ethylene injected in R1, R2
and R3,
respectively; with the proviso that ES R1+ ESR2+ ESR3 = 100%. This is
accomplished
by adjusting the ethylene flow rates in the following streams: stream D (R1),
stream E
(R2) and stream F (R3).
In the present disclosure, at least 1 weight percent of the total ethylene
injected
into reactor 1, reactor 2 and reactor 3, is injected into reactor 3 (i.e. ESR3
is at least
1%).
In an embodiment of the disclosure, at least 10 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3 (i.e.
ESR3 is at least 10%).
In an embodiment of the disclosure, at least 20 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3 (i.e.
ESR3 is at least 20%).
In an embodiment of the disclosure, at least 30 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3 (i.e.
ESR3 is at least 30%).
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In an embodiment of the disclosure, at least 40 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3 (i.e.
ESR3 is at least 40%).
In an embodiment of the disclosure, at least 50 weight percent of the total
ethylene injected into reactor 1, reactor 2 and reactor 3, is injected into
reactor 3 (i.e.
ESR3 is at least 50%).
In embodiments of the disclosure, the upper limit on ESR1 is about 80%, or
about 75%, or about 70%, or about 65%; or about 60%, or about 55%; and the
lower
limit on ES R1 is about 10%, or about 15%, or about 20%.
In embodiments of the disclosure, the upper limit on ESR2 is about 60%, or
about 55% or about 50%; or about 45%, or about 40%, or about 35%, or from
about
30%; and the lower limit on ESR2 is about 5%, or about 10%, or about 15%, or
about
20%, or about 25%.
In embodiments of the disclosure, the upper limit on ESR3 is about 50%, or
about 40%, or about 35%, or about 30%, or about 25%, or about 20%; and the
lower
limit on ESR3 is about 1%, or about 5%, or about 10%.
In operating the continuous solution polymerization process embodiments
shown in Figures 1-3, the ethylene concentration in each reactor may also be
controlled. For example, the ethylene concentration in reactor 1, hereafter
"EC'", is
defined as the weight of ethylene in reactor 1 divided by the total weight of
everything
added to reactor 1. An "ECR2" and "ECR3" may be similarly defined.
In embodiments of the disclosure, the ethylene concentration in the reactors
(ECR1 or ECR2 or ECR3) may vary from about 5 weight percent to about 25 weight
percent, or from about 7 weight percent (wt %) to about 25 wt %, or from about
8 wt %
to about 20 wt %, or from about 9 wt % to about 17 wt %.
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In operating the continuous solution polymerization process embodiments
shown in Figures 1-3 the total amount of ethylene converted in each reactor
may be
monitored. The term "QR1" refers to the percent of the ethylene added to R1
that is
converted into a polyethylene polymer by the catalyst system. Similarly,"QR2"
and
"QR3" represent the percent of the ethylene added to R2 and R3 that was
converted
into a polyethylene polymer, in the respective reactors.
Ethylene conversions can vary significantly depending on a variety of process
conditions, e.g. catalyst concentration, catalyst system, impurities and
poisons.
In embodiments of the disclosure, the upper limit on both QR1 and QR2 may be
about 99%, or about 95%, or about 90%; while the lower limit on both QR1 and
0R2
may be from about 65%, or about 70%, or about 75%.
In embodiments of the disclosure, the upper limit on 0R3 may be about 99%, or
about 95%, or about 90%; while the lower limit on 0R3 may be 1%, or about 5%,
or
about 10%.
The term -CITOTAL" represents the total or overall ethylene conversion across
the
entire continuous solution polymerization plant; i.e. QT = 100 x [weight of
ethylene in
the polyethylene product}/([weight of ethylene in the polyethylene
productHweight of
unreacted ethylene]). The upper limit on QT in some cases is about 99%, in
other
cases about 95% and in still other cases about 90%; the lower limit on QT in
some
cases is about 75%, in other cases about 80% and in still other cases about
85%.
Optionally, a-olefin may be added to the continuous solution polymerization
process. If added, a-olefin may be proportioned or split between R1, R2 and
R3. This
operational variable is referred to as the Comonomer Split (CS), i.e. "CSR1",
"CSR2"
and "CSR3" refer to the weight percent of a-olefin comonomer that is injected
in R1, R2
and R3, respectively; with the proviso that CSR1+ csR2 CSR3 100%. This is
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accomplished by adjusting a-olefin flow rates in the following streams: stream
G (R1),
stream H (R2) and stream I (R3).
The upper limit on CSR1 in some cases is 100% (Le. 100% of the a-olefin is
injected into R1), in other cases about 95% and in still other cases about
90%. The
= 5 lower limit on CSR1 in some cases is 0% (ethylene
homopolymer produced in R1), in
other cases about 5% and in still other cases about 10%. The upper limit on
CSR2 in
some cases is about 100% (i.e. 100% of the a-olefin is injected into reactor
2), in other
cases about 95% and in still other cases about 90%. The lower limit on CSR2 in
some
cases is 0% (ethylene homopolymer produced in R2), in other cases about 5% and
in
still other cases about 10%. The upper limit on CSR3 in some cases is 100%, in
other
cases about 95% and in still other cases about 90%. The lower limit on CSR3 in
some
cases is 0%, in other cases about 5% and in still other cases about 10%.
In an embodiment of the disclosure, a first polyethylene is produced with a
single-site catalyst system in reactor 1. Referring to the embodiments shown
in
Figures 1-3, if the optional a-olefin is not added to reactor 1 (R1), then the
first
polyethylene produced in R1 is an ethylene homopolymer. If an a-olefin is
added,
then the first polyethylene produced in R1 is an ethylene copolymer and the
following
weight ratio is one parameter to control the density of the first
polyethylene: ((a-
olefin)/(ethylene))R1 . The upper limit on ((a-olefin)/(ethylene))R1 may be
about 3; in
other cases about 2 and in still other cases about 1. The lower limit on ((a-
olefin)/(ethylene))R1 may be 0; in other cases about 0.25 and in still other
cases about
0.5. Hereafter, the term "d1" refers to the density of the first polyethylene
produced in
R1. The upper limit on d1 may be about 0.975 g/cm3; in some cases about 0.965
g/cm3 and; in other cases about 0.955 g/cm3. The lower limit on dl 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 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 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 9/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 0.880 g/cm3 to
0.912
g/cm3.
Methods to determine the CDBI50 (Composition Distribution Branching Index) of
an ethylene polymer are well known to those skilled in the art. The CDB150,
expressed
as a percent, is defined as the percent of the ethylene polymer whose
comonomer
composition is within 50% of the median comonomer composition. It is also well
known to those skilled in the art that the CDBI50 of ethylene polymers
produced with
single-site catalyst systems are higher relative to the CDBI50 of a-olefin
containing
ethylene polymers produced with heterogeneous catalyst systems. The upper
limit on
the CDBI50 of the first polyethylene (produced with a single-site catalyst
system) may
be about 98%, in other cases about 95% and in still other cases about 90%. The
lower limit on the CDBI50 of the first polyethylene may be about 70%, in other
cases
about 75% and in still other cases about 80%.
As is well known to those skilled in the art the Mw/Mn of ethylene polymers
produced with single site catalyst systems are lower relative to ethylene
polymers
produced with heterogeneous catalyst systems. The upper limit on the Mw/Mn of
the
first polyethylene may be about 2.8, in other cases about 2.5, in other cases
about
2.4, and in still other cases about 2.2. The lower limit on the Mw/Mn the
first
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polyethylene may be about 1.4, in other cases 1.6, in other cases about 1.7,
in other
cases about 1.8 and in still other cases about 1.9.
The first polyethylene may contain catalyst residues that reflect the chemical
composition of the single-site catalyst system used. Those skilled in the art
will
understand that catalyst residues are typically quantified by the parts per
million of
metal in the first polyethylene, where metal refers to the metal in component
(a), e.g.
the metal in the "phosphinimine complex", herein referred to as M1. The upper
limit on
the ppm of the metal M1 in the first polyethylene may be about 5.0 ppm, in
other cases
about 2.5 ppm, or 2.0 ppm, or 1.0 ppm, or 0.9 ppm and in still other cases
about 0.8
ppm. The lower limit on the ppm of metal M1 in the first polyethylene may be
about
0.01 ppm, in other cases about 0.1 ppm and in still other cases about 0.2 ppm.
The amount of hydrogen added to reactor 1 can vary over a wide range
allowing the continuous solution process to produce polyethylenes that differ
greatly in
melt index, hereafter 121 (melt index is measured at 190 C using a 2.16 kg
load
following the procedures outlined in ASTM D1238). This is accomplished by
adjusting
the hydrogen flow rate in stream M (see Figures 1-3). The quantity of hydrogen
added to R1 is expressed as the parts-per-million (ppm) of hydrogen in R1
relative to
the total mass in reactor .R1; hereafter H2R1 (ppm). In some cases H2R1 (ppm)
ranges
from about 100 ppm to 0 ppm, in other cases from about 50 ppm to 0 ppm, in
alternative cases from about 20 ppm to 0 ppm and in still other cases from
about 2
ppm to 0 ppm. The upper limit on 121 may be about 200 dg/min, in some cases
about
100 dg/min; in other cases about 50 dg/min, and; in still other cases about 1
dg/min.
The lower limit on 121 may be about 0.01 dg/min, in some cases about 0.05
dg/min; in
other cases about 0.1 dg/min, and; in still other cases about 0.5 dg/min.
In embodiments of the disclosure the melt index of the first polyethylene 121
may
be from about 0.01 dg/min to about 100 dg/min, or from about 0.05 dg/min to
about 50
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dg/min, or from about 0.10 dg/min to about 50 dg/min, or from about 0.01
dg/min to
about 25 dg/min, or from about 0.05 dg/min to about 25 dg/min, or from about
0.10
dg/min to about 25 dg/min, or from about 0.01 dg/min to about 10 dg/min, or
from
about 0.05 dg/min to about 10 dg/min, or from about 0.10 dg/min to about 10
dg/min,
or from about 0.01 dg/min to about 5.0 dg/min, or from about 0.05 dg/min to
about 5.0
dg/min, or from about 0.10 dg/min to about 5.0 dg/min, or from about 0.10
dg/min to
about 3.0 dg/min, or from about 0.05 dg/min to about 3.0 dg/min, or from about
0.05 to
2.5 dg/min.
In an embodiment of the disclosure the melt index of the first polyethylene
121
may be less than about 1.0 dg/min.
In an embodiment of the disclosure, the first polyethylene has a weight
average
molecular weight, Mw of from about 40,000 to about 400,000, or from about
45,000 to
about 300,000, or from about 50,000 to about 300,000, or from about 50,000 to
about
250,000, or from about 50,000 to about 200,000; or from about 60,000 to about
400,000, or from about 60,000 to about 350,000, or from about 60,000 to about
300,000 or from about 60,000 to about 250,000, or from about 60,000 to about
200,000.
The upper limit on the weight percent (wt%) of the first polyethylene in the
final
polyethylene polymer product may be about 80 wt%, in other cases about 75 wt%,
or
about 70 wt%, or about 65 wt%, or about 60 wt%, or about 55 wt% and in still
other
cases about 50 wt%. The lower limit on the wt % of the first polyethylene in
the final
polyethylene product may be about 15 wt%; in other cases about 25 wt%, in
other
cases about 30 wt%, in other cases bout 35%, in still other cases about 40%.
In an embodiment of the disclosure, a second polyethylene is produced with a
__ single-site catalyst system in reactor 2. The second polyethylene may be an
ethylene
homopolymer or an ethylene copolymer. Referring to the embodiments shown in
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Figures 1-3, if optional a-olefin is not added to reactor 2 through a-olefin
stream H,
then the second polyethylene produced in reactor 2 is an ethylene homopolymer.
If
an optional a-olefin is present then the second polyethylene produced in R2 is
an
ethylene copolymer and the following weight ratio is one parameter to control
the
density of the second polyethylene produced in R2: ((a-olefin)/(ethylene))R2.
The
upper limit on ((a-olefin)/(ethylene))R2 may be about 3; in other cases about
2 and in
still other cases about 1. The lower limit on ((a-olefin)/(ethylene))R2 may be
0; in other
cases about 0.25 and in still other cases about 0.5. Hereafter, the term "d2"
refers to
the density of the second polyethylene produced in R2. The upper limit on d2
may be
about 0.975 g/cm3; in some cases about 0.965 g/cm3 and; in other cases about
0.955
g/cm3. Depending on the single site catalyst system used, the lower limit on
d2 may
be about 0.89 g/cm3, in some cases about 0.90 g/cm3, and; in other cases about
0.91
g/cm3.
In embodiments of the disclosure the density, d2 may be from about 0.921
g/cm3 to about 0.975 g/cm3, or from about 0.926 g/cm3 to about 0.975 g/cm3, or
from
about 0.930 g/cm3to about 0.975 g/cm3, or from about 0.936 g/cm3 to about
0.975
g/cm3, or from about 0.940 g/cm3 to about 0.975 g/cm3, or from about 0.945
g/cm3 to
about 0.975 g/cm3, or from about 0.950 g/cm3 to about 0.975 g/cm3, or from
about
0.951 9/cm3 to about 0.975 g/cm3, or from about 0.953 g/cm3 to about 0.970
g/cm3, or
from about 0.953 g/cm3to about 0.959 g/cm3, or from about 0.955 g/cm3 to about
0.975 g/cm3, or from about 0.951 g/cm3 to about 0.959 g/cm3, or from 0.936 to
about
0.970 g/cm3, or from about 0.940 g/cm3 to about 0.970 g/cm3, or from about
0.945
g/cm3 to about 0.970 g/cm3, or from about 0.950 g/cm3 to about 0.970 g/cm3.
