Note: Descriptions are shown in the official language in which they were submitted.
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SOLUTION POLYMERIZATION PROCESS
FIELD OF THE INVENTION
Catalyst modifiers comprise at least one long chain amine and are employed in
combination with a phosphinimine polymerization catalyst in a solution
polymerization
process.
BACKGROUND OF THE INVENTION
Amine modifiers have been used in slurry and gas phase polymerization
processes. European Patent Application No. 630,910 discusses reversibly
reducing
the activity of a metallocene catalyst using a Lewis base compound such as for
example an amine compound.
Long chain substituted alkanolamine compounds in particular, have been used
in combination with metallocenes to reduce the amount of reactor fouling in
fluidized
bed polymerization processes. The use of substituted alkanolamines in
combination
with metallocene catalysts to improve reactor operability and reduce static
levels is
described in European Patent Application No. 811,638 and in U.S. Pat. Nos.
5,712,352; 6,201,076; 6,476,165; 6,180,729; 6,977,283; 6,114,479; 6,140,432;
6,124,230; 6,117,955; 5,763,543; and 6,180,736. Alkanolamines have been added
to
a metallocene catalyst prior to addition to a reaction zone, as described in
U.S. Pat.
Nos. 6,140,432; 6,124,230 and 6,114,479. Alkanolamines have also been added
directly to a reactor or other associated parts of a fluidized bed reactor
processes
such as the recycle stream loop as is taught in European Patent Application
No.
811,638 and in U.S. Pat. No. 6,180,729 respectively.
SUMMARY OF THE INVENTION
The present invention is directed to the use of a catalyst modifier comprising
at
least one long-chain amine in a solution polymerization process.
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Provided is a process for polymerizing ethylene and optionally an alpha olefin
in a solution reactor with a polymerization catalyst comprising: i) a
phosphinimine
catalyst; ii) a cocatalyst; and iii) a catalyst modifier; wherein the catalyst
modifier
comprises at least one long-chain amine compound.
In an embodiment of the invention, a catalyst modifier comprises at least one
compound represented by the formula: R1N((CH2)n0H)((CH2)m0H) where R1 is a
hydrocarbyl group having anywhere from 5 to 30 carbon atoms, and n and m are
integers from 1-20.
In an embodiment of the invention, a catalyst modifier comprises at least one
compound represented by the formula: R1N((CH2)n0H)2 where R1 is an hydrocarbyl
group having anywhere from 6 to 30 carbon atoms, and n is an integer from 1-
20.
In an embodiment of the invention, a catalyst modifier comprises at least one
compound represented by the formula: R1N(CH2CH2OH)2 where R1 is a hydrocarbyl
group having anywhere from 6 to 30 carbon atoms.
In an embodiment, the catalyst modifier is defined by the formula RaRbRc
wherein Ra and Rb are each independently a C6 to C30 hydrocarbyl and RC is
selected
from the group consisting of hydrogen and Ci to C30 hydrocarbyl.
In an embodiment of the invention, a phosphinimine catalyst has the formula:
(L)(PI)MX2, where M is Ti, Zr or Hf; PI is a phosphinimine ligand having the
formula
R3P=N-, where R is independently selected from the group consisting of
hydrogen,
halogen, and Ci-C20 hydrocarbyl; L is a ligand selected from the group
consisting of
cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl,
fluorenyl,
and substituted fluorenyl; and X is an activatable ligand.
In an embodiment of the invention, a cocatalyst is selected from the group
consisting of ionic activators, alkylaluminoxanes and mixtures thereof.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
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The Catalyst Modifier
The catalyst modifier employed in the present invention comprises a long chain
amine compound. In the present invention, the terms "long chain substituted
amine"
or "long chain amine" are defined as tri-coordinate nitrogen compounds (i.e.
amine
based compounds) containing at least one hydrocarbyl group having at least 5
carbon
atoms, preferably from 6 to 30 carbon atoms. The terms "hydrocarbyl" or
"hydrocarbyl
group" includes branched or straight chain hydrocarbyl groups which may be
fully
saturated groups (i.e. have no double or triple bonding moieties) or which may
be
partially unsaturated (i.e. they may have one or more double or triple bonding
moieties). The long chain hydrocarbyl group may also contain un-saturation in
the
form of aromatic ring moieties attached to or part of the main chain.
Preferably, the
long chain amine (i.e. the tri-coordinate nitrogen compound) will also have at
least one
heteroatom containing hydrocarbyl group. Such heteroatom containing
hydrocarbyl
groups can be branched or straight chain hydrocarbyl groups or substituted
hydrocarbyl groups having one or more carbon atoms and at least one
heteroatom.
Heteroatom containing hydrocarbyl groups may also contain unsaturated
moieties.
Suitable heteroatoms include for example, oxygen, nitrogen, phosphorus or
sulfur.
Other groups which may be attached to nitrogen in a long chain substituted
amine
compound are generally selected from hydrocarbyl groups having one or more
carbon
atoms and/or a hydrogen group (H).
In embodiments of the invention, the long chain amine is a long chain
substituted monoalkanolamine, or a long chain substituted dialkanolamine.
These
amines have one or two alcoholhydrocarbyl groups respectively as well as a
hydrocarbyl group having at least 5 carbons.
In an embodiment of the invention, the catalyst modifier employed comprises at
least one long chain amine compound represented by the formula:
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R1R2xN((CH2)n0H)y where R1 is a hydrocarbyl group having from 5 to 30 carbon
atoms, R2 is hydrogen or a hydrocarbyl group having from 1 to 30 carbon atoms,
x is
1 or 0, y is 1 when x is 1, y is 2 when x is 0, each n is independently an
integer from 1
to 30 when y is 2, and n is an integer from 1 to 30 when y is 1.
In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted monoalkanolamine represented by the formula
R1R2N((CH2)n0H) where R1 is a hydrocarbyl group having anywhere from 5 to 30
carbon atoms, R2 is a hydrogen or a hydrocarbyl group having anywhere from 1
to 30
carbon atoms, and n is an integer from 1-20.
In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted dialkanolamine represented by the formula:
Ri N((CH2)n0H)((CH2)rn0H) where R1 is a hydrocarbyl group having anywhere from
5
to 30 carbon atoms, and n and m are integers from 1-20.
In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted dialkanolamine represented by the formula:
R1N((CH2)n0H)2
where R1 is a hydrocarbyl group having anywhere from 6 to 30 carbon atoms, and
n is
an integer from 1-20.
In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted dialkanolamine represented by the formula:
R1N((CH2)n0H)2
where R1 is a hydrocarbyl group having anywhere from 6 to 30 carbon atoms, and
n is
2 or 3.
In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted dialkanolamine represented by the formula:
R1N((CH2)n0H)2
where R1 is a linear hydrocarbyl group having anywhere from 6 to 30 carbon
atoms,
and n is 2 or 3.