The upper limit on the CDBI50 of the second polyethylene (produced with a
single-site catalyst system) may be about 98%, in other cases about 95% and in
still
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other cases about 90%. The lower limit on the CDB150 of the second
polyethylene
may be about 70%, in other cases about 75% and in still other cases about 80%.
The upper limit on the Mw/Mn of the second polyethylene may be about 2.8, in
other cases about 2.5, in other cases about 2.4 and in still other cases about
2.2. The
lower limit on the Mw/Mn the second polyethylene may be about 1.4, in other
cases
about 1.6, in other cases about 1.7, in other cases about 1.8 and in still
other cases
about 1.9.
The second polyethylene may contain catalyst residues that reflect the
chemical composition of the single-site catalyst system used. Those skilled in
the art
will understand that catalyst residues are typically quantified by the parts
per million of
metal in the second ethylene polymer, where metal refers to the metal in
component
(a), i.e., the metal in the "phosphinimine complex", herein referred to as M2.
The
upper limit on the ppm of the metal M2 in the second polyethylene may be about
5.0
ppm, or about 2,5 ppm, or about 1.0 ppm, or in other cases about 0.9 ppm and
in still
other cases about 0.8 ppm. The lower limit on the ppm of metal M2 in the
second
polyethylene may be about 0.01 ppm, in other cases about 0.1 ppm and in still
other
cases about 0.2 ppm.
The amount of hydrogen added to R2 can vary over a wide range allowing the
continuous solution process to produce second polyethylenes that differ
greatly in melt
index, hereafter 122 (melt index is measured at 190 C using a 2.16 kg load
following
the procedures outlined in ASTM D1238). This is accomplished by adjusting the
hydrogen flow rate in stream N (see Figures 1-3). The quantity of hydrogen
added to
R2 is expressed as the parts-per-million (ppm) of hydrogen in R2 relative to
the total
mass in reactor R2; hereafter H2R2 (ppm). In some cases H2R2 (ppm) ranges from
about 100 ppm to 0 ppm, in other cases from about 50 ppm to 0 ppm, in
alternative
cases from about 20 ppm to 0 ppm and in still other cases from about 2 ppm to
0 ppm.
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The upper limit on 122 may be about 20,000 dg/min; in some cases about 10,000
dg/min; in other cases about 1500 dg/min, and; in still other cases about 1000
dg/min.
The lower limit on 122 may be about 0.3 dg/min, in some cases about 0.4
dg/min, in
other cases about 0.5 dg/min, and; in still other cases about 0.6 dg/min.
In embodiments of the disclosure the melt index of the second polyethylene 122
may be from about 0.5 dg/min to about 10,000 dg/min, or from about 0.5 dg/min
to
about 1000 dg/min, or from about 1.0 dg/min to about 10,000 dg/min, or from
about
1.0 dg/min to about 1000 dg/min, or from about 0.5 dg/min to about 500 dg/min,
or
from about 1.0 dg/min to about 500 dg/min, or from about 0.5 dg/min to about
100
dg/min, or from about 1.0 dg/min to about 100 dg/min, or from about 0.5 dg/min
to
about 75 dg/min, or from about 1.0 dg/min to about 75 dg/min, or from about
0.5
dg/min to about 50 dg/min, or from about 1.0 dg/min to about 50 dg/min, or
from about
0.5 dg/min to about 25 dg/min, or from about 1.0 dg/min to about 25 dg/min, or
from
about 0.5 dg/min to about 20 dg/min, or from about 1.0 dg/min to about 20
dg/min, or
from about 0.5 dg/min to about 15 dg/min, or from about 1.0 dg/min to about 15
dg/min, or from about 0.5 dg/min to about 10 dg/min, or from about 1.0 dg/min
to
about 12.0 dg/min, or from about 1.0 dg/min to about 10 dg/min.
In an embodiment of the disclosure, the second polyethylene has a weight
average molecular weight, Mw of from about 20,000 to about 150,000, or from
about
25,000 to about 130,000, or from about 20,000 to about 120,000, or from about
25,000 to about 100,000, or from about 30,000 to about 120,000; or from about
30,000 to about 100,000.
The upper limit on the weight percent (wt%) of the second polyethylene in the
final polyethylene product may be about 85 wt%, in other cases about 80 wt%,
in
other cases 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% or about 35 wt%. The lower
limit on
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the wt % of the second polyethylene in the final polyethylene product may be
about 5
wt%, or about 10 wt%, or about 15wt%, or about 20 wt%, or in other cases about
30
wt%.
In an embodiment of the disclosure, the first polyethylene may have a higher
weight average molecular weight Mw, than the weight average molecular weight
Mw, of
the second polyethylene polymer.
Optionally, a second catalyst system may be added to the third reactor, R3.
The second catalyst system may be a single site catalyst system or a Ziegler-
Natta
catalyst system.
A third polyethylene is produced in reactor 3. Either active catalyst flows
from
reactor 1 and/or 2, and/or a fresh polymerization catalyst system is added to
reactor 3.
If optional a-olefin is not added to reactor 3, either by fresh a-olefin
stream I or carried
over from reactors 1 and/or 2 in combined exits streams 1' and 2' (Figure 1),
or exit
stream 1' (Figure 2), or exit stream 2' (Figure 3), then the third polymer
formed in
reactor 3 is an ethylene homopolymer. If optional a-olefin is added to reactor
3, either
by fresh a-olefin stream I and/or carried over from reactors 1 and/or 2 in
combined
exits streams 1' and 2' (Figure 1), or exit stream 1' (Figure 2), or exit
stream 2' (Figure
3), then the third polymer formed in reactor 3 is an ethylene copolymer and
the
following weight ratio determines the density of the third polyethylene: ((a-
olefin)/(ethylene))R3. In the continuous solution polymerization process ((a-
olefin)/(ethylene))R3 is one of the control parameters used to produce a third
ethylene
polyethylene with a desired density. The upper limit on ((a-
olefin)/(ethylene))R3 may
be about 3; in other cases about 2 and in still other cases about 1. The lower
limit on
((a-olefin)/(ethylene))R3 may be 0; in other cases about 0.25 and in still
other cases
about 0.5. Hereafter, the term "d3" refers to the density of the ethylene
polymer
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produced in R3. The upper limit on d3 may be about 0.975 g/cm3; in some cases
about 0.965 g/cm3 and; in other cases about 0.955 g/cm3. Depending on the
catalyst
system used, the lower limit on d3 may be about 0.865 g/cm3, in some cases
about
0.875 g/cm3, in some cases about 0.88 g/cm3, in some cases about 0.89 g/cm3,
in
some cases about 0.90 g/cm3, and; in other cases about 0.91 g/cm3.
In embodiments of the disclosure the density of the third polyethylene, d3 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 about 0.955 g/cm3, or from about
0.875
9/cm3 to about 0.950 g/cm3, or from about 0.88 9/cm3 to about 0.945 g/cm3, or
from
about 0.89 g/cm3 to about 0.941 g/cm3, or from about 0.89 g/cm3 to about 0.940
g/cm3, or from about 0.89 g/cm3 to about 0.936 g/cm3, or from about 0.875
g/cm3 to
about 0.936 g/cm3, or from about 0.880 g/cm3 to about 0.936 g/cm3, or from
about
0.880 g/cm3 to about 0.935 9/cm3, or from about 0.880 g/cm3 to about 0.932
g/cm3, or
from about 0.88 g/cm3 to about 0.930 g/cm3, or from about 0.875 g/cm3 to about
0.925
g/cm3, or from about 0.89 g/cm3 to about 0.926 g/cm3.
The upper limit on the Mw/Mn of the third polyethylene may be about 8.0, or
about 7.0, or about 6.5, or about 6.0, in other cases about 5.5, or about 5.0
and in still
other cases about 4.8. The lower limit on the Mw/Mn of the third polyethylene
may be
about 4.0, or about 3.5, or about 3.0, or about 2.6, or about 2.5.
In an embodiment of the disclosure, the Mw/Mn of the third polyethylene may be
from about 2.2 to about 7.0, or from about 2.4 to about 6.5, or from about 2.6
to about
6.0, or from about 2.8 to about 5.5, or from about 3.0 to about 6.0, or from
about 3.0 to
about 5.5.
In an embodiment of the disclosure, the Mw/Mn of the third polyethylene is
higher than the Mw/Mn of the first polyethylene.
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In an embodiment of the disclosure, the Mw/Mn of the third polyethylene is
higher than the Mw/Mn of the second polyethylene.
In an embodiment of the disclosure, the Mw/Mn of the third polyethylene is
higher than the Mw/Mn of both the first and second polyethylene.
In an embodiment of the disclosure the third polyethylene has a higher weight
average molecular weight than the weight average molecular weight of the
second
polyethylene.
In an embodiment of the disclosure the first polyethylene and the third
polyethylene each have a higher weight average molecular weight than the
weight
average molecular weight of the second polyethylene.
= Referring to the embodiments shown in Figures 1-3, optional hydrogen may
be
added to the reactor 3 via stream 0. The amount of hydrogen added to R3 may
vary
over a wide range. Adjusting the amount of hydrogen in R3, hereafter H2R3
(ppm),
allows the continuous solution process to produce third polyethylenes that
differ widely
in melt index, hereafter V. The amount of optional hydrogen added to R3 ranges
from about 50 ppm to 0 ppm, in some cases from about 25 ppm to 0 ppm, in other
cases from about 10 to 0 and in still other cases from about 2 ppm to 0 ppm.
The
upper limit on 123 may be about 2000 dg/min; in some cases about 1500 dg/min;
in
other cases about 1000 dg/min, and; in still other cases about 500 dg/min. The
lower
limit on 123 may be about 0.5 dg/min, in some cases about 0.6 dg/min, in other
cases
about 0.7 dg/min, and; in still other cases about 0.8 dg/min.
In embodiments of the disclosure the melt index of the third polyethylene 123
may be from about 0.01 pig/min to about 10,000 dg/min or from about 0.05
dg/min to
about 10,000 dg/min, or from about 0.10 to about 10,000, or from about 0.5
dg/min to
about 10,000 dg/min, or from about 1.0 dg/min to about 10,000 dg/min, or from
about
0.1 dg/min to about 5000 dg/min, or from about 0.5 dg/min to about 5000
dg/min, or
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from about 0.01 dg/min to about 1000 dg/min, or from about 0.05 to 1000
dg/min, or
from about 0.10 dg/min to about 1000 dg/min, or from about 0.5 dg/min to about
1000
dg/min, or from about 1.0 dg/min to about 1000 dg/min, or from about 0.01
dg/min to
about 500 dg/min, or from about 0.05 dg/min to about 500 dg/min, or from about
0.10
dg/min to about 500 dg/min, or from about 0.1 dg/min to about 250 dg/min, or
from
about 0.5 dg/min to about 250 dg/min, or from about 1.0 dg/min to about 250
dg/min,
or from about 0.01 dg/min to about 200 dg/min, or from about 0.05 dg/min to
about
200 dg/min, or from about 0.1 dg/min to about 200 dg/min, or from about 0.01
dg/min
to about 100 dg/min, or from about 0.05 dg/min to about 100 dg/min, or from
about
0.10 dg/min to 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or
from
about 0.05 dg/min to about 50 dg/min, or from about 0.10 dg/min to about 50
dg/min,
or from about 0.01 dg/min to about 25 dg/min, or from about 0.05 dg/min to
about 25
dg/min, or from about 0.10 dg/min to about 25 dg/min, or from 0.01 dg/min to
about 10
dg/min, or from 0.50 dg/min to about 10 dg/min, or from 0.10 dg/min to about
10
dg/min, or from about 0.01 dg/min to about 5.0 dg/min, or from about 0.1
dg/min to
about 5 dg/min, or from about 0.01 dg/min to about 3 dg/min, or from about 0.1
dg/min
to about 3 dg/min.
In an embodiment of the disclosure, the third polyethylene has a weight
average molecular weight, Mw of from about 20,000 to about 400,000, or from
about
20,000 to about 300,000, or from about 20,000 to about 250,000, or from about
25,000 to about 225,000, or from about 25,000 to about 200,000; or from about
20,000 to about 175,000, or from about 20,000 to about 150,000.
The upper limit on the weight percent (wt%) of the third ethylene polymer in
the
final ethylene polymer product may be about 45 wt%, in other cases about 40
wt%, in
other cases about 35 wt%, and in still other cases about 30 wt%. The lower
limit on
the wt % of the optional third ethylene polymer in the final ethylene polymer
product
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may be about 1 wt%; in other cases about 5 wt%, in other cases about 10 wt%,
in
other cases about 15 wt%, in other cases about 20 wt%, and in still other
cases about
25 wt%.
The Final Polyethylene Product Composition
The "final polyethylene product composition" (used herein interchangeably with
the terms "polyethylene product composition" and "polyethylene product")
comprises a
= first polyethylene, a second polyethylene and a third polyethylene (as
described
above). Despite this fact, in an embodiment of the disclosure, the
polyethylene
product composition has a unimodal profile in a gel permeation chromatography
(GPC) curve 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 06474-99. 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 polyethylene product satisfies the
following relationship: [(weight average molecular weight of the second
polyethylene)
- (weight average molecular weight of the first polyethylene)] / (weight
average
molecular weight of the second polyethylene) x 100% -140%. In an embodiment of
the disclosure, the polyethylene product satisfies the following relationship:
[(weight
average molecular weight of the second polyethylene) - (weight average
molecular
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weight of the first polyethylene)] / (weight average molecular weight of the
second
polyethylene) x 100% -130%. In an embodiment of the disclosure, the
polyethylene
product satisfies the following relationship: [(weight average molecular
weight of the
second polyethylene) - (weight average molecular weight of the first
polyethylene)] /
(weight average molecular weight of the second polyethylene) x 100% -120%. In
an embodiment of the disclosure, the polyethylene product satisfies the
following
relationship: [(weight average molecular weight of the second polyethylene) -
(weight
average molecular weight of the first polyethylene)] / (weight average
molecular
weight of the second polyethylene) x 100% -110%. In an embodiment of the
disclosure, the polyethylene product satisfies the following relationship:
[(weight
average molecular weight of the second polyethylene) - (weight average
molecular
weight of the first polyethylene)] / (weight average molecular weight of the
second
polyethylene) x 100% 7100%.
In an embodiment of the disclosure, the polyethylene product satisfies the
following relationship: [(weight average molecular weight of the third
polyethylene) -
(weight average molecular weight of the second polyethylene)] / (weight
average
molecular weight of the third polyethylene) x 100% -100%. In an embodiment of
the disclosure, the polyethylene product satisfies the following relationship:
[(weight
average molecular weight of the third polyethylene) - (weight average
molecular
weight of the second polyethylene)] / (weight average molecular weight of the
third
polyethylene) x 100% a. -75%. In an embodiment of the disclosure, the
polyethylene
product satisfies the following relationship: [(weight average molecular
weight of the
third polyethylene) - (weight average molecular weight of the second
polyethylene)] /
(weight average molecular weight of the third polyethylene) x 100% -50%. In an
embodiment of the disclosure, the polyethylene product satisfies the following
relationship: [(weight average molecular weight of the third polyethylene) -
(weight
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average molecular weight of the second polyethylene)] / (weight average
molecular
weight of the third polyethylene) x 100% -40%. In an embodiment of the
disclosure,
the polyethylene product,satisfies the following relationship: [(weight
average
molecular weight of the third polyethylene) - (weight average molecular weight
of the
.. second polyethylene)] / (weight average molecular weight of the third
polyethylene) x
100% -30%.
In an embodiment of the disclosure, the polyethylene composition satisfies the
following relationship: [(weight average molecular weight of the third
polyethylene) -
(weight average molecular weight of the first polyethylene)] / (weight average
.. molecular weight of the third polyethylene) x 100% -350%. In an embodiment
of the
disclosure, the polyethylene composition satisfies the following relationship:
[(weight
average molecular weight of the third polyethylene) - (weight average
molecular
weight of the first polyethylene)] / (weight average molecular weight of the
third
polyethylene) x 100% a :300%. In an embodiment of the disclosure, the
polyethylene
composition satisfies the following relationship: [(weight average molecular
weight of
the third polyethylene) - (weight average molecular weight of the first
polyethylene)] /
(weight average molecular weight of the third polyethylene) x 100% a -250%. In
an
embodiment of the disclosure, the polyethylene composition satisfies the
following
relationship: [(weight average molecular weight of the third polyethylene) -
(weight
.. average molecular weight of the first polyethylene)] / (weight average
molecular
weight of the third polyethylene) x 100% -225%. In an embodiment of the
disclosure, the polyethylene composition satisfies the following relationship:
[(weight
average molecular weight of the third polyethylene) - (weight average
molecular
weight of the first polyethylene)] / (weight average molecular weight of the
third
polyethylene) x 100% -200%. In an embodiment of the disclosure, the
polyethylene
composition satisfies the following relationship: [(weight average molecular
weight of
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the third polyethylene) - (weight average molecular weight of the first
polyethylene)] /
(weight average molecular weight of the third polyethylene) x 100% -175%. In
an
embodiment of the disclosure, the polyethylene composition satisfies the
following
relationship: [(weight average molecular weight of the third polyethylene) -
(weight
average molecular weight of the first polyethylene)] / (weight average
molecular
weight of the third polyethylene) x 100% -150%. In an embodiment of the
disclosure, the polyethylene composition satisfies the following relationship:
[(weight
average molecular weight of the third polyethylene) - (weight average
molecular
weight of the first polyethylene)] / (weight average molecular weight of the
third
polyethylene) x 100% -100%. In an embodiment of the disclosure, the
polyethylene
composition satisfies the following relationship: [(weight average molecular
weight of
the third polyethylene) - (weight average molecular weight of the first
polyethylene)] /
(weight average molecular weight of the third polyethylene) x 100% -50%.
The upper limit on the density of the polyethylene product may be about 0.975
g/cm3; in some cases about 0.965 g/cm3 and; in other cases about 0.955 g/cm3.
The
lower limit on the density of the polyethylene product may be about 0.869
g/cm3, in
some cases about 0.879 g/cm3, and; in other cases about 0.889 g/cm3.
In embodiments of the disclosure, the density of the polyethylene product may
be from about 0.879 g/cm3 to about 0.940 g/cm3, or from about 0.879 g/cm3 to
about
0.939 g/cm3, or from about 0.879 g/cm3 to about 0.936 g/cm3, or from about
0.890
g/cm3 to about 0.939 g/cm3, or from about 0.890 to about 0.936 g/cm3, or from
about
0.879 g/cm3 to about 0.932 g/cm3, or from about 0.89 g/cm3 to about 0.934
g/cm3, or
from about 0.890 g/cm3 to about 0.932 g/cm3, or from about 0.890 g/cm3 to
about
0.930 g/cm3, or from about 0.890 to about 0.928 g/cm3, or from about 0.890 to
about
0.926 g/cm3, or from about 0.890 g/cm3 to about 0.924 g/cm3, or from about
0.890
g/cm3 to about 0,921 g/cm3, or from about 0.890 g/cm3 to about 0.918 g/cm3.
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In an embodiments of the disclosure, the density of the polyethylene product
may be less than about 0.941 g/cm3, or less than about 0.940 g/cm3, or less
than
about 0.939 g/cm3, or :5_ about 0.939 g/cm3.
The upper limit on the CDBI50 of the final polyethylene product may be about
97%, in other cases about 90% and in still other cases about 85%. A final
polyethylene product with a CDBI50 of 97% may result if an a-olefin is not
added to the
continuous solution polymerization process; in this case, the final
polyethylene product
is an ethylene homopolymer. The lower limit on the CDBI50 of a final
polyethylene
product may be about 20%, in other cases about 40% and in still other cases
about
60%.
In an embodiment of the disclosure the polyethylene product may have a
CDE3150of greater than about 40%. In further embodiments of the disclosure the
polyethylene product may have a CDBI50 of from about 35 to 95%, or from 40 to
85%,
or from about 40 to about 75%.
The upper limit on the Mw/Mn of the final polyethylene product may be about
25,
in other cases about 15 and in still other cases about 9. The lower limit on
the Mw/Mn
of the final polyethylene product may be 2.0, in other cases about 2.1, or
about 2.2.
In an embodiment of the disclosure the polyethylene product, may have a
Mw/Mn of from about 2.1 to about 3.6, or from about 2.0 to about 3.5, or from
about 2.1
to about 3.4, or from about 2.1 to about 3.2, or from about 2.1 to about 3.0,
or from
about 2.0 to about 3.0, or from about 2.0 to about 2.8.
In an embodiment of the disclosure the polyethylene product, may have a
Mz/Mw of less than about 4.0, or less than about 3.5, or less than about 3.0,
or less
than about 2.5, or less than about 2.3, or less than about 2.1. In embodiments
of the
disclosure, the polyethylene product may have a Mz/Mw from about 1.6 to about
4.5,
or from about 1.6 to about 4.0, or from about 1.6 to about 3.5, or from about
1.6 to
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about 3.2, or from about 1.6 to about 3.0, or from about 1.8 to about 3.2, or
from about
1.8 to about 3.0, or from about 1.6 to about 3.0, or from about 1.8 to about
2.8, or from
about 1.8 to about 2.5, or from about 1.6 to about 2.3, or from about 1.8 to
about 2.3.
In an embodiment of the disclosure, the polyethylene product has a stress
exponent of less than 1.5, or less than 1.4, or less than 1.3, wherein the
stress
exponent is defined by the following relationship: S.Ex.= log
(16/12)/log(6480/2160);
wherein 16 and 12 are the melt indexes measured at 190 C using 6.48 kg and
2.16 kg
loads respectively.
Catalyst residues may be quantified by measuring the parts per million of
catalytic metal in the final polyethylene product. Catalytic metals originate
from two or
optionally three sources, specifically: 1) metals that originate from
component (a) that
was used to form the single-site catalyst system used in reactors 1 and 2; and
optionally "metals" that originate from the second system that may be used in
reactor
3.
The upper limit on melt index 12 of the polyethylene product may be about 500
dg/min, in some cases about 400 dg/min; in other cases about 300 dg/min, and;
in still
other cases about 200 dg/min. The lower limit on the melt index of the final
polyethylene product may be about 0.1 dg/min, or 0.2 dg/min, or 0.3 dg/min, in
some
cases about 0.4 dg/min; in other cases about 0.5 dg/min, and; in still other
cases
about 0.6 dgimin.
In embodiments of the present disclosure, the polyethylene product may have a
melt index 12 of from about 0.05 dg/min to about 500 dg/min, or from about 0.1
dg/min
to about 400 dg/min, or from 0.1 dg/min to about 300 dg/min, or from about 0.1
dg/min
to about 200 dg/min, or from about 0.1 dg/min to about 100 dg/min, or from 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
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0.1 dg/min to about 10 dg/min, or from about 0.1 dg/min to about 5.0 dg/min,
or from
about 0.1 dg/min to about 3.0 dg/min.
In an embodiment of the disclosure, the polyethylene product may have a melt
index ratio, 121/12 of from about 10 to about 35, wherein 121 and 12 are the
melt indexes
measured at 190 C using 21.16 kg and 2.16 kg loads respectively. In another
embodiment of the disclosure, the polyethylene product may have a melt index
ratio,
121/12 of from about 10 to about 30. In yet another embodiment of the
disclosure, the
polyethylene product may have a melt index ratio 121/12 of less than about 30.
In an embodiment of the disclosure the polyethylene product may have a
unimodal profile in a gel permeation chromatograph.
In an embodiment of the disclosure the polyethylene product may have a
multimodal TREF profile in a temperature rising elution fractionation graph.
In the
context of TREF analysis, the term "multimodal" connotes a TREF profile in
which two
=
or more distinct elution peaks are observable.
In an embodiment of the disclosure the polyethylene product may have a
trimodal TREF profile in a temperature rising elution fractionation graph. In
the
context of TREF analysis, the term "trimodal" connotes a TREF profile in which
three
distinct elution peaks are observable.
In an embodiment of the disclosure the polyethylene product may have at least
about 10 weight percent of the product eluting at a temperature of from 90 C
to 100 C
in a TREF analysis. In another embodiment of the disclosure the polyethylene
product may have at least about 15 weight percent of the product eluting at a
temperature of from 90 C to 100 C in a TREF analysis. In another embodiment of
the
disclosure the polyethylene product may have at least about 17.5 weight
percent of
the product eluting at a temperature of from 90 C to 100 C in a TREF analysis.
In
another embodiment of the disclosure the polyethylene product may have at
least
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about 20 weight percent of the product eluting at a temperature of from 90 C
to 100 C
in a TREF analysis. In another embodiment of the disclosure the polyethylene
product may have at least about 22.5 weight percent of the product eluting at
a
temperature of from 90 C to 100 C in a TREF analysis. In another embodiment of
the
disclosure the polyethylene product may have at least about 25 weight percent
of the
=
product eluting at a temperature of from 90 C to 100 C in a TREF analysis.
In an embodiment of the disclosure the polyethylene product may have a
multimodal profile in a differential scanning calorimetry (DSC) graph. In the
context of
DSC analysis, the term "multimodal" connotes a DSC profile in which two or
more
distinct peaks are observable.
In an embodiment of the disclosure the polyethylene product may have a
trimodal profile in a differential scanning calorimetry (DSC) graph. In the
context of
DSC analysis, the term "trimodal" connotes a DSC profile in which three
distinct peaks
are observable.
In an embodiment of the disclosure, the polyethylene product will have will
have an inverse (i.e. "reverse") or partially inverse 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 "reverse comonomer distribution" and "partially
reverse
comonomer distribution" mean that in the GPC-FTIR data obtained for the
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 the ethylene copolymer, comonomer contents for the various
polymer
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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".
In an embodiment of the disclosure the polyethylene product has a reversed
comonomer distribution profile as measured using GPC-FTIR.
In an embodiment of the disclosure the polyethylene product has a partially
.. reverse comonomer distribution profile as measured using GPC-FTIR.
In an embodiment of the disclosure the polyethylene product has a "partially
reverse" comonomer distribution profile and shows a peak or a maximum in the
comonomer distribution profile as measured using GPC-FTIR.
In an embodiment of the disclosure the polyethylene product is produced in a
.. continuous solution polymerization process.
In an embodiment of the disclosure the polyethylene product is produced in a
continuous solution polymerization process comprising a first and second
reactor
configured in parallel in parallel to one another.