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In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted dialkanolamine represented by the formula:
R1N(CH2CH2OH)2
where R1 is a linear hydrocarbyl group having anywhere from 6 to 30 carbon
atoms.
In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted dialkanolamine represented by the formula:
R1N(CH2CH2OH)2
where R1 is a linear, saturated alkyl group having anywhere from 6 to 30
carbon
atoms.
In an embodiment of the invention, the catalyst modifier comprises at least
one
long chain substituted dialkanolamine represented by the formula:
R1N(CH2CH2OH)2
where R1 is a hydrocarbyl group having anywhere from 8 to 22 carbon atoms.
In an embodiment of the invention, the catalyst modifier comprises a long
chain
substituted dialkanolamine represented by the formula: C18H37N(CH2CH2OH)2.
In an embodiment of the invention, the catalyst modifier comprises long chain
substituted dialkanolamines represented by the formulas: C13H27N(CH2CH2OH)2
and
C15H31N(CH2CH2OH)2.
In an embodiment of the invention, the catalyst modifier comprises a mixture
of
long chain substituted dialkanolamines represented by the formula:
R1N(CH2CH2OH)2
where R1 is a hydrocarbyl group having anywhere from 8 to 18 carbon atoms.
Non limiting examples of catalyst modifiers which can be used in the present
invention are KEMAMINE AS-990, KEMAMINE AS-650, ARMOSTAT 1800, bis-
hydroxy-cocoamine, 2,2'-octadecyl-amino-bisethanol, and ATMER 163.
The long chain substituted amine may also be a polyoxyethylenehydrocarbyl
amine.
In an embodiment of the invention, the catalyst modifier comprises a
polyoxyethylenehydrocarbyl amine represented by the formula:
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R1N((CH2CF120)nFI)((CH2CH20)mH), where R1 is a hydrocarbyl group having from 5
to
30 carbons, and n and m are integers from 1-10 or higher (i.e. polymeric).
The Polymerization Catalyst
In the present invention, the (olefin) polymerization catalyst comprises: i) a
phosphinimine catalyst, ii) a cocatalyst, and iii) a catalyst modifier.
The Phosphinimine Catalyst
Some non-limiting examples of phosphinimine catalysts can be found in U.S.
Pat. Nos. 6,342,463; 6,235,672; 6,372,864; 6,984,695; 6,063,879; 6,777,509 and
6,277,931 all of which are incorporated by reference herein.
Preferably, the phosphinimine catalyst is based on metals from group 4, which
includes titanium, hafnium and zirconium. The most preferred phosphinimine
catalysts are group 4 metal complexes in their highest oxidation state.
The phosphinimine catalysts described herein, usually require activation by
one
or more cocatalytic or activator species in order to provide polymer from
olefins.
A phosphinimine catalyst is a compound (typically an organometallic
compound) based on a group 3, 4 or 5 metal and which is characterized as
having at
least one phosphinimine ligand. Any compounds/complexes having a phosphinimine
ligand and which display catalytic activity for ethylene (co)polymerization
may be
called "phosphinimine catalysts".
In an embodiment of the invention, a phosphinimine catalyst is defined by the
formula: (L)n(PI)mMXp where M is a transition metal selected from Ti, Hf, Zr;
PI is a
phosphinimine ligand; L is a cyclopentadienyl-type ligand or a heteroatom
ligand; X is
an activatable ligand; m is 1 or 2; n is 0 or 1; and p is determined by the
valency of the
metal M. Preferably m is 1, n is 1 and p is 2.
In an embodiment of the invention, a phosphinimine catalyst is defined by the
formula: (L)(PI)MX2 where M is a transition metal selected from Ti, Hf, Zr; PI
is a
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phosphinimine ligand; L is a cyclopentadienyl type ligand; and X is an
activatable
ligand.
The phosphinimine ligand is defined by the formula: R3P=N-, where N bonds to
the metal, and wherein each R is independently selected from the group
consisting of
a hydrogen atom; a halogen atom; C1-20 hydrocarbyl radicals which are
unsubstituted
or further substituted by one or more halogen atom and/or C1-20 alkyl radical;
C1-8
alkoxy radical; C6-10 aryl or aryloxy radical (the aryl or aryloxy radical
optionally being
unsubstituted or further substituted by one or more halogen atom and/or C1-20
alkyl
radical); amido radical; silyl radical of the formula: -SiR'3 wherein each R'
is
independently selected from the group consisting of hydrogen, a C1-8 alkyl or
alkoxy
radical, C6-10 aryl or aryloxy radicals; and germanyl radical of the formula: -
GeR'3
wherein R' is as defined above.
In an embodiment of the invention the phosphinimine ligand is chosen so that
each R is a hydrocarbyl radical. In a particular embodiment of the invention,
the
phosphinimine ligand is tri-(tertiarybutyl)phosphinimine (i.e. where each R is
a tertiary
butyl group, or "t-Bu" for short).
In an embodiment of the invention, the phosphinimine catalyst is a group 4
compound/complex which contains one phosphinimine ligand (as described above)
and one ligand L which is either a cyclopentadienyl-type ligand or a
heteroatom
ligand.
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
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versions of indenyl and fluorenyl ligands are also contemplated for use in the
current
invention, 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,
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;
for
example a suitable C6-10 aryl group is a perfluoroaryl group such as ¨C6F5);
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 C1-8 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.
As used herein, the term "heteroatom ligand" refers to a ligand which contains
at least one heteroatom selected from the group consisting of boron, nitrogen,
oxygen,
silicon, phosphorus or sulfur. The heteroatom ligand may be sigma or pi-bonded
to
the metal. Exemplary heteroatom ligands include but are not limited to
"silicon
containing" ligands, "amido" ligands, "alkoxy" ligands, "boron heterocycle"
ligands and
"phosphole" ligands.
Silicon containing ligands are defined by the formula: -(p)SiRxRYRz where the
"-
"denotes a bond to the transition metal and p is sulfur or oxygen. The
substituents on
the Si atom, namely Rx, RY and Rz are required in order to satisfy the bonding
orbital
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of the Si atom. The use of any particular substituent Rx, RY or Rz is not
especially
important. In an embodiment of the invention, each of Rx, RY and Rz is a C1-2
hydrocarbyl group (i.e. methyl or ethyl) simply because such materials are
readily
synthesized from commercially available materials.
The term "amido" is meant to convey its broad, conventional meaning. Thus,
these ligands are characterized by (a) a metal-nitrogen bond and (b) the
presence of
two substituents (which are typically simple alkyl or silyl groups) on the
nitrogen atom.
The term "alkoxy" is also intended to convey its conventional meaning. Thus,
these ligands are characterized by (a) a metal oxygen bond, and (b) the
presence of a
hydrocarbyl group bonded to the oxygen atom. The hydrocarbyl group may be a
ring
structure and may optionally be substituted (e.g. 2,6 di-tertiary butyl
phenoxy).