In an embodiment of the disclosure the polyethylene product is produced in a
.. continuous solution polymerization process comprising a first, second and
third
reactor, where the first and second reactor are configured in parallel to one
another,
and the third reactor receives the combined effluent streams from the first
and second
reactors.
In an embodiment of the disclosure the first polyethylene is produced with a
single site catalyst system.
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In an embodiment of the disclosure the first polyethylene is homogeneous
polyethylene.
In an embodiment of the disclosure the second polyethylene is produced with a
single site catalyst system.
In an embodiment of the disclosure the second polyethylene is homogeneous
polyethylene.
In an embodiment of the disclosure the third polyethylene is produced with
single site catalyst system.
In an embodiment of the disclosure the third polyethylene is produced with a
Ziegler-Natta catalyst system.
In an embodiment of the disclosure the first polyethylene and the second
polyethylene are produced with a single site catalyst system.
In an embodiment of the disclosure the first polyethylene and the second
polyethylene are homogeneous polyethylenes.
In an embodiment of the disclosure the first polyethylene, the second
polyethylene and the third polyethylene are produced with a single site
catalyst
system.
In an embodiment of the disclosure the first polyethylene and the second
polyethylene are produced with a single site catalyst system, while the third
polyethylene is produced with a Ziegler-Natta catalyst system.
In an embodiment of the disclosure the polyethylene product has substantially
no long chain branching. By the term "substantially no long chain branching",
it is
meant that the polyethylene product has less than 0.03 long chain branches per
thousand carbons.
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In an embodiment of the disclosure the polyethylene product has a storage
modulus G'(@G"=500 Pa) value of less than about 38, or less than about 36, or
less
than about 34.
In an embodiment of the disclosure, the polyethylene product has a DRI, of
less
than about 0.55, wherein the DRI, is the "dow rheology index" , defined by the
equation: DR/4365000(To/no)-1]/10; wherein TO is the characteristic relaxation
time of
the polyethylene and no is the zero shear viscosity of the material. The DRI
is
calculated by least squares fit of the rheological curve (dynamic complex
viscosity
versus applied frequency eg. 0.01-100 rads/s) as described in U.S. Pat. No.
6,114,486
with the following generalized Cross equation, i.e. n(w)=n0/[1+(wTo)]; wherein
n is the
power law index of the material, n(w) and w are the measured complex viscosity
and
applied frequency data respectively.
In an embodiment of the disclosure, the polyethylene product has a DRI of 5
0.55, or 5 0.50, or 5 0.45, or 5 0.40, or 5 0.35, or 5. 0.30.
The catalyst residues in the polyethylene product reflect the chemical
compositions of: the single-site catalyst system employed in reactors 1 and 2,
and if
present, the second catalyst system employed in reactor 3.
The catalyst residues in the polyethylene product reflect the chemical
compositions of: the single-site catalyst system employed in reactors 1 and 2,
and if
present, the second catalyst system employed in reactor 3.
The polyethylene products 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 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
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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.
Depending on the end-use application, the disclosed polyethylene products
may be converted into films that span a wide range of thicknesses. Non-
limiting
examples include, food packaging films where thicknesses may range from about
0.5
mil (13 pm) to about 4 mil (102 pm), and; in heavy duty sack applications film
thickness may range from about 2 mil (51 pm) to about 10 mil (254 pm).
The polyethylene products disclosed herein may be used in monolayer films;
where the monolayer may contain more than one polyethylene product and/or
additional thermoplastics; non-limiting examples of thermoplastics include
polyethylene polymers and propylene polymers. The lower limit on the weight
percent
of the polyethylene product in a monolayer film may be about 3 wt%, in other
cases
about 10 wt% and in still other cases about 30 wt%. The upper limit on the
weight
percent of the polyethylene product in the monolayer film may be 100 wt%, in
other
cases about 90 wt% and in still other cases about 70 wt%.
The polyethylene products disclosed herein may also be used in one or more
layers of a multilayer film; non-limiting examples of multilayer films include
three, five,
seven, nine, eleven or more layers. The thickness of a specific layer
(containing an
polyethylene product) within a multilayer film may be about 5%, in other cases
about
15% and in still other cases about 30% of the total multilayer film thickness.
In other
embodiments, the thickness of a specific layer (containing the polyethylene
product)
within a multilayer film may be about 95%, in other cases about 80% and in
still other
cases about 65% of the total multilayer film thickness. Each individual layer
of a
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multilayer film may contain more than one polyethylene product and/or
additional
thermoplastics.
Additional embodiments include laminations and coatings, wherein mono or
multilayer films containing the disclosed polyethylene products are extrusion
laminated or adhesively laminated or extrusion coated. In extrusion lamination
or
adhesive lamination, two or more substrates are bonded together with a
thermoplastic
or an adhesive, respectively. In extrusion coating, a thermoplastic is applied
to the
surface of a substrate. These processes are well known to those experienced in
the
art. Frequently, adhesive lamination or extrusion lamination are used to bond
dissimilar materials, non-limiting examples include the bonding of a paper web
to a
thermoplastic web, or the bonding of an aluminum foil containing web to a
thermoplastic web, or the bonding of two thermoplastic webs that are
chemically
incompatible, e.g. the bonding of a polyethylene product containing web to a
polyester
or polyamide web. Prior to lamination, the web containing the disclosed
polyethylene
product(s) may be monolayer or multilayer. Prior to lamination the individual
webs
may be surface treated to improve the bonding, a non-limiting example of a
surface
treatment is corona treating. A primary web or film may be laminated on its
upper
surface, its lower surface, or both its upper and lower surfaces with a
secondary web.
A secondary web and a tertiary web could be laminated to the primary web;
wherein
the secondary and tertiary webs differ in chemical composition. As non-
limiting
examples, secondary or tertiary webs may include; polyamide, polyester and
polypropylene, or webs containing barrier resin layers such as EVOH. Such webs
may also contain a vapor deposited barrier layer; for example a thin silicon
oxide
(SiOx) or aluminum oxide (A10x) layer. Multilayer webs (or films) may contain
three,
five, seven, nine, eleven or more layers.
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The polyethylene products 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 polyethylene product include laminates and/or
multilayer
films; sealants and tie layers in multilayer films and composites; laminations
with
paper; aluminum foil laminates or laminates containing vacuum deposited
aluminum;
polyamide laminates; polyester laminates; extrusion coated laminates, and; hot-
melt
adhesive formulations. The manufactured articles summarized in this paragraph
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contain at least one film (monolayer or multilayer) comprising at least one
embodiment
of the disclosed polyethylene products.
Desired film physical properties (monolayer or multilayer) typically depend on
the application of interest. Non-limiting examples of desirable film
properties include:
optical properties (gloss, haze and clarity), dart impact, Elmendorf tear,
modulus (1%
and 2% secant modulus), 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
polyethylene products are easy to process on film lines. Those skilled in the
art
frequently use the term "processability" to differentiate polymers with
improved
.. processability, relative to polymers with inferior processability. A
commonly used
measure to quantify processability is extrusion pressure; more specifically, a
polymer
with improved processability has a lower extrusion pressure (on a blown film
or a cast
film extrusion line) relative to a polymer with inferior processability.
In an embodiment of the disclosure, a film or film layer comprises the
polyethylene product described above.
In embodiments of the disclosure, a film will have a dart impact of 500 g/mil,
or 550 g/mil, or 600 g/mil, or 650 g/mil, or 700 g/mil. In another
embodiment of
the disclosure, a film will have a dart impact of from 500 g/mil to 950 g/mil.
In a further
embodiment of the disclosure, a film will have dart impact of from 550 g/mil
to 850
g/mil. In yet another embodiment of the disclosure, the film will have dart
impact of
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from 600 g/mil to 850 g/mil. In still yet another embodiment of the
disclosure, a film
will have dart impact of from 600 g/mil to 800 g/mil.
In embodiments of the disclosure, a 1 mil film will have a machine direction
(MD) secant modulus at 1% strain of 150 MPa, or 160 MPa, or 170 MPa, or
175 MPa, or 180 MPa, or 185 MPa, or 190 MPa, or 195 MPa, or 200 MPa.
In an embodiment of the disclosure, a 1 mil film will have a machine direction
(MD)
secant modulus at 1% strain of from 150 MPa to 240 MPa. In an embodiment of
the
disclosure, a 1 mil film will have a machine direction (MD) secant modulus at
1%
strain of from 160 MPa to 230 MPa. In another embodiment of the disclosure, a
1 mil
film will have a machine direction (MD) secant modulus at 1% strain of from
170 MPa
to 230 MPa. In yet another embodiment of the disclosure, a 1 mil film will
have a
machine direction (MD) secant modulus at 1% strain of from 170 MPa to 220 MPa.
In an embodiment of the disclosure, a 1 mil film will have a transverse
direction
(TD) secant modulus at 1% strain of 190 MPa, or 200 MPa, or ?. 210 MPa, or
220 MPa, or 230 MPa.. In an embodiment of the disclosure, a 1 mil film will
have a
transverse direction (TD) secant modulus at 1% strain of from 180 MPa to 400
MPa.
In another embodiment of the disclosure, a 1 mil film will have a transverse
direction
(TD) secant modulus at 1% strain of from 180 MPa to 300 MPa. In yet another
embodiment of the disclosure, a 1 mil film will have a transverse direction
(TD) secant
modulus at 1% strain of from 200 MPa to 280 MPa.
In embodiments of the disclosure, a 1 mil film will have a machine direction
(MD) tensile strength at break of 35 MPa, or 40 MPa, or 45 MPa, or 50 MPa,
or 55 MPa. In an embodiment of the disclosure, a 1 mil film will have a
machine
direction tensile strength at break of from 30 MPa to 70 MPa. In an embodiment
of
the disclosure, a 1 mil film will have a machine direction (MD) tensile
strength at break
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of from 35 MPa to 65 MPa. In another embodiment of the disclosure, a 1 mil
film will
have a machine direction (MD) tensile strength at break of from 40 MPa to 65
MPa.
In embodiments of the disclosure, a film will have a machine direction (MD)
tear
strength of 200 g/mil, or 210 g/mil, or 220 g/mil, or 230 g/mil, or 240 g/mil,
or
250 g/mil, or ?. 260 g/mil, or 270 g/mil, or 275 g/mil. In an embodiment of
the
disclosure, a film will have a machine direction (MD) tear strength of from
220 g/mil to
375 g/mil. In an embodiment of the disclosure, a film will have a machine
direction
(MD) tear strength of from 230 g/mil to 375 g/mil. In an embodiment of the
disclosure,
a film will have a machine direction (MD) tear strength of from 240 g/mil to
375 g/mil.
In an embodiment of the disclosure, a film will have a machine direction (MD)
tear
strength of from 250 g/mil to 375 g/mil. In an embodiment of the disclosure, a
film will
have a machine direction (MD) tear strength of from 250 g/mil to 350 g/mil.
In embodiments of the disclosure, a 1 mil film will have a slow puncture
resistance value of 55 J/mm, or 60 J/mm, or 65 J/mm, or 70 J/mm, or 75
J/mm, or 80 J/mm, or 85 J/mm. In embodiments of the disclosure, a 1 mil film
will
have a slow puncture value of from 55 J/mm to 95 J/mm, or from 60 J/mm to 90
J/mm,
or from 65 J/mm to 90 J/mm.
In embodiments of the disclosure, a 1 mil film will have a haze of 5. 16%, or
5
15%, 5. 14%, or 13%, or 5 12%, or 5 11%, or 10%. In embodiments of the
disclosure, a 1mil film will have a haze of from 6% to 16%, or from 8% to 14%.
In embodiments of the disclosure, a 1 mil film will have a seal initiation
temperature of 115 C, or 5_ 110 C, or 105 C, or 100 C. In an embodiment of the
disclosure, a 1 mil film will have a seal initiation temperature (SIT) of
between 90 C
and 115 C. In an embodiment of the disclosure, a film will have a seal
initiation
temperature (SIT) of between 95 C and 105 C. In an embodiment of the
disclosure, a
film will have a seal initiation temperature (SIT) of between 95 C and 100 C.
In an
73
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embodiment of the disclosure, a film will have a seal initiation temperature
(SIT) of
between 90 C and 100 C.
Some embodiments of the present disclosure provide films with improvements
in at least two or more of the following properties: dart impact, machine
direction (MD)
modulus (1% and/or 2%), machine direction (MD) tensile strength at break,
machine
direction (MD) tear, slow puncture resistance, haze, and seal initiation
temperature
relative to films formed from comparative polyethylenes. Hence, in an
embodiment of
the disclosure, a 1 mil film has a dart impact strength of 600 g/mil, a MD 1%
secant
modulus of 170 MPa, a MD tensile strength at break of 40 MPa, a machine
direction (MD) tear of 250 g/mil, a slow puncture value of 65 J/mm, a haze of
less
5 14%, and a seal initiation temperature (SIT) of 5 105 C. In another
embodiment of
the disclosure, a 1 mil film has a dart impact strength of 600 g/mil, a MD 1%
secant
modulus of 170 MPa, a slow puncture value of 65 J/mm, a machine direction (MD)
tear of 250 g/mil, and seal initiation temperature (SIT) of 5 105 C.