The "boron heterocyclic" ligands are characterized by the presence of a boron
atom in a closed ring ligand. This definition includes heterocyclic ligands
which also
contain a nitrogen atom in the ring. These ligands are well known to those
skilled in
the art of olefin polymerization and are fully described in the literature
(see, for
example, U.S. Pat. Nos. 5,637,659 and 5,554,775 and the references cited
therein).
The term "phosphole" is also meant to convey its conventional meaning.
"Phospholes" are cyclic dienyl structures having four carbon atoms and one
phosphorus atom in the closed ring. The simplest phosphole is C4PH4 (which is
analogous to cyclopentadiene with one carbon in the ring being replaced by
phosphorus). The phosphole ligands may be substituted with, for example, C1-20
hydrocarbyl radicals (which may, optionally, contain halogen substituents);
phosphido
radicals; amido radicals; silyl or alkoxy radicals. Phosphole ligands are also
well
known to those skilled in the art of olefin polymerization and are described
as such in
U.S. Pat. No. 5,434,116.
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The term "activatable ligand" refers to a ligand which may be activated by a
cocatalyst (also referred to as an "activator"), to facilitate olefin
polymerization. An
activatable ligand X may be cleaved from the metal center M via a protonolysis
reaction or abstracted from the metal center M by suitable acidic or
electrophilic
catalyst activator compounds (also known as "co-catalyst" compounds)
respectively,
examples of which are described below. The activatable ligand X 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
invention,
the activatable ligand, X is independently selected from the group consisting
of a
hydrogen atom; a halogen atom; a Ci-io hydrocarbyl radical; a Ci-io alkoxy
radical; a
C6-10 aryl oxide radical, each of which said hydrocarbyl, alkoxy, and aryl
oxide radicals
may be unsubstituted by or further substituted by a halogen atom, a C1-8 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; and a phosphido
radical
which is unsubstituted or substituted by up to two C1-8 alkyl radicals. Two
activatable
X ligands may also be joined to one another and form for example, a
substituted or
unsubstituted diene ligand (i.e. 1,3-diene); or a delocalized heteroatom
containing
group such as an acetate group.
The number of activatable ligands depends upon the valency of the metal and
the valency of the activatable ligand. The preferred phosphinimine catalysts
are
based on group 4 metals in their highest oxidation state (i.e. 4').
Particularly suitable
activatable ligands are monoanionic such as a halide (e.g. chloride) or a
hydrocarbyl
(e.g. methyl, benzyl).
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In some instances, the metal of the phosphinimine catalyst may not be in the
highest oxidation state. For example, a titanium (III) component would contain
only
one activatable ligand.
In an embodiment of the invention, the phosphinimine catalyst has the formula,
(L)(PI)MX2, where M is Ti, Zr or Hf; PI is a phosphinimine ligand having the
formula
R3P=N-, where R is independently selected from the group consisting of
hydrogen,
halogen, and C1-C20 hydrocarbyl; L is a ligand selected from the group
consisting of
cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl,
fluorenyl,
and substituted fluorenyl; and X is an activatable ligand.
In an embodiment of the invention, the phosphinimine catalyst has the formula,
(L)(PI)MX2, where M is Ti, Zr or Hf; PI is a phosphinimine ligand having the
formula
R3P=N-, where R is independently selected from the group consisting of
hydrogen,
halogen, and C1-C20 hydrocarbyl; L is a substituted cyclopentadienyl ligand;
and X is
an activatable ligand.
In an embodiment of the invention, the phosphinimine catalyst has the formula,
(L)((t-Bu)3P=N)MX2, where M is Ti, Zr or Hf; L is a substituted
cyclopentadienyl ligand;
and X is an activatable ligand.
In an embodiment of the invention, the phosphinimine catalyst contains a
phosphinimine ligand, a cyclopentadienyl ligand ("Cp" for short) and two
chloride or
two methyl ligands bonded to the group 4 metal.
In an embodiment of the invention, the phosphinimine catalyst contains a
phosphinimine ligand, a substituted cyclopentadienyl ligand and two chloride
or two
methyl ligands bonded to the group 4 metal.
In an embodiment of the invention, the phosphinimine catalyst contains a
phosphinimine ligand, a perfluoroaryl substituted cyclopentadienyl ligand and
two
chloride or two methyl ligands bonded to the group 4 metal.
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In an embodiment of the invention, the phosphinimine catalyst contains a
phosphinimine ligand, a perfluorophenyl substituted cyclopentadienyl ligand
(i.e.
Cp-C6F5) and two chloride or two methyl ligands bonded to the group 4 metal.
In an embodiment of the invention, the phosphinimine catalyst contains a 1,2-
substituted cyclopentadienyl ligand and a phosphinimine ligand which is
substituted by
three tertiary butyl substituents.
In an embodiment of the invention, the phosphinimine catalyst contains a 1,2
substituted cyclopentadienyl ligand (e.g. a 1,2-(R*)(Ar-F)Cp) where the
substituents
are selected from R* a hydrocarbyl group, and Ar-F a perfluorinated aryl
group, a 2,6
(i.e. ortho) fluoro substituted phenyl group, a 2,4,6 (i.e. ortho/para) fluoro
substituted
phenyl group, or a 2,3,5,6 (i.e. ortho/meta) fluoro substituted phenyl group
respectively.
In the present invention, 1,2 substituted cyclopentadienyl ligands such as for
example 1,2-(R*)(Ar-F)Cp ligands may contain as impurities 1,3 substituted
analogues
such as for example 1,3-(R*)(Ar-F)Cp ligands. Hence, phosphinimine catalysts
having
a 1,2 substituted Cp ligand may contain as an impurity, a phosphinimine
catalyst
having a 1,3 substituted Cp ligand. Alternatively, the current invention
contemplates
the use of 1,3 substituted Cp ligands as well as the use of mixtures of
varying
amounts of 1,2 and 1,3 substituted Cp ligands to give phosphinimine catalysts
having
1,3 substituted Cp ligands or mixed phosphinimine catalysts having 1,2 and 1,3
substituted Cp ligands.
In an embodiment of the invention, the phosphinimine catalyst has the formula:
(1,2-(R*)(Ar-F)Cp)M(N=P(t-Bu)3)X2 where R* is a hydrocarbyl group; Ar-F is a
perfluorinated aryl group, a 2,6 (i.e. ortho) fluoro substituted phenyl group,
a 2,4,6 (i.e.
ortho/para) fluoro substituted phenyl group, or a 2,3,5,6 (i.e. ortho/meta)
fluoro
substituted phenyl group; M is Ti, Zr or Hf; and X is an activatable ligand.
In an
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embodiment of the invention, the phosphinimine catalyst has the formula: (1,2-
(R*)(Ar-
F)Cp)M(N=P(t-Bu)3)X2 where R* is an alkyl group; Ar-F is a perfluorinated aryl
group,
a 2,6 (i.e. ortho) fluoro substituted phenyl group, a 2,4,6 (i.e. ortho/para)
fluoro
substituted phenyl group or a 2,3,5,6 (i.e. ortho/meta) fluoro substituted
phenyl group;
M is Ti, Zr or Hf; and X is an activatable ligand. In an embodiment of the
invention,
the phosphinimine catalyst has the formula: (1,2-(R*)(Ar-F)Cp)M(N=P(t-Bu)3)X2
where
R* is a hydrocarbyl group having from 1 to 20 carbons; Ar-F is a
perfluorinated aryl
group; M is Ti, Zr or Hf; and X is an activatable ligand. In an embodiment of
the
invention, the phosphinimine catalyst has the formula: (1,2-(R*)(Ar-
F)Cp)M(N=P(t-
Bu)3)X2 where R* is a straight chain alkyl group; Ar-F is a perfluorinated
aryl group, a
2,6 (i.e. ortho) fluoro substituted phenyl group, a 2,4,6 (i.e. ortho/para)
fluoro
substituted phenyl group, or a 2,3,5,6 (i.e. ortho/meta) fluoro substituted
phenyl group;
M is Ti, Zr or Hf; and X is an activatable ligand. In an embodiment of the
invention,
the phosphinimine catalyst has the formula: (1,2-(n-R*)(Ar-F)Cp)Ti(N=P(t-
Bu)3)X2
where R* is a straight chain alkyl group; Ar-F is a perfluorinated aryl group;
M is Ti, Zr
or Hf; and X is an activatable ligand. In an embodiment of the invention, the
phosphinimine catalyst has the formula: (1,2-(R*)(C6F5)Cp)M(N=P(t-Bu)3)X2
where R*
is a hydrocarbyl group having 1 to 20 carbon atoms; M is Ti, Zr or Hf; and X
is an
activatable ligand. In an embodiment of the invention, the phosphinimine
catalyst has
the formula: (1,2-(n-R*)(C6F5)Cp)M(N=P(t-Bu)3)X2 where R* is a straight chain
alkyl
group; M is Ti, Zr or Hf; and X is an activatable ligand. In further
embodiments, M is Ti
and R* is selected from the group consisting of n-propyl, n-butyl and n-hexyl,
and X is
selected from chloride or methide. In further embodiments, M is Ti and R* is
any one
of a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-
octyl group. In
further embodiments, X is chloride or methide.
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The term "perfluorinated aryl group" means that each hydrogen atom attached
to a carbon atom in an aryl group has been replaced with a fluorine atom as is
well
understood in the art (e.g. a perfluorinated phenyl group or substituent has
the formula
¨C6F5). In embodiments of the invention, Ar-F is selected from the group
comprising
perfluorinated phenyl or perfluorinated naphthyl groups.
Some phosphinimine catalysts which may be used in the present invention
include: ((C6F5)Cp)Ti(N=P(t-Bu)3)C12; (1,2-(n-propyl)(C6F5)Cp)Ti(N=P(t-
Bu)3)C12, (1,2-
(n-butyl)(C6F5)Cp)Ti(N=P(t-Bu)3)C12 and (1,2-(n-hexyl)(C6F5)Cp)Ti(N=P(t-
Bu)3)C12;
((C6F5)Cp)Ti(N=P(t-Bu)3)Me2, (Cp)Ti(N=P(t-Bu)3)Cl2 and (Cp)Ti(N=P(t-Bu)3)Me2.
The Cocatalyst
In the present invention, the phosphinimine catalyst is used in combination
with
at least one activator (or "cocatalyst") to form an active polymerization
catalyst system
for olefin polymerization. Activators (i.e. cocatalysts) include ionic
activator
cocatalysts and hydrocarbyl aluminoxane cocatalysts.
The activator used to activate the phosphinimine catalyst can be any suitable
activator including one or more activators selected from the group consisting
of
alkylaluminoxanes and ionic activators, optionally together with an alkylating
agent.
The alkylaluminoxanes are complex aluminum compounds of the formula:
R32A110(R3A110)mA11 R32, wherein each R3 is independently selected from the
group
consisting of C1-20 hydrocarbyl radicals and m is from 3 to 50. Optionally a
hindered
phenol can be added to the alkylaluminoxane to provide a molar ratio of
All:hindered
phenol of from 2:1 to 5:1 when the hindered phenol is present.
In an embodiment of the invention, R3 of the alkylaluminoxane, is a methyl
radical and m is from 10 to 40.
The alkylaluminoxanes are typically used in substantial molar excess compared
to the amount of group 4 transition metal in the phosphinimine catalyst. The
All:group
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4 transition metal molar ratios are from 10:1 to 10,000:1, preferably about
30:1 to
500:1.
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. Commercially
available
alkylaluminoxane activators include MAO (methylaluminoxane) and MMAO (modified
methylaluminoxane).
Alternatively, the activator of the present invention may be a combination of
an
alkylating agent (which may also serve as a scavenger) with an activator
capable of
ionizing the group 4 metal of the phosphinimine catalyst (i.e. an ionic
activator). In this
context, the activator can be chosen from one or more alkylaluminoxane and/or
an
ionic activator.
When present, the alkylating agent may be selected from the group consisting
of (R4)pmgx221, wherein X2 is a halide and each R4 is independently selected
from the
group consisting of Ci-io alkyl radicals and p is 1 or 2; R4Li wherein in R4
is as defined
above, (R4)ciZnX22-ci wherein R4 is as defined above, X2 is halogen and q is 1
or 2;
(R4)sAl2X23-s wherein R4 is as defined above, X2 is halogen and s is an
integer from 1
to 3. Preferably in the above compounds R4 is a C1-4 alkyl radical, and X2 is
chlorine.
Commercially available compounds include triethyl aluminum (TEAL), diethyl
aluminum chloride (DEAC), dibutyl magnesium ((Bu)2Mg), and butyl ethyl
magnesium
(BuEtMg or BuMgEt).
In an embodiment, the ionic activator may be selected from the group
consisting of: (i) compounds of the formula [R5] [B(R6)4]- wherein B is a
boron atom,
R5 is a cyclic C5-7 aromatic cation or a triphenyl methyl cation and each R6
is
independently selected from the group consisting of phenyl radicals which are
unsubstituted or substituted with from 3 to 5 substituents selected from the
group
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consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is
unsubstituted or
substituted by a fluorine atom; and a silyl radical of the formula --Si--
(R7)3; wherein
each R7 is independently selected from the group consisting of a hydrogen atom
and
a C1-4 alkyl radical; and (ii) compounds of the formula [(R8)tZH] [B(R6)4]-
wherein B is
a boron atom, H is a hydrogen atom, Z is a nitrogen atom or phosphorus atom, t
is 2
or 3 and R8 is selected from the group consisting of C1_30 alkyl radicals
(with the
proviso that at least one R8 contains from 6 to 0 carbon atoms), a phenyl
radical which
is unsubstituted or substituted by up to three C1-4 alkyl radicals, and R6 is
as defined
above; and (iii) compounds of the formula B(R6) 3 wherein R6 is as defined
above.