In an embodiment of the disclosure, the films manufactured using the inventive
compositions will have good hot tack performance. Good hot tack performance is
generally associated with good film performance in bag or pouch packaging
lines,
such as vertical-form-fill-seal (VFFS) applications lines. Without wishing to
be bound
by theory, in the hot tack profile (seal temperature vs. force), good hot tack
performance is indicated by an early (or low) hot tack initiation temperature,
then a
relatively high force over a wide range of seal temperatures.
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,
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colorants, dyes, filler materials, light stabilizers, light absorbers,
lubricants, pigments,
plasticizers, nucleating agents and combinations thereof.
The ethylene polymer products disclosed herein may be used to produce rigid
manufactured articles, non-limiting examples include: deli containers,
margarine tubs,
drink cups and produce trays; household and industrial containers, cups,
bottles, pails,
crates, tanks, drums, bumpers, lids, industrial bulk containers, industrial
vessels,
material handling containers, bottle cap liners, bottle caps, living hinge
closures; toys,
playground equipment, recreational equipment, boats, marine and safety
equipment;
wire and cable applications such as power cables, communication cables and
conduits; flexible tubing and hoses; pipe applications including both pressure
pipe and
non-pressure pipe markets, e.g. natural gas distribution, water mains,
interior
plumbing, storm sewer, sanitary sewer, corrugated pipes and conduit; foamed
articles
manufactured from foamed sheet or bun foam; military packaging (equipment and
ready meals); personal care packaging, diapers and sanitary products;
cosmetic,
pharmaceutical and medical packaging, and; truck bed liners, pallets and
automotive
dunnage. The rigid manufactured articles summarized in this paragraph contain
one
or more of the ethylene polymer products disclosed herein or a blend of at
least one of
the ethylene polymer products disclosed herein with at least one other
thermoplastic.
Such rigid manufactured articles may be fabricated using the following non-
limiting processes: injection molding, compression molding, blow molding,
rotomolding, profile extrusion, pipe extrusion, sheet thermoforming and
foaming
processes employing chemical or physical blowing agents.
The desired physical properties of rigid manufactured articles depend on the
application of interest. Non-limiting examples of desired properties include:
flexural
modulus (1% and 2% secant modulus); tensile toughness; environmental stress
crack
resistance (ESCR); slow crack growth resistance (PENT); abrasion resistance;
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hardness; deflection temperature under load; VICAT softening point; IZOD
impact
strength; ARM impact resistance; Charpy impact resistance, and; color
(whiteness
and/or yellowness index).
A further objective, of the present disclosure is to provide rigid
manufactured
.. articles comprising the ethylene polymer products disclosed herein that
have
improvements in at least one desirable physical property; relative to rigid
manufactured articles formed from comparative ethylene polymers.
The rigid manufactured articles described in this section may optionally
include,
depending on its intended use, additives and adjuvants. Non-limiting examples
of
additives and adjuvants include, antioxidants, slip agents, processing aids,
anti-static
additives, colorants, dyes, filler materials, heat stabilizers, light
stabilizers, light
absorbers, lubricants, pigments, plasticizers, nucleating agents and
combinations
thereof.
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
Test Methods
Prior to testing, each specimen was conditioned for at least 24 hours at 23
2 C and 50 10% relative humidity and subsequent testing was conducted at 23
2 C and 50 10% relative humidity. Herein, the term "ASTM conditions" refers
to a
laboratory that is maintained at 23 2 C and 50 10% relative humidity; and
specimens to be tested were conditioned for at least 24 hours in this
laboratory prior
to testing. ASTM refers to the American Society for Testing and Materials.
Polyethylene product densities were determined using ASTM D792-13
(November 1, 2013).
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Polyethylene product melt index was determined using ASTM D1238 (August
1, 2013). Melt indexes, 12, 16, ho and 121 were measured at 190 C, using
weights of
2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively. Herein, the term "stress
exponent"
or its acronym "S.Ex.", is defined by the following relationship: S.Ex. log
.. (16/12)/log(6480/2160); wherein 16 and 12 are the melt flow rates measured
at 190 C
using 6.48 kg and 2.16 kg loads, respectively.
Polyethylene product molecular weights, Mn, Mw and Mz, as well the as the
polydispersity (Mw/Mn), were determined using ASTM D6474-12 (December 15,
2012).
This method illuminates the molecular weight distributions of polyethylene
polymer
products by high temperature gel permeation chromatography (GPC). The method
uses commercially available polystyrene standards to calibrate the GPC.
The "Composition Distribution Branching Index" or "CDBI" of the Inventive
Examples and Comparative Examples were determined using a crystal-TREF unit
commercially available form Polymer ChAR (Valencia, Spain). The acronym "TREF"
refers to Temperature Rising Elution Fractionation. A sample of ethylene
polymer
product (80 to 100 mg) was placed in the reactor of the Polymer ChAR crystal-
TREF
unit, the reactor was filled with 35 ml of 1,2,4-trichlorobenzene (TCB),
heated to 150 C
and held at this temperature for 2 hours to dissolve the sample. An aliquot of
the TCB
solution (1.5 mL) was then loaded into the Polymer ChAR TREF column filled
with
stainless steel beads and the column was equilibrated for 45 minutes at 110 C.
The
polyethylene product was then crystallized from the TCB solution, in the TREF
column, by slowly cooling the column from 110 C to 30 C using a cooling rate
of
0.09 C per minute. The TREF column was then equilibrated at 30 C for 30
minutes.
The crystallized polyethylene product was then eluted from the TREF column by
passing pure TCB solvent through the column at a flow rate of 0.75 mL/minute
as the
temperature of the column was slowly increased from 30 C to 120 C using a
heating
77
HACMCBSpec\2016028Canadadocx
rate of 0.25 C per minute. Using Polymer ChAR software a TREF distribution
curve
was generated as the polyethylene product was eluted from the TREF column,
i.e. a
TREF distribution curve is a plot of the quantity (or intensity) of
polyethylene product
eluting from the column as a function of TREF elution temperature. A CDBI50
was
calculated from the TREF distribution curve for each polyethylene product
analyzed.
The "CDBI50" is defined as the weight percent of ethylene polymer whose
composition
is within 50% of the median comonomer composition (50% on each side of the
median comonomer composition); it is calculated from the TREF composition
distribution curve and the normalized cumulative integral of the TREF
composition
distribution curve. Those skilled in the art will understand that a
calibration curve is
required to convert a TREF elution temperature to comonomer content, i.e. the
amount of comonomer in the polyethylene product fraction that elutes at a
specific
temperature. The generation of such calibration curves are described in the
prior art,
e.g. Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages
441-455. The
"CDBI25" is defined as the weight percent of polyethylene product whose
composition
is within 25% of the median comonomer composition (25% on each side of the
median comonomer composition).
Dynamic mechanical analyses were carried out with a rheometer, namely
Rheometrics Dynamic Spectrometer (RDS-II) or Rheometrics 5R5 or ATS
Stresstech,
on compression molded samples under nitrogen atmosphere at 190 C, using 25 mm
diameter cone and plate geometry. The oscillatory shear experiments were done
within the linear viscoelastic range of strain (10% strain) at frequencies
from 0.05 to
100 rad/s. The values of storage modulus (G'), loss modulus (G"), complex
modulus
(G*) and complex viscosity (i*) were obtained as a function of frequency. The
same
rheological data can also be obtained by using a 25 mm diameter parallel plate
geometry at 190 C under nitrogen atmosphere.
78
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CA 2964563 2017-04-19
Film dart impact strength was determined using ASTM D1709-09 Method A
(May 1, 2009). In this disclosure the dart impact test employed a 1.5 inch (38
mm)
diameter hemispherical headed dart.
Film "puncture", or "slow puncture" is the energy (J/mm) required to break the
film was determined using ASTM D5748-95 (originally adopted in 1995,
reapproved in
2012).
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 pm) thick, 5.5 inch (14 cm) wide and 6 inch (15 cm) long) were
mounted in
the Instron and punctured.
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.
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%;
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given these two points the 1% secant modulus is calculated and is expressed in
terms
of force per unit area (MPa). The 2% secant modulus is calculated similarly.
This
method is used to calculated film modulus because the stress-strain
relationship of
polyethylene does not follow Hook's law; i.e. the stress-strain behavior of
polyethylene
is non-linear due to its viscoelastic nature. Secant moduli were measured
using a
conventional Instron tensile tester equipped with a 200 lbf load cell. Strips
of
monolayer film samples were cut for testing with following dimensions: 14 inch
long, 1
inch wide and 1 mil thick; ensuring that there were no nicks or cuts on the
edges of
the samples. Film samples were cut in both the machine direction (MD) and the
transverse direction (TD) and tested. ASTM conditions were used to condition
the
samples. The thickness of each film was accurately measured with a hand-held
micrometer and entered along with the sample name into the Instron software.
Samples were loaded in the Instron with a grip separation of 10 inch and
pulled at a
rate of 1 inch/min generating the strain-strain curve. The 1% and 2% secant
modulus
=
were calculated using the Instron software.
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 tear performance was determined by ASTM D1922-09 (May 1, 2009); an
equivalent term for tear is "Elmendorf tear". Film tear was measured in both
the
machine direction (MD) and the transverse direction (TD) of the blown films.
Film optical properties were measured as follows: Haze, ASTM D1003-13
(November 15, 2013), and; Gloss ASTM D2457-13 (April 1,2013).
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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 - M) thick film), i.e. when
the
polyolefin macromolecules that comprise the film are in a semi-molten state.
This test
simulates the heat sealing of polyethylene films on high speed automatic
packaging
machines, e.g., vertical or horizontal form, fill and seal equipment. The
following
parameters were used in the J&B Hot Tack Test: film specimen width, 1 inch
(25.4
mm); film sealing time, 0.5 second; film sealing pressure, 0.27 N/mnn2; delay
time, 0.5
second; film peel speed, 7.9 in/second (200 mm/second); testing temperature
range,
203 F to 293 F (95 C to 145 C); temperature increments, 9 F (5 C); and five
film
samples were tested at each temperature increment to calculate average values
at
each temperature. The following data was recorded for the Inventive Example
films
and Comparative Example films: the "Tack Onset @ 1.0 N ( C)", the temperature
at
which a hot tack force of 1N was observed (average of 5-film samples); "Max
Hot tack
Strength (N)", the maximum hot tack force observed (average of 5-film samples)
over
the testing temperature range, and; "Temperature ¨ Max. Hot tack ( C)", the
temperature at which the maximum hot tack force was observed.
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 (51-1.tm) 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
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sealing time, 0.5 second; film sealing pressure, 40 psi (0.28 N/mm2);
temperature
range, 212 F to 302 F (100 C to 150 C) and temperature increment, 9 F (5 C).
After
aging for at least 24 hours at ASTM conditions, seal strength was determined
using
the following tensile parameters: pull (crosshead) speed, 12 inch/min (2.54
cm/min);
direction of pull, 900 to seal, and; 5 samples of film were tested at each
temperature
increment. The Seal Initiation Temperature, hereafter S.I.T., is defined as
the
temperature required to form a commercially viable seal; a commercially viable
seal
has a seal strength of 2.0 lb per inch of seal (8.8 N per 25.4 mm of seal).
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 p.m) 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 (wC6): wC6 100 x (w1-wf)/wi.
Polymerization
Embodiments of the polyethylene products were prepared in a pilot plant using
two CSTR reactors configured in parallel (reactors 1 and 2), followed by a
tubular
reactor (reactor 3) as represented by the continuous solution polymerization
process
shown in Figure 1. In the inventive examples, ethylene was fed to reactor 3.
Comparative polyethylene products were prepared similarly and according to the
continuous solution polymerization process shown in Figure 1, expect for that
fact that
ethylene was not fed to reactor 3.
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
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(12 L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L) and
the
volume of the tubular reactor (R3) was 0.58 gallons (2.2 L) or 4.8 gallons (18
L). The
R1 pressure was from about 14 MPa to about 18 MPa; the R2 pressure was from
about 14 MPa to about 18 MPa. Reactor 3 was operated at a lower pressure to
facilitate continuous flow from reactors 1 and 2 toward reactor 3. R1 and R2
were
configured in parallel to each other, and the combined exit streams from
reactor 1 and
2, streams 1' and 2' respectively were fed to reactor 3. Both CSTR's were
agitated to
give conditions in which the reactor contents were well mixed. The process was
operated continuously by feeding fresh process solvent, ethylene, 1-octene and
hydrogen to the reactors, as described under the reactor conditions given in
Table 1.
The single site catalyst system components were fed to both of reactors 1 and
2 and included: component (a), cyclopentadienyl tri(tertiary
butyl)phosphinimine
titanium dichloride, Cp((t-Bu)3PN)TiC12; component (b), modified
methylaluminoxane
(M MAO-07); component (c), trityl tetrakis(pentafluoro-phenyl)borate, and;
component
(d), 2,6-di-tert-butyl-4-ethylphenol.
The single site catalyst system component solvents used were methylpentane
for catalyst components (b) and (d) and xylene for catalyst components (a) and
(c).
The average residence time of the solvent in a reactor was primarily
influenced
by the amount of solvent flowing through each reactor and the total amount of
solvent
flowing through the solution process. The following are representative or
typical
values for the examples shown in Table 1: average reactor residence times
were:
about 8.2 seconds in R1, about 36 seconds in R2, about 6 seconds for an R3
volume
of 0.58 gallons (2.2 L), and about 65 seconds for an R3 volume of 4.8 gallons
(18L).