In the above compounds preferably R6 is a pentafluorophenyl radical, and R5 is
a triphenylmethyl cation, Z is a nitrogen atom and R8 is a C1-4 alkyl radical
or one R8
taken together with a nitrogen atom forms an anilinium radical (e.g. PhR82NH+,
which
is substituted by two R8 radicals such as for example two C1-4 alkyl
radicals).
Examples of compounds capable of ionizing the phosphinimine catalyst include
the following compounds: triethylammonium tetra(phenyl)boron,
tripropylammonium
tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium
tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tripropylammonium tetra (o,p-
dimethylphenyl)boron,
tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-
trifluoromethylphenyl)boron, tributylammonium tetra(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
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tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl
borate,
benzene (diazonium) tetrakispentafluorophenyl borate, tropillium phenyltris-
pentafluorophenyl borate, triphenylmethylium phenyl-trispentafluorophenyl
borate,
benzene (diazonium) phenyltrispentafluorophenyl borate, tropillium tetrakis
(2,3,5,6-
tetrafluorophenyl) borate, triphenylmethylium tetrakis (2,3,5,6-
tetrafluorophenyl)
borate, benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate,
tropillium tetrakis
(3,4,5-trifluorophenyl) borate, benzene (diazonium) tetrakis (3,4,5-
trifluorophenyl)
borate, tropillium tetrakis (1,2,2-trifluoroethenyl) borate,
trophenylmethylium 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; N,N-bisoctadecyl methylammonium
tetrakis(pentafluorophenyl)borate).
Commercially available activators which are capable of ionizing the group 4
metal of the phosphinimine catalyst include:
N,N-dimethylaniliniumtetrakispentafluorophenyl borate
("[Me2NHPh][B(C6F5)4]"); triphenylmethylium tetrakispentafluorophenyl borate
("[Ph3C][B(C6F5)4]"); and trispentafluorophenyl boron.
The ionic activators compounds may be used in amounts which provide a
molar ratio of group 4 transition metal to boron that will be from 1:1 to 1:6.
Optionally, mixtures of alkylaluminoxanes and ionic activators can be used as
activators in the polymerization catalyst.
Optionally, scavengers are added to the polymerization process. The present
invention can be carried out in the presence of any suitable scavenger or
scavengers.
Scavengers are well known in the art.
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In an embodiment of the invention, scavengers are organoaluminum
compounds having the formula: A13(X3)n(X4)3-n, where (X3) is a hydrocarbyl
having
from 1 to about 20 carbon atoms; (X4) is selected from alkoxide or aryloxide,
any one
of which having from 1 to about 20 carbon atoms; halide; or hydride; and n is
a
number from 1 to 3, inclusive; or hydrocarbyl aluminoxanes having the formula:
R32A110(R3A110)mAl1R32
wherein each R3 is independently selected from the group consisting of C1-20
hydrocarbyl radicals and m is from 3 to 50. Some non-limiting preferred
scavengers
useful in the current invention include triisobutylaluminum, triethylaluminum,
trimethylaluminum or other trihydrocarbyl aluminum compounds.
The scavenger may be used in any suitable amount but by way of non-limiting
examples only, can be present in an amount to provide a molar ratio of Al:M
(where M
is the metal of the phosphinimine catalyst) of from about 20 to about 2000, or
from
about 50 to about 1000, or from about 100 to about 500.
Polyethylene Copolymer
The polymer compositions made using the present invention are most
preferably copolymers of ethylene and one or more an alpha olefin(s).
In an embodiment of the invention an alpha olefin selected for polymerization
with ethylene can be one or more alpha olefins selected from the group
consisting of
1-butene, 1-hexene and 1-octene.
In embodiments of the invention, the copolymer composition will comprise at
least 75 weight % of ethylene units, or at least 80 wt% of ethylene units, or
at least 85
wt% of ethylene units with the balance being an alpha-olefin unit, based on
the weight
of the copolymer composition.
Polymer properties such as average molecular weight (e.g. Mw, Mn and Mz),
molecular weight distribution (i.e. Mw/Mn), density, melt indices (e.g. 12,
15, 121, ho),
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melt index or melt flow ratios (e.g. 121/12, 121/15), comonomer distribution
breadth index
(CDBI), TREF-profile, comonomer distribution profile, and the like as these
terms are
defined further below and in for example co-pending CA Application No.
2,734,167 (to
the same Applicant) are not specifically defined, but by way of non-limiting
example
only, the polymer compositions made using the present invention, may have a
density
of from 0.910 g/cc to 0.93 g/cc, a melt index of from 0.25 to 10.0 g/10min, a
melt flow
ratio (121/12) of less than 20, a weight average molecular weight of from
25,000 to
300,000, and a unimodal or bimodal TREE profile.
In embodiments of the invention, the copolymer will have a melt index of from
0.1 to 5.0 g/10min, or from 0.25 to 5.0 g/10min, or from 0.25 to 4.5 g/10min,
or from
0.25 to 4.0 g/10min, or from 0.25 to 3.5 g/10min, or from 0.25 to 3.0 g/10min,
or from
0.75 to 5.0 g/10min, or from 0.75 to 4.5 g/10min, or from 0.75 to 4.0 g/10min,
or from
0.75 to 3.5 g/10min, or from 0.25 to 3 g/10min, or from 0.25 to 2.5 g/10min,
or from
0.5 to 2.0 g/10min, or from 0.75 to 1.5 g/10min.
In embodiments of the invention, the copolymer will have a density of from
0.910 g/cm3 to 0.930 g/cm3, or from 0.911 g/cm3 to 0.930 g/cm3, or from 0.912
g/cm3
to 0.930 g/cm3, or from 0.910 g/cm3 to 0.927 g/cm3, or from 0.910 g/cm3 to
0.925
g/cm3, or from 0.910 g/cm3 to 0.920 g/cm3, or from 0.911 g/cm3 to 0.927 g/cm3,
or
from 0.911 g/cm3 to 0.925 g/cm3, or from 0.911 g/cm3 to 0.920 g/cm3, or from
0.916
g/cm3 to 0.930 g/cm3, from 0.916 g/cm3 to 0.927 g/cm3, or from 0.916 9/cm3 to
0.925
g/cm3, or from 0.916 g/cm3 to 0.920 g/cm3, from 0.917 g/cm3 to 0.927 g/cm3, or
from
0.917 g/cm3 to 0.925 g/cm3, or from 0.917 g/cm3 to 0.920 g/cm3.