Hence, if the polymerization reaction was left to proceed in reactor 3 for a
relatively
short period of time, then a catalyst deactivator was added to reactor 3 at a
point at
which about 2.2 L of volume of the reactor was utilized for polymerization
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(Comparative Example 1); alternatively, if the polymerization reaction was
left to
proceed in reactor 3 for a relatively long period of time, then a catalyst
deactivator was
added to reactor 3 to terminate the reaction near the exit of the tubular
reactor (R3), at
a point at which about 18L of volume of the reactor was utilized for
polymerization
(Comparative Example 2, and Inventive Examples 1-5). For the Inventive
Examples,
ethylene monomer was fed to the third reactor at a point at which about 2.2 L
of
volume of the reactor was utilized for polymerization (Inventive Examples 1-
5). For
the Comparative Examples 1 and 2, no ethylene monomer was fed to the third
reactor.
The catalyst deactivator used was octanoic acid (caprylic acid), commercially
available from P&G Chemicals, Cincinnati, OH, U.S.A. The catalyst deactivator
was
added such that the moles of fatty acid added were 50% of the total molar
amount of
titanium and aluminum added to the polymerization process; to be clear, the
moles of
octanoic acid added = 0.5 x (moles titanium + moles aluminum); this mole ratio
was
consistently used in all examples.
A two-stage devolitizing process was employed to recover the final
polyethylene product from the process solvent, i.e. two vapor/liquid
separators were
used and the second bottom stream (from the second V/L separator) was passed
through a gear pump/pelletizer combination.
Prior to pelletization the polyethylene product was stabilized by adding 500
ppm of Irganox 1076 (a primary antioxidant) and 500 ppm of Irgafos 168 (a
secondary
antioxidant), based on weight of the polyethylene polymer product.
Antioxidants were
dissolved in process solvent and added between the first and second V/L
separators.
Catalyst system details, reactor conditions and some final polyethylene
product
properties are given in Table 1. Table 1 also discloses process parameters
such as
ethylene and comonomer (i.e. 1-octene) splits ("ES" and "CS") between the
reactors,
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ethylene concentrations in each reactor, ethylene conversions ("Q") in each
reactor,
etc. When carrying out the polymerization process for each of the examples in
Table
1 the targeted polyethylene product was one having a melt index(12) (ASTM
D1239,
2.16kg load,190 C) or 1 g/10min and a density of 0.917 g/cm3 (ASTM D792).
HACliffµCBSpec\2016028Canada.docx
TABLE 1
Example No. Comp. 1 Comp. 2 Inv. 1
Inv. 2
Total solution rate
500.0 500.0 515.7 525.3
(kg/h)
ECR1 (R1 ethylene
8.3 8.1 8.0 8.2
concentration (wt%))
ECR2 (R2 ethylene
13.0 11.9 11.5 11.96
concentration (wt%))
cr,
cr,
ECR3 (R3 ethylene
9.1 8.8 9.5 9.76
concentration (wt%))
ESR1 (%) 70.00 70.00 63.0
63.0
ESR2 ( /0) 30.00 30.00 27.0
27.0
ESR3 (%) 0.0 0.0 10.0
10.0
Comonomer 1-octene 1-octene 1-octene
1-octene
((1-octene)/
0.817 0.850 0.824 0.731
(ethylene))' (wt%)
86
HAClifACBSpec\2016028Canada.docx
. .
. .
CSR1 ( /0) 100.0 100.0 100.0
100.0
csR2 (%) 0 0 0
0.0
CSR3 (%) 0 0 0
0.0
R1 inlet temp ( C) ' 35.0 35.0 35.0
30.0
R2 inlet temp ( C) 54.9 54:9 54.9
44.7
R3 Fresh Feed
130.1 129.2 129.7
130.1
Temperature ( C)
0
QR1 (%) 89.0 89.0 89.0
89.0 .
cõ
0,
QR2 (%) 96.2 96.0 96.8
96.0
,
i
QR3 (%) 27.26 66.6 78.4
82.2 2 ,
QTOTAL (cyc) 93.4 96.9 96.0
92.7
R1 Mean temp ( C) 138.3 135.8 135.0
133.2
R2 Mean temp ( C) 195.4 195.0 189.9
189.8
H2R1 (ppm) 0.40 0.20 0.20
0.20
H2R2 (ppm) 0.47 0.42 0.44
0.10
H2R3 (ppm) 0.0 0.0 0.50
0.52
87
HAClifilCBSpec\2016028Canada.docx
. .
,
R1 Agitator speed (rpm) 690.0 690.0 900.0
800.0
R2 Agitator speed (rpm) ' 690.0 690.0 690.0
690.0
Reactor 1 Pressure 16.0 16.0 16.0
16.0
R1 (a) (ppm) 0.26 0.29 0.26
0.34
_
R1 (b)/(a) mole ratio 65 . 65 65
65 .
R1 (d)/(b) mole ratio 0.30 0.30 0.30
0.30
R1 (c)/(a) mole ratio 1.20 1.20 1.20
1.20
0
R1 Diluent Temperature 29.9 29.9 30.0
15.3 .
cõ
0,
R2 (a) (ppm) 0.27 0.41 0.26
0.98 " ,
i
R2 (b)/(a) mole ratio 65 65 65
65 2 ,
R2 (d)/(b) mole ratio 0.30 0.30 0.30
0.30
R2 (c)/(a) mole ratio 1.50 1.50 1.50
1.50
R2 Diluent Temperature 40.28 41.63 41.69
30.3
R3 inlet temp (actual)
158.0 156.9 154.5 153.5
( C)
88
1-1:1Cliff\CBSpec12016028Canada.docx
=
R3 outlet temp (actual)
172.9 175.4 180.0
( C)
180.7
Heat exchanger outlet
226.7 227.2 229.7
226.6
temperature ( C)
Delta T (the difference
between T(outlet) Heat
54 52 50
46
Exchanger and
T(outlet) of Reactor 3
Reduction in IPS feed
0 4 8
15
heater delta T (%)
Prod. Rate (kg/h) 49.5 50.1 55.1
57.5
Polyethylene Properties
Density (g/cm3) 0.9193 0.9179 0.9174
0.9176
Melt Index 12 (g/10 min) 0.99 0.96 0.97
0.94
Melt Flow Ratio (121/12) 20.1 21 21.2
21.9
Stress Exponent 1.18 1.19 1.2
1.22
89
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Branch Freq/1000C 12.1 13.7 13.9
14.3
Mn 42056 41461 44652
34817
Mw 99753 101177 103913
97619
Mz 185845 184183 193461
185579
Polydispersity Index
2.37 2.44 2.33
2.8
(Mw/Mn)
TABLE 1. CONTINUED
Example No. Inv. 3 Inv. 4
Inv. 5
Total solution rate
525.0 525.0
525.0 2
(kg/h)
ECR1 (R1 ethylene
7.9 8.1
7.6
concentration (wt%))
ECR2 (R2 ethylene
11.4 8.95
12.7
concentration (wt%))
ClifINCBSpe62016028Canada.docx
. ,
ECR3 (R3 ethylene
10.3 10.52
11.4
concentration (wt%))
ESR1 (%) 55.9 56.0
45.0
ESR2 (%) 24.1 24.0
25.0
ESR3 (%) 20.0 20.0
30.0
.
.
Comonomer 1-octene 1-octene
1-octene
((1-octene)/
0.800 0.750
0.760 0
(ethylene)) R1 (wt%)
.
cõ
0,
L.,
CSR1 ( /0) 100.0 100.0
100.0
,
.i,
CSR2 (%) 0 0.0
0 .
CSR3 (%) 0 0.0
0
R1 inlet temp ( C) 35.0 30.0
30.0
R2 inlet temp ( C) 54.9 44.7
40.2
R3 Fresh Feed
129.7 129.8
130.1
Temperature ( C)
cr (%) 89.0 89.1
89.0
91
HACliff\CBSpect2016028Canada.docx
, QR2 (0/0) 96.4
96.0 86.2
QR3 (%) 83.8 81.3 ,
82.4
QTOTAL (%) 95.6 89.6
94.0
R1 Mean temp ( C) 134.3 131.1
127.3
R2 Mean temp ( C) . 190.2 190.8.
195.2
H2R1 (ppm) 0.20 0.20
0.20
H2R2 (ppm) 0.48 0.10
0.10
0
H2R3 (ppm) 0.50 0.62
0.63 .
cõ
0,
L.,
R1 Agitator speed (rpm) 690.0 800.0
690.0 " ,
i
.
.
R2 Agitator speed (rpm) 690.0 690.0
690.0 .
Reactor 1 Pressure 16.0 16.0
16.0
R1 (a) (ppm) 0.31 0.32
0.30
R1 (b)/(a) mole ratio 65 65
65
R1 (d)/(b) mole ratio 0.30 0.30
0.30
R1 (c)/(a) mole ratio 1.20 1.20
1.20
R1 Diluent Temperature 29.9 26.1
18.8
92
HACIMCBSpec\2016028Canada.docx
R2 (a) (ppm) 0.27 1.04
0.52
R2 (b)/(a) mole ratio 65 65
65
R2 (d)/(b) mole ratio 0.30 0.30
0.30
R2 (c)/(a) mole ratio 1.50 1.50
1.50
R2 Diluent Temperature 39.12 48.0
43.17
R3 inlet temp (actual)
154.2 151.6
149.6
( C)
R3 outlet temp (actual)
cr,
188.2 186.2
193.7
cr,
( C)
Heat exchanger outlet
233.5 230.2
237.2
temperature ( C)
Delta T (the difference
between T(outlet) Heat
45 44
44
Exchanger and
T(outlet) of Reactor 3
93
HACliffiCBSpec12016028Canada.docx
Reduction in IFS feed
16 18
19
heater delta T (%)
Prod. Rate (kg/h) 60.7 61.1
66.3
Polyethylene Properties
Density (g/cm3) 0.9175 0.917
0.9163
Melt Index 12 (g/10 min) 1.14 1.03
0.97
Melt Flow Ratio (121/12) 21.6 22
24
Stress Exponent 1.2 1.22
1.24
cr,
cr,
Branch Freq/1000C 14.3 14.8
15.1
Mn 39596 42795
37386 .7
M w 98041 100485
104311
Mz 184559 194174
232013
Polydispersity Index
2.48 2.35 2.79
(Mw/Mn)
94
F1:1Cliff1CBSpec\2016028Canada.docx
CA 2964563 2017-04-19
As can been seen in the data provided in Table 1, in each of the Inventive
examples, where fresh ethylene is fed directly to reactor 3, the productivity
(kg of
polyethylene product per hour) of the polymerization reaction improved
relative to
either of the Comparative Examples, in which no fresh ethylene was fed to
reactor 3.
The productivity generally increased as the amount of ethylene fed to reactor
3
increased.
Also, and importantly, the Inventive Examples show that as the reactor 3
ethylene split ESR3 increased so did the temperature of the reactor 3 effluent
stream
(the "R3 exit temperature"), which in turn reduced the energy burden on the
downstream heat exchanger. Or put another way, since the reactor 3 exit
temperature had increased, less heat must be added by way of the heat
exchanger
prior to feeding the final polyethylene product stream to the solvent
separation system
(i.e. the devolatilization system) in order to carry out efficient separation.
This is
further evidenced by the decrease in the temperature difference between the
reactor 3
outlet temperature and the heat exchanger outlet temperature as well as the
corresponding relative percent decrease in the temperature difference of the
same
relative to Comparative Example 1 (see Table 1).
As a high heat exchanger outlet temperature is desired for efficient
solvent/polymer separation, the present Inventive Examples, provide
improvements in
energy consumption by increasing the temperature of the reactor 3 exit stream
relative
to the Comparative Examples. These improvements reduce energy inputs, improve
cost, and lower environmental impacts.
Polyethylene product composition properties are provided in Table 2. Details
of the polyethylene product composition components, the first, second and
third
polyethylene, were calculated using Copolymerization Reactor modelling in
substantially the same manner as described in U.S. Pat, No. 9,074,082 except
that
CA 2964563 2017-04-19
the model was adapted to the use of three reactors instead of two. The results
of this
modelling are provided in Table 3.