In an embodiment of the invention, the polymer composition will have a density
of greater than 0.911 g/cm3 and lower than 0.925 g/cm3.
In an embodiment of the invention, the copolymer will have a unimodal profile
in a gel permeation chromatography (GPC) curve generated according to the
method
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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. In contrast, by the
term
"bimodal" it is meant that 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 "multi-modal" denotes the presence of more than two
maxima
in a molecular weight distribution curve generated according to the method of
ASTM
D6474-99.
In embodiments of the invention, the copolymer will have a molecular weight
distribution (Mw/Mn) as determined by gel permeation chromatography (GPC) of
less
than 3.0, or less than 2.7, or from 1.6 to 2.6, or from 1.7 to 2.5, or from
1.7 to 2.4, or
from 1.7 to 2.3, or from 1.7 to 2.2, or from 1.8 to 2.4, or from 1.8 to 2.3,
or from 1.8 to
2.2.
In yet another embodiment of the invention, the copolymer will have a
molecular weight distribution (Mw/Mn) of 5 2.5. In still another embodiment of
the
invention, the copolymer will have a molecular weight distribution (Mw/Mn) of
5 2.4. In
yet another embodiment of the invention, the copolymer will have a molecular
weight
distribution (Mw/Mn) of 5 2.3. In yet further embodiments of the invention,
the
copolymer will have a molecular weight distribution (Mw/Mn) of 5 2.2, or 5
2.1, or 5 2Ø
In embodiments of the invention, the copolymers of the invention will exhibit
a
weight average molecular weight (Mw) as determined by gel permeation
chromatography (GPC) of from 30,000 to 250,000, or from 50,000 to 200,000, or
from
50,000 to 175,000, or from 75,000 to 150,000, or from 80,000 to 125,000.
In an embodiment of the invention, the copolymer will have a flat comonomer
incorporation profile as measured using Gel-Permeation Chromatography with
Fourier
Transform Infra-Red detection (GPC-FTIR). In an embodiment of the invention,
the
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copolymer will have a negative (i.e. "normal") comonomer incorporation profile
as
measured using GPC-FTIR. In an embodiment of the invention, the copolymer will
have an inverse (i.e. "reversed") or partially inverse comonomer incorporation
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" or "negative". If the comonomer incorporation is approximately
constant with
molecular weight, as measured using GPC-FTIR, the comonomer distribution is
described as "flat". The terms "reversed comonomer distribution" and
"partially
reversed 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 segments.
If
the comonomer incorporation rises with molecular weight, the distribution is
described
as "reversed". Where the comonomer incorporation rises with increasing
molecular
weight and then declines, the comonomer distribution is described as
"partially
reversed".
In an embodiment of the invention, the copolymer will have a melt flow ratio
(the MFR = 121/12) of less than 20, or less than 18, or less than 17, or less
than 16.5. In
further embodiments of the invention, the copolymer will have an 121/12 of
from 10 to
19.5, or from 11 to 19, or from 14 to 19, or from 13 to 17, or from 14 to 17,
or from 14
to 16.5.
In embodiments of the invention, the copolymer will have a comonomer
distribution breadth index (CDBI50), as determined by temperature elution
fractionation
(TREE), of at least 40 weight percent (wt%), or at least 50 wt%, or at least
60 wt%, or
at least 65 wt%, or at least 70 wt%, or at least 75 wt%. In further
embodiments of the
invention, the copolymer will have a comonomer distribution breadth index
(CDBI50),
as determined by temperature elution fractionation (TREE) of from 40 wt% to 85
wt%,
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or from 45 wt% to 85 wt%, or from 50 wt% to 85 wt%, or from 55 wt% to 80 wt%,
or
from 60 wt% to 80 wt%, or from 60 wt% to 75 wt%, or from 65 wt% to 75 wt%.
In embodiments of the invention, the copolymer will have a CY a-parameter
(also called the Carreau-Yasuda shear exponent) of from 0.4 to 1.0, or from
0.5 to 0.9,
or from 0.5 to 0.8.
In an embodiment of the invention, the copolymer will have a bimodal TREF
profile.
In an embodiment of the invention, the copolymers will have a TREF profile, as
measured by temperature rising elution fractionation, comprising: a primary
peak at a
temperature Ti; a secondary peak at a temp T2; and from 1 to 30 wt% of the
copolymer is represented at a temperature of from 90 C to 105C ; wherein T2 >
Ti
and the difference in temperature between T1 and T2 is less than 30 C. By the
term
"primary" peak, it is meant that the peak corresponds to an elution intensity
maximum
in a TREF profile which corresponds to a majority fraction of the copolymer.
By the
term "secondary" peak, it is meant that the peak corresponds to an elution
intensity
maximum in a TREF profile which corresponds to a minority fraction of the
copolymer.
Hence, for clarity, the primary and secondary peaks have a maximum which
occurs at
temperatures Ti and T2 respectively.
In embodiments of the invention, the difference in temperature between Ti and
T2 will be 5. 30 C, or 5. 20 C, or 5 15 C, or 5 10 C.
In embodiments of the invention, less than 30 wt%, or less than 25 wt%, or
less
than 20 wt%, or less than 15 wt%, or less than 10 wt%, or less than 7.5 wt% of
the
copolymer will be represented within a temperature range of from 90 C to 105 C
in a
TREF profile. In an embodiment of the invention, from 1 to 30 wt% of the
copolymer
will be represented within a temperature range of from 90 C to 105 C in a TREF
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profile. In another embodiment of the invention, from 3 to 25 wt% of the
copolymer
will be represented at a temperature range of from 90 C to 105 C in a TREF
profile.
In yet another embodiment of the invention, from 5 to 25 wt% of the copolymer
will be
represented at a temperature range from 90 C to 105 C in a TREF profile. In
yet
another embodiment of the invention, from 3 to 20 wt% of the copolymer will be
represented at a temperature range from 90 C to 105 C in a TREF profile. In a
further
embodiment of the invention, from 5 to 20 wt% of the copolymer will be
represented at
a temperature range of from 90 C to 105 C in a TREF profile. In still another
embodiment of the invention, from 10 to 25 wt% of the copolymer will be
represented
at a temperature from 90 C to 105 C in a TREF profile. In still yet another
embodiment of the invention, from 10 to 20 wt% of the copolymer will be
represented
at a temperature of from 90 C to 105 C in a TREF profile.
In an embodiment of the invention, T2 is greater than 90 C.
In an embodiment of the invention, Ti is in the range of from 70 to 90 C and
T2 is in the range of 85 to 100 C, provided that T2 is greater than Ti.
In an embodiment of the invention, Ti is in the range of from 80 to 90 C and
T2 is in the range of 90 to 100 C, provided that T2 is greater than Ti.
In embodiments of the invention, the copolymer will have a hexane extractables
level of _51.0 wt%, or 5 0.75 wt%, or 5 0.5 wt%, or < 0.5 wt%, or < 0.4 wt%,
or _5 0.3
wt%. In an embodiment of the invention, the copolymer has a hexane
extractables
level of from 0.1 to 0.3 wt%.
In an embodiment of the present invention, the copolymer will have little or
no
long chain branching. Without wishing to be bound by any single theory, the
melt
index ratio, 110/12 and its comparison with Mw/Mn for a given copolymer may be
a useful
proxy for the presence of long chain branching. Ethylene copolymers which have
low
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110/12 ratios (i.e. of below about 7.0) and which satisfy the relationship
110/12 ¨ 4.63 <
Mw/Mn are consistent with low levels or an absence of long chain branching
(see
European Pat. No. 751,967).
In an embodiment of the present invention, the copolymer will have a melt
index ratio, 110/12 value of 5. 7Ø In other embodiments of the invention,
the copolymer
will have an 110/12 of 5 6.5, or 5. 6Ø
In an embodiment of the present invention, the copolymer will satisfy the
relationship 110/12 ¨ 4.63 < Mw/Mn.
Catalyst Modifier Addition
The amount of catalyst modifier added to a reactor (or other associated
process equipment) is conveniently represented herein as the parts per million
(ppm)
of catalyst modifier based on the weight of copolymer produced.
The amount of catalyst modifier included in a polymerization catalyst is
conveniently represented herein as a weight percent (wt%) of the catalyst
modifier
based on the combined weight of the phosphinimine catalyst and the cocatalyst.
In
order to avoid any ambiguity, the phrase "weight of the polymerization
catalyst"
includes the weight of the phosphinimine catalyst and the cocatalyst, but not
the
weight of the catalyst modifier.
The total amount of catalyst modifier included in the polymerization catalyst
can
range anywhere from about 0.1 to 10 weight percent (or smaller ranges within
this
range) based on the combined weight of the phosphinimine catalyst and the
cocatalyst.
In an embodiment of the invention, the polymerization catalyst comprises: i) a
phosphinimine catalyst; ii) a cocatalyst (including the aluminoxane, if
present); and iii)
a catalyst modifier; wherein the catalyst modifier comprises a "long chain
amine"
compound as described above in "The Catalyst Modifier" section and which is
present
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in from 0.25 to 6.0 weight percent based on the weight of i), ii) and iii) of
the
polymerization catalyst.
In an embodiment of the invention, the polymerization catalyst comprises: i) a
phosphinimine catalyst; ii) a cocatalyst; and iii) a catalyst modifier;
wherein the
catalyst modifier is present from 0.25 to 6.0 weight percent based on the
weight of i),
ii) and iii) of the polymerization catalyst and comprises a compound having
the
formula: R1R2xN((CH2)n0H)y where R1 is a hydrocarbyl group having from 5 to 30
carbon atoms, R2 is hydrogen or a hydrocarbyl group having from 1 to 30 carbon
atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is 0, each n is
independently an
integer from 1 to 30 when y is 2, and n is an integer from 1 to 30 when y is
1.
In an embodiment of the invention, the polymerization process is carried out
in the
presence of a polymerization catalyst comprising: i) a phosphinimine catalyst;
ii) a
cocatalyst; and iii) a catalyst modifier; wherein the catalyst modifier is
present from
0.25 to 6.0 weight percent based on the weight of i), ii) and iii) of the
polymerization
catalyst and comprises a compound having the formula: R1R2xN((CH2)n0H)y where
R1
is a hydrocarbyl group having from 5 to 30 carbon atoms, R2 is hydrogen or a
hydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x
is 1, y
is 2 when x is 0, each n is independently an integer from 1 to 30 when y is 2,
and n is
an integer from Ito 30 when y is 1.
In an embodiment of the invention, the polymerization process is carried out
in
the presence of a polymerization catalyst comprising: i) a phosphinimine
catalyst; ii) a
cocatalyst; and iii) a catalyst modifier; wherein the catalyst modifier is
present from
0.25 to 5.0 weight percent based on the weight of i), ii) and iii) of the
polymerization
catalyst and comprises a compound having the formula: R1R2xN((CH2)n0H)y where
R1
is a hydrocarbyl group having from 5 to 30 carbon atoms, R2 is hydrogen or a
hydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x
is 1, y
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is 2 when x is 0, each n is independently an integer from 1 to 30 when y is 2,
and n is
an integer from 1 to 30 when y is 1.
In an embodiment of the invention, a polymerization process comprises
polymerizing ethylene and an alpha olefin in a solution reactor in the
presence of a
polymerization catalyst to give a polyethylene copolymer having a density of
from
0.910 g/cm3 to 0.927 g/cm3, a melt index (12) of from 0.25 to 5.0 g/10min, a
melt flow
ratio (121/12) <20, and a molecular weight distribution (Mw/Mn) 5 3.0; where
the
polymerization catalyst comprises: i) a phosphinimine catalyst; ii) a
cocatalyst; and iii)
a catalyst modifier; and where the catalyst modifier is present in from 0.25
to 6.0
weight percent based on the weight of i), ii) and iii) of the polymerization
catalyst and
comprises a compound having the formula: R1R2xN((CH2)n0H)y where R1 is a
hydrocarbyl group having from 5 to 30 carbon atoms, R2 is hydrogen or a
hydrocarbyl
group having from Ito 30 carbon atoms, xis 1 or 0, y is 1 when xis 1, y is 2
when xis
0, each n is independently an integer from 1 to 30 when y is 2, and n is an
integer
from 1 to 30 when y is 1.
The presence of a catalyst modifier in the polymerization catalyst may also
affect the properties of ethylene copolymers produced during polymerization of
ethylene and an alpha-olefin as well as the properties of films made with
those
copolymers.
Ethylene copolymers can be defined by a composition distribution breadth
index (CDB150), which is a measure as to how comonomers are distributed in an
ethylene copolymer. The definition of composition distribution breadth index
(CDBI50)
can be found in U.S. Pat. No. 5,206,075 and PCT publication WO 93/03093. The
CDBI50 is conveniently determined using techniques which isolate polymer
fractions
based on their solubility (and hence their comonomer content). For example,
temperature rising elution fractionation (TREF) as described by Wild et al. J.
Poly.
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Sci., Poly. Phys. Ed. Vol. 20, p441, 1982 can be employed. From the weight
fraction
versus composition distribution curve, the CDBI50 is determined by
establishing the
weight percentage of a copolymer sample that has a comonomer content within
50%
of the median comonomer content on each side of the median. Generally,
ethylene
copolymers with a CDBI50 of less than about 50%, are considered
"heterogeneously
branched" copolymers with respect to the short chain branching. Such
heterogeneously branched materials may include a highly branched fraction, a
medium branched fraction and a higher density fraction having little or no
short chain
branching. In contrast, ethylene copolymers with a CDBI50 of greater than
about 50%
are considered "homogeneously branched" copolymers with respect to short chain
branching in which the majority of polymer chains may have a similar degree of
branching.