TABLE 2
Example No. Comp. 1 Comp. 2 Inv. 1 Inv. 2
Density
0.9193 0.9179 0.9174 0.9176
(g/cm3)
Melt Index 12
0.99 0.96 0.97 0.94
(g/10 min)
Melt Index 16
3.62 3.54 3.6 3.58
(g/10 min)
Melt Index lio
6.16 6.24 6.31 6.28
(g/10 min)
Melt Index 121
19.8 20.1 20.6 20.7
(g/10 min)
Melt Flow
20.1 21 21.2 21.9
Ratio (121/12)
Stress
1.18 1.19 1.2 1.22
Exponent
Melt Flow
6.36 6.52 6.64 6.74
Ratio (110/12)
=
Rheological Properties
Zero Shear
Viscosity - 8057 8453 8405 9356
190 C (Pa-s)
96
CA 2964563 2017-04-19
Crossover
Frequency- 134.88 106.94 113.81 112.04
190 C (rad/s)
DR I 0.13 0.14 0.13 0.19
agG"500Pa
19.1 19.8 18.4 25.8
Branch Frequency - FTIR
Branch
12.1 13.7 13.9 14.3
Freq/1000C
Comonomer 1-octene 1-octene 1-octene 1-octene
Comonomer
Content 2.4 2.7 2.8 2.9
(mole%)
Comonomer
9.1 10.1 10.3 10.5
Content (wt%)
Internal
0.02 0.023 0.02 0.02
Unsattl 00C
Side Chain
0 0 0.001 0
Unsat/100C
Terminal
0.006 0.008 0.006 0.005
Unsat/100C
CTREF
First Elution
94.9 94.9 95.5 95.4
Peak ( C)
97
CA 2964563 2017-04-19
Second
Elution Peak 78.6 74.6 72.8 72.1
( C)
Third Elution
Peak ( C)
Highest
eluting peak
temp. -
19.3 20.3 22.7 23.3
Lowest
eluting peak
temp. ( C)
CDBI 25 49.8 50.2 52 47.6
CDBI 50 62.6 62 63 61.7
wt.% of
polyethylene
4.6 7.2 7.4 8.6
eluting at from
25 C to 60 C
wt.% of
polyethylene
39.9 46.3 55.3 53.3
eluting at from
65 C to 75 C
wt.% of
=
polyethylene
30.4 22.1 12.5 13.4
eluting at from
75 C to 90 C
98
CA 2964563 2017-04-19
wt.% of
polyethylene
eluting at from 25.1 24.4 24.8 24.7
90 C to
105 C
DSC
First Melting
102.36 101.69 100.18 99.93
Peak ( C)
Second
Melting Peak 121.13 120.86 121.1 121
( C)
Third Melting
124.34 124.36 124.85 124.78
Peak ( C)
Heat of
132.03 127.31 125.53 129.12
Fusion (Jig)
Crystallinity
45.53 43.90 43.28 44.52
(To)
GPC - Conventional
Mn 42056 41461 44652 34817
Mw 99753 101177 103913 97619
Mz 185845 184183 193461 185579
Polydispersity
2.37 2.44 2.33 2.8
Index (Mw/Mn)
Mz/Mw 1.86 1.82 1.86 1.90
99
CA 2964563 2017-04-19
Hexane
Extractables 0.21 0.79 0.55 0.55
= (%) - Plaque
Table 2 CONTINUED
Example No. Inv. 3 Inv. 4 Inv. 5
Density (g/cm3) 0.9175 0.917 0.9163
Melt Index 12 (g/10
1.14 1.03 0.97
min)
Melt Index 16 (g/10
4.26 3.9 3.76
min)
Melt Index ho
7.36 6.58 6.73
(g/10 min) .
Melt Index 121
24.5 22.6 23.2
(g/10 min)
Melt Flow Ratio
21.6 22 24
(121/12)
Stress Exponent 1.2 1.22 1.24
Melt Flow Ratio
6.64 6.8 7.08
(11o/12)
Rheological Properties
Zero Shear
Viscosity - 190 C 7443 9231 9359
=
(Pa-s)
100
CA 2964563 2017-04-19
Crossover
Frequency - 190 C 141.02 121.46 103.74
(rad/s)
DRI 0.17 0.24 0.26
G'@G"500Pa = 21.3 32.4 30.3
Branch Frequency - FTIR
Branch
14.3 14.8 15.1
Freq/1000C
Comonomer ID 1-octene 1-octene 1-octene
Comonomer
2.9 3 3
Content (mole%)
Comonomer
10.5 10.9 11.1
Content (wt%)
Internal .
0.021 0.021 0.023
Unsat/100C
Side Chain
0.001 0.001 0.002
Unsat/100C
Terminal
0.007 0.005 0.007
Unsat/100C
CTREF
First Elution Peak
95.4 95.3 95.2
( C)
Second Elution
83.3 84.4 86.4
Peak ( C)
101
CA 2964563 2017-04-19
Third Elution Peak
70.6 69.6 63.4
( C)
Highest eluting
peak temp. -
24.8 25.7 31.8
Lowest eluting
peak temp. ( C)
CDBI 25 44 43.3 23.4
CDBI 5o 61.8 60.3 46.7
wt.% of
polyethylene
9.2 10.4 19.3
eluting at from
25 C to 60 C
wt.% of
polyethylene
52.4 52.2 35
eluting at from =
65 C to 75 C
wt.% of
polyethylene
14.6 13.9 17.8
eluting at from
75 C to 90 C
wt.% of
polyethylene
23.8 23.5 27.9
eluting at from
90 C to 105 C
DSC
102
CA 2964563 2017-04-19
First Melting Peak
100.12 98.5 95.33
( C)
Second Melting
121.4 121 121.92
Peak ( C)
Third Melting Peak.
125.8 124.6 124.7
( C)
Heat of Fusion
118.66 128.7 133.49
(J/g)
Crystallinity (%) 40.91 44.40 46.03
GPC - Conventional
Mn 39596 42795 37386
Mw 98041 100485 104311
Mz 184559 194174 232013
Polydispersity
2.48 2.35 2.79
Index (Mw/Mn)
Mz/Mw 1.88 1.93 2.22
Hexane
Extractables (%) - 0.56 0.57 0.57
Plaque
TABLE 3
Example No. Comp. 1 Comp. 2 Inv. 1 Inv. 2
Density (g/cm3) 0.9193 0.9179 0.9174 0.9176
103
CA 2964563 2017-04-19
12 (g/10min.) 0.99 0.96 , 0.97 0.94
S.Ex. 1.18 1.19 1.2 1.22
.
MFR(121/12) 20.1- 21 21.2 21.9
Mn 42056 . 41461 44652 34817
Mw . 99753 101177 103913 97619
Mz 185845 184183 193461 185579
Mw/Mn 2.37 2.44 2.33 2.80
Mz/Mw 1.86 1.82 1.86 1.90
First Polyethylene
(R1)
weight fraction, w1 0.708 0.677 0.616 0.613
Mnl 59506 63213 63490 67033
Mw1 119013 126427 126981 134066
Mw/Mn1 2.00 2.00 2.00 2.00
= short chain
branches per 1000
carbons 16 16 18 16
121 (g/10min.) 0.51 0.4 0.4 0.32
dl (g/cm3) 0.9032 0.9016 0.8995 0.9022
Second
Polyethylene (R2)
weight fraction, w2 0.277 0.264 0.239 0.241
Mn2 28833 28821 28718 28713
Mw2 57667 57642 57437 57426
' 104
CA 2964563 2017-04-19
Mw/Mn2 2.00 2.00 2.00 2.00
short chain '
branches per 1000
carbons 0 0 0 0
_
122 (g/10min) 7.56 7.58 7.7 7.71
d2 (g/cm3) 0.9559 0.9559 0.9559 0.9559
Third Polyethylene
(R3)
weight fraction, w3 0.016 0.059 0.145 0.146
Mn3 12074 5520 12696 14050
Mw3 24299 15044 44683 50887
Mw/Mn3 2.01 2.73 3.52 3.62
short chain
branches per 1000
carbons 30 47 26 24
123 (g/10min) 221 1566 23.4 14.2
d3 (g/cm3)" 0.8982 0.8815 0.9033 0.9057
(R2 Mw2 - R1
Mw1)/R2 Mw2 -106.4% -119.3% -121.1% -133.5%
(R3 Mw3 - R2
Mw2)/R3 Mw3 -137.3% -283.2% -28.5% -12.9%
(R3 Mw3 - R1
Mwl )/R3 Mw3 -389.8% -740.4% -184.2% -163.5%
105
CA 2964563 2017-04-19
TABLE 3 CONTINUED
Example No. Inv. 3 Inv. 4 Inv. 5
Density (g/cm3) 0.9175 0.917 0.9163
12 (g/10min.) 1.14 1.03 0.97
S.Ex. 1.2 1.22 1.24
MFR (121/12) 21.6 22 24
Mn 39596 42795 37386
Mw 98041 100485 104311
Mz 194559 194174 232013
Mw/Mn 2.48 2.35 2.79
Mz/Mw 1.98 1.93 2.22
First Polyethylene
(R1)
weight fraction, w1 0.558 0.555 0.467
=
= Mn1 59688 61496
56384
Mwl 119376 122990 112769
Mw/Mn1 2.00 2.00 2.00
short chain
branches per 1000
carbons 19 18 22
121 (g/10min.) 0.5 0.44 0.61
dl (g/cm3) 0.8976 0.8991 0.8929
Second
Polyethylene (R2)
106
= CA 2964563 2017-04-19
weight fraction, w2 0.214 0.214 0.226
Mn2 31966 31958
28829
Mw2 63932 63917
57659
= Mw/Mn2 2.00
2.00 2.00
short chain
branches per 1000
carbons 0 0 0
122 (g/1 Omin.) 5.07 5.07 7.57
d2 (g/cm3) 0.955 0.955
0.9559
Third
Polyethylene (R3)
weight fraction, w3 0.228 0.231 0.307
Mn3 19607 19642
26449
Mw3 85474 90488
122892
Mw/Mn3 4.36 4.61 4.65
short chain
branches per 1000
carbons . 17 17 13
123 (g/10min.) 2.25 1.55 0.53
d3 (g/cm3) 0.9128 0.9132 0.9185
(R2 Mw2 - Al
Mw1)/R2 Mw2 -86.7% -92.4% -95.6%
(R3 Mw3 - R2
Mw2)/R3 Mw3 25.2% 29.4% 53.1%
107
CA 2964563 2017-04-19
(R3 Mw3 R1
Mw1)/R3 Mw3 -39.7% -35.9% 8.2%
108
CA 2964563 2017-04-19
With reference to Figures 4A and 4B, a person skilled in the art will
recognize
that the inventive polyethylene product compositions have a reverse comonomer
incorporation, and indeed that in some cases (inventive examples 2, 4 and 5)
the
comonomer incorporation is partially reverse (i.e. it first rises as molecular
weight
increases, and then falls as the molecular weight increases still further).
With reference to Figures 5A and 5B, a person skilled in the art will
recognize
that the inventive polyethylene product compositions have a multimodal TREF
profile.
For comparative examples 1 and 2, as well as inventive examples 1 and 2 the
TREF
profile is bimodal. For inventive examples 3, 4 and 5 the TREF profile is
trimodal. In
each of the inventive examples 1, 2, 3, 4 and 5, more than 10 weight percent
of the
polyethylene product composition elutes at a temperature of between about 90 C
and
about 100 C.
With reference to Figure 6A and 6B, a person skilled in the art will recognize
that the inventive polyethylene product compositions have a multimodal DSC
profile.
For examples 1, 2, 3, 4 and 5 the DSC profile is at least trimodal.
Blown films were generated by using a 2.5-inch Gloucester blown film line (L/D
= 24) with a die diameter of 4-inch. 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 fixed conditions were die gap of 35 mils (0.0889 cm), frost line
height of
about 17 inches and output of 100 lbs/hr. Films were collected under different
orientation conditions. The monolayer 1-mil film was produced with a blow up
ratio
(BUR) of 2.5 and the 1-mil films 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. Data for film blown from the polyethylene product
compositions of
the present disclosure is provided in Table 4, along with data for films made
from
various comparative resins.
109
CA 2964563 2017-04-19
Comparative Example A is a film made from FP117-CTm, a resin commercially
available from the NOVA Chemicals Company. FP117-CTm has a density of 0.917
g/cm3 and a melt index 12 of 1 dg/min. Comparative Example B is a film made
from
Exceed 1018CATm, a resin commercially available from ExxonMobil. Exceed
1018CATm has a density of about 0.918 g/cm3 and a melt index 12 of about 0.94
dg/min. Comparative Example C is a film made from Marlex D139TM, a resin
commercially available from ChevronPhillips. Marlex D139Tm has a density of
about
0.918 g/cm3 and a melt index 12 of about 0.9 dg/min. Comparative Example D is
a film
made from Elite 5400GTM, a resin commercially available from the Dow Chemical
Company. Elite 5400GTM has a density of about 0.916 g/cm3 and a melt index 12
of
about 1 dg/min. Comparative Example E is a film made from a resin made
according
to US Pat. Appl. No. 2016/0108221. The resin has a density of about 0.917
g/cm3, a
melt index 12 of about 0.96 dg/min, and is made in a multi reactor solution
process in
which a first reactor and a second reactor are configured in series with one
another.
The resin is an ethylene/1 -octene copolymer. In Table 4, Comparative Examples
1
and 2 are films which were made from Comparative polyethylenes 1 and 2. As
already described above, these comparative resins were made using a three
reactor
process, in which the first and second reactors are configured in parallel,
but in which
ethylene monomer was not added to the third reactor. In Table 4, the Inventive
Examples 1-5, are films made from the Inventive polyethylene product
compositions
1-5.
110
TABLE 4
Comp. A Comp. B Comp. C Comp. D Comp. E
Comp. 1
Film Physical
Properties
Thickness Profile Ave 1.01 1.01 1.03 1.03 1.04
1.03
. _
Film Toughness
Dart Impact (g/mil) 470 827 688 818 812
677
0
Slow Puncture -
.
85 80 77 63 98 56
cõ
0,
Lube/Tef (J/mm)
.,
i
Puncture (J/mm) 97 66
.