EXAMPLES
Example 1
Part B: Solution Polymerization
The Continuous Solution Polymerization
All the polymerization experiments described below were conducted on a
continuous solution polymerization reactor. The process is continuous in all
feed
streams (solvent, monomers and catalyst) and in the removal of product. All
feed
streams were purified prior to the reactor by contact with various absorption
media to
remove catalyst killing impurities such as water, oxygen and polar materials
as is
known to those skilled in the art. All components were stored and manipulated
under
an atmosphere of purified nitrogen.
All the examples below were conducted in a reactor of 75 cc internal volume.
In
each experiment the volumetric feed to the reactor was kept constant and as a
consequence so was the reactor residence time.
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The catalyst solutions were pumped to the reactor independently but there was
contact between the activator and the catalyst before they entered the
reactor. The
polymerizations were carried out in cyclohexane at a pressure of 1500 psi.
Ethylene
was supplied to the reactor by a calibrated thermal mass flow meter at the
rates
shown in the Tables and was dissolved in the reaction solvent prior to the
polymerization reactor. Under these conditions the monomer conversion is a
dependent variable controlled by the catalyst concentration, reaction
temperature and
catalyst activity, etc.
The internal reactor temperature is monitored by a thermocouple in the
polymerization medium and can be controlled at the required set point to +/-
0.5 C.
Downstream of the reactor the pressure was reduced from the reaction pressure
(1500 psi) to atmospheric.
The ethylene conversion was determined by a dedicated on line gas
chromatograph by reference to propane which was used as an internal standard.
The
average polymerization rate constant was calculated based on the reactor hold-
up
time, the catalyst concentration in the reactor and the ethylene conversion
and is
expressed in 1/(mmormin).
where: Q is the percent ethylene conversion; [M] is the catalyst (metal)
concentration in the reactor expressed in mM; and HUT is the reactor hold-up
time in
minutes.
The catalyst used in all experiments was a titanium (IV) complex having one
cyclopentadienyl ligand, two methyl ligands and one tri (tertiary butyl)
phosphinimine
ligand ("CpTiNP(tBu)3Me"). The cocatalysts were a commercially available
methylalumoxane (MAO") and a commercially available borate ("Ph3CB(C6F5)4"). A
hindered phenol (2,6 di-tertiary butyl, 4-ethyl, phenol) was also used.
The molar ratios of the catalyst components follow:
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Al/Ti: 80/1
BM: 1.2/1
OH/Al: 0.3/1
The flow rate of ethylene to the reaction was 3.5 grams per minute.
The titanium concentration in the reactor was 0.8 to 1.1 pM.
The experiments were conducted at a temperature of 190 C.
Experiment 1-C is a control/comparative experiment using the phosphinimine
catalyst system described above. As shown in Table 1, this catalyst system
produced
a polymer having a weight average molecular weight (Mw) of about 4.7 x 104 at
a
catalyst productivity of about 2.4 x 106 grams of polymer per gram of Ti.
Inventive
experiment 2 was conducted in the presence of a long chain amine (sold under
the
trademark ATMER 163) at a mole ratio of 1.2/1 on the basis of the titanium in
the
catalyst (i.e. N/Ti ratio = 1.2/1). Expressed differently, the weight % of the
amine as a
percentage of the total catalyst composition is 1%. As shown in Table 1, the
long
chain amine did not have an adverse impact upon the catalyst productivity or
polymer
molecular weight under these conditions.
Inventive experiment 3 was conducted in same manner as experiment 2 except
a different long chain amine (sold under the trade name ARMOSTAT 1800) was
used.
The weight % of ARMOSTAT 1800 (based on the total catalyst composition) was
1.2%. As shown in Table 1, this amine did not have an adverse impact upon the
catalyst productivity or the molecular weight of the polymer. In addition, the
Mw/Mn of
all polymers was observed to be less than 2 (not shown in Table 1).
Stable operating conditions were observed for both of inventive experiments 2
and 3 and there was no visual evidence of any reactor.
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TABLE 1
Atmer Armostat Q Kp
Productivity Br./1000 MW
163:Ti 1800:Ti (%) (L/(mmol.min)) (gPE/gTi)
(mol:mol) (mol:mol) x 10-6 x 10-
4
1-C 0 0 90.14 3192 2.4 9.5 4.7
2 1.2 0 90.79 3442 2.4 9.7 4.6
3 0 1.2 90.52 4071 2.9 8.6 5.0
4-C 0 0 90.7 4247 3.0 8.9 4.9
Br = branches
MW= weight average molecular weight
Example 2
The experiments of this example were completed in the same polymerization
reactor described above in Example 1 and using the same catalyst system
(except as
noted below) and the same polymerization conditions.
The catalyst used in some experiments was the same as used in Example 1
("CpTiNP(tBu)3Me2") or the similar dichloride form, ("CpTiNP(tBu)3C12"), as
indicated
by "C12" or "Me2" under the "Catalyst" column in Table 2. The preparation of
CpTiNP(tBu)3Me2is described below.
At room temperature, 43.7mL of MeMgBr (3.0M in diethyl ether, 131.1mmol,
2.5 equiv.) was added dropwise (over lhr.) to a yellow solution of
Cp(tBu3PN)TiCl2
(20.985g, 52.4mmol) in toluene (300 mL). At the end of the addition the
reaction was
dark green and was allowed to stir at r.t. overnight. All solvent was removed
under
vacuum and the green residue was slurried in 100 mL of toluene and then dried
under
vacuum. The green residue was re-slurried in a 50:50 mixture of
heptane:toluene and
filtered through celite. The filtrate was dried under vacuum leaving the
product as a
light green solid (16.647 g, 88% yield).
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The same MAO and hindered phenol used in Example 1 were also used in
these experiments. The molar ratios of the components were also the same in
both
examples (Al/Ti = 80/1 and OH/AI = 0.3/1.
The comparative experiments of this example used the same borate as used in
Example 1 (Ph3CB(C6F5)4). The B/Ti mole ratio was 1.2/1.
The inventive experiments were conducted using an activator that is a complex
of a long chain amine catalyst modifier and a borate. The preparation of the
borate/amine complex is described below.
The long chain amine used in this example was prepared from a hydrogenated
bis (long chain alkyl) methyl amine. The long chain alkyl groups are reported
by the
supplier to contain an average of 16 ¨ 18 carbon atoms, so the amine may be
represented by the formula (C16-18)2NMe.
The long chain amine, ARMEEN M2HT, (42.713g, 81.967mmo1) was ground
into fine pieces using a ceramic mortar and pestle, and then added to a 2 L
round-
bottom flask