Film Tear Resistance '
Tear-MD (g/mil) 308 241 186 247 293
248
Tear - TD (g/mil) 516 358 454 485 540
392
Film Stiffness
1% Sec Modulus - MD
129 156.8 177.6 165 150.4 187.6
(Mpa)
111
1% Sec Modulus - TD
131.4 168.8 185 175 167.8
238.8
(Mpa)
2% Sec Modulus - MD
117 150.2 166.4 151 141.4
184.4
(Mpa)
2% Sec Modulus - TD
= 123.8 161.4 170.2 = 155
149.2 227.4
(Mpa)
Film Tensile Strength
0
Tensile Break Str - MD
46.4 50.7 47.8 44 45.4
34.9
(Mpa)
Tensile Break Str - TD
48 61.1 47.8 45.5 44.6
43
(Mpa)
Elongation at Break -
534 566 505 486 521
506
MD (%)
Elongation at Break -
796 741 692 725 747
663
TD (%)
112
Tensile Yield Str - MD
8.8 9.7 10.1 9.1 9.1
10.9
(Mpa)
_
Tensile Yield Str - TD
8.8 9.9 9.2 8.7 8.9
11.6
(Mpa)
Tensile Elong at Yield -
22 15 16 = 13 13
18 =
MD (%)
Tensile Elong at Yield -
17 14 12 13 14
13 0
TD (%)
.
cõ
0,
Film Opticals
,
i
Gloss at 45 50 39 84 64 72
63 2 ,
Haze (%) 12 16.2 3.3 7.8 5.8
8.7
Cold Seal Properties
S.I.T. @ 8.8N Seal
98.8 102.8 102.4 100.4 98.2
107
Strength ( C)
Max Force (N) 19.9 20.6 23.4 24.9 23.7
20.1
113
=
Temp. @ Max Force
130 140 120 150 160
160
( C)
Hot Tack Properties
Tack Onset @ 1.0N
100.5 101.2 98.6 92.5 95.4
98.1
( C) - 2 mil film
Max Hottack Strength
4.1 5.3 5.7 5.4 4.4
4.5
(N) - 2 mil film
Temperature - Max.
115 120 120 110 115
120
Hottack ( C) - 2 mil film
114
TABLE 4 CONTINUED
Example No. Comp. 2 Inv. 1 Inv. 2 Inv. 3 Inv. 4
Inv. 5
Film Physical
Properties
Thickness Profile Ave t04 1.04 1.01 1.01 0.99
1.02
Film Toughness
Dart Impact (g/mil) 918 712 722 646 658
790
Slow Puncture -
86 82 67 72 70
77
LubefTef (J/mm)
Puncture (J/mm) 119 111
129
Film Tear Resistance
Tear - MD (g/mil) 251 306 294 338 282
337
Tear - TD (gimp 477 493 521 551 570
597
Film Stiffness
1% Sec Modulus - MD
199.8 191.6 198 184 176
204
(Mpa)
115
1% Sec Modulus - TD
254.4 246.2 358 232.8 217 244
(Mpa)
2% Sec Modulus - MD
181.4 179 232 166 158 179
(Mpa)
2% Sec Modulus - TD
218.4 213.2 268 205.6 = 180 206
(Mpa)
Film Tensile Strength
0
Tensile Break Str - MD
cr,
42.8 46.3 57.2 41.6 55.2 58.8
cr,
(Mpa)
Tensile Break Str - TD
52.5 56.2 50.2 55.6 50.8 47.1
(Mpa)
Elongation at Break -
536 548 652 552 626
644
MD (%)
Elongation at Break -
730 744 803 770 790
792
TD (%)
116
Tensile Yield Str - MD
10.1 9.9 9.5 10.8 12.1
(Mpa)
Tensile Yield Str - TD
10.7 10.4 10.4 10.6 12.6 11.9
(Mpa)
Tensile Elong at Yield -
= 14 14 17 14 =
14 12 =
MD (%)
Tensile Elong at Yield -
12 11 15 13 12
13
TD (%)
cr,
cr,
Film Opticals
Gloss at 45 68 59 59 56 57
49
Haze (%) 7.5 9.1 9.6 9.9 10.2
13.1
Cold Seal Properties
S.I.T. @ 8.8N Seal
111.2 102.5 102 102.1 97.8 100.5
Strength ( C)
Max Force (N) 18.3 19.1 22.9 20.4 22.6
24
117
Temp. @ Max Force
150 150 150 130 130
150
( C)
Hot Tack Properties
Tack Onset @ 1.0N
97.2 95.6 95.7 94 92.9
91.6
( C) - 2 mil film
Max Hottack Strength
4.1 5.1 4.9 5.3 4.5
4.9
(N) - 2 mil film
Temperature - Max.
115 115 115 120 120
120
Hottack ( C) - 2 mil film
118
CA 2964563 2017-04-19
The data provided in Table 4 demonstrate that the inventive polyethylene
product compositions have a good balance of film properties, including good
dart
impact, stiffness, puncture, tear and sealing properties. Films made from the
inventive
polyethylene products also have good tensile strength and optical properties.
Finally, films made from the inventive polyethylene products also have good
hot
tack performance. Without wishing to be bound by theory, in the hot tack
profile (seal
temperature vs. force), good hot tack performance is indicated by an early (or
low) hot
tack initiation temperature, then a relatively high force over a wide range of
seal
temperatures. See for example the shape the curves in Figure 7A for inventive
compositions 1, 2, 3, 4 and 5, relative to comparative resins 1 and 2 and
comparative
resins A, B, C, and D, in Figure 7B. The shape of the hot tack curve for
inventive
composition 5, is particularly good and has an early hot tack initiation
temperature
combined by a high force over a wide range of seal temperatures.
Good cold seal properties are evidenced by the curves given in Figure 8A for
the inventive polyethylene compositions. The cold seal properties of some
comparative polyethylene compositions are provided in Table 8B. A person
skilled in
the art will recognize that inventive example 5, has an early cold seal
initiation
temperature in combination with a relatively high force over a wide range of
cold seal
temperatures.
Non-limiting embodiments of the present disclosure include the following:
Embodiment A. A continuous solution polymerization process comprising:
injecting ethylene, a process solvent, a first catalyst system, optionally one
or
more a-olefins and optionally hydrogen into each of a first reactor and a
second
reactor configured in parallel to each other to produce a first exit stream
containing a
first polyethylene made in the first reactor and a second exit stream
containing a
second polyethylene made in the second reactor;
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passing the first exit stream and the second exit stream into a third reactor
and
injecting into the third reactor, ethylene, and optionally each of:
a process solvent,
one or more a-olefins,
hydrogen and
a second catalyst system,
to produce a third exit stream containing a final polyethylene product;
passing the third exit stream to a devolatilization system to recover the
final
polyethylene product; wherein
the first reactor is operated at lower temperature than the second reactor;
the first catalyst system is a single site catalyst system; and
if injected into the third reactor, the second catalyst system is a single
site
catalyst system or a Ziegler-Natta catalyst system.
Embodiment B. The process of Embodiment A wherein the first catalyst
system is a single site catalyst system comprising:
a) a phosphinimine complex defined by the formula
(LA)aM(P0b(Q)n
wherein LA is selected from the group consisting of unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; M is a
metal selected from titanium, hafnium and zirconium; P1 is a phosphinimine
ligand; and 0 is independently selected from the group consisting of a
hydrogen atom, a halogen atom, a Ci-io hydrocarbyl radical, a Ci-io alkoxy
radical and a C5-10 aryl oxide radical; wherein each of the hydrocarbyl,
alkoxy,
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and aryl oxide radicals may be unsubstituted or further substituted by a
halogen
atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy
radical,
an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl
radicals or a phosphido radical which is unsubstituted or substituted by up to
two Cie alkyl radicals; wherein a is 1; b is 1; n is 1 or 2; and (a+b+n) is
equivalent to the valence of the metal M;
b) an alkylaluminoxane co-catalyst;
c) an ionic activator, and;
d) optionally, a hindered phenol.
Embodiment C. The process of Embodiment B wherein the alkylalunninoxane
co-catalyst is methylaluminoxane (MAO).
Embodiment D. The process of Embodiment C wherein the ionic activator is
trityl tetrakis (pentafluora-phenyl) borate.
Embodiment E. The process of Embodiment A, B, C, or D wherein at least 10
weight percent of the total ethylene injected into reactor 1, reactor 2 and
reactor 3, is
injected into reactor 3.
Embodiment F. The process of Embodiment A, B, C, or D wherein at least 20
weight percent of the total ethylene injected into reactor 1, reactor 2 and
reactor 3, is
injected into reactor 3.
Embodiment G. The process of Embodiment A, B, C, D, E, or F wherein the
first, second and third reactors operate at a temperature from about 80 C to
about
300 C and a pressure from about 3 MPag to about 45 MPag.
Embodiment H. The process of Embodiment A, B, C, D, E, F, or G wherein the
first reactor operates at a temperature at least 25 C lower than the
temperature at
which the second reactor operates.
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Embodiment I. The process of Embodiment A, B, C, D, E, F, or G wherein the
first reactor operates at a temperature at least 45 C lower than the
temperature at
which the second reactor operates.
Embodiment K. The process of Embodiment A, B, C, D, E, F, or G wherein the
first reactor operates at a temperature of from about 10 C to about 100 C
lower than
the temperature at which the second reactor operates.
Embodiment L. The process of Embodiment A, B, C, D, E, F, or G wherein the
first reactor operates at a temperature of from about 125 C to about 155 C and
the
second reactor operates at a temperature of from about 185 C to about 205 C.
Embodiment M. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, or L
wherein one or more a-olef ins is fed exclusively to the first reactor.
Embodiment N. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, L,
or M wherein a second catalyst is fed to the third reactor.
Embodiment 0. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, L,
M, or N wherein the first reactor and the second reactor are continuously
stirred tank
reactors.
Embodiment P. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, L,
M, N, or 0 wherein the third reactor is a tubular reactor.
Embodiment 0. The process of Embodiment N wherein the second catalyst
system is a single site catalyst system comprising:
a) a phosphinimine complex defined by the formula
(LA)aM(PI)b(Q)n
wherein LA is selected from the group consisting of unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
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substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; M is a
metal selected from titanium, hafnium and zirconium; PI is a phosphinimine
ligand; and Q is independently selected from the group consisting of a
hydrogen atom, a halogen atom, a Ci-io hydrocarbyl radical, a Ci-io alkoxy
radical and a C5-10 aryl oxide radical; wherein each of the hydrocarbyl,
alkoxy,
and aryl oxide radicals may be unsubstituted or further substituted by a
halogen
atom, a C1-18 alkyl, radical, a C1-8 alkoxy radical, a Cs-u) aryl or aryloxy
radical,
an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl
radicals or a phosphido radical which is unsubstituted or substituted by up to
two C1-8 alkyl radicals; wherein a is 1; b is 1; n is 1 or 2; and (a+b+n) is
equivalent to the valence of the metal M;
b) an alkylaluminoxane co-catalyst;
c) an ionic activator, and;
d) optionally, a hindered phenol.
Embodiment R. The process of Embodiment N wherein the second catalyst
system is a Ziegler-Natta catalyst system.
Embodiment S. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, L,
M, N, 0, P, Q, or R wherein the process solvent is one or more C5 to C12
alkanes.
Embodiment T. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, L,
M, N, 0, P, Q, R, or S wherein the one or more a-olefins are C3 to Cio a-
olefins.
Embodiment U. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, L,
M, N, 0, P, 0, R, S, or T wherein the one or more a-olefins are 1-hexene or 1-
octene
or a mixture of 1-hexene and 1-octene.
Embodiment V. The process of Embodiment A, B, C, D, E, F, G, H, I, J, K, L,
M, N, 0, P, C), R, S, T, or U wherein the first exit stream and the second
exit stream
are combined upstream of the third reactor.
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Embodiment W. A polyethylene product produced according to Embodiment A,
B, C, D, E, F, G, H, I, J, K, L, M, N, 0, P, 0, R, S, T, U, or V,
Embodiment X. A continuous solution polymerization process comprising:
injecting ethylene, a process solvent, a first catalyst system, optionally one
or
more a-olefins and optionally hydrogen into each of a first reactor and a
second
reactor configured in parallel to each other to produce a first exit stream
containing a
first polyethylene made in the first reactor and a second exit stream
containing a
second polyethylene made in the second reactor;
passing the first exit stream into a third reactor and injecting into the
third
reactor, ethylene, and optionally each of:
a process solvent,
one or more a-olefins,
hydrogen and
a second catalyst system,
to produce a third exit stream;
combining the second exit stream with the third exit stream to produce a final
product stream containing a final polyethylene product;
passing the final product stream to a devolatilization system to recover the
final
polyethylene product; wherein
the first reactor is operated at lower temperature than the second reactor;
the first catalyst system is a single site catalyst system; and
if injected into the third reactor, the second catalyst system is a single
site
catalyst system or a Ziegler-Natta catalyst system.
Embodiment Y. A continuous solution polymerization process comprising:
injecting ethylene, a process solvent, a first catalyst system, optionally one
or
more a-olefins and optionally hydrogen into each of a first reactor and a
second
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reactor configured in parallel to each other to produce a first exit stream
containing a
first polyethylene made in the first reactor and a second exit stream
containing a
second polyethylene made in the second reactor;
passing the second exit stream into a third reactor and injecting into the
third
reactor, ethylene, and optionally each of:
a process solvent,
one or more a-olefins,
hydrogen and
a second catalyst system,
to produce a third exit stream;
combining the first exit stream with the third exit stream to produce a final
product stream containing a final polyethylene product;
passing the final product stream to a devolatilization system to recover the
final
polyethylene product; wherein
the first reactor is operated at lower temperature than the second reactor;
the first catalyst system is a single site catalyst system; and
if injected into the third reactor, the second catalyst system is a single
site
catalyst system or a Ziegler-Natta catalyst system.
=
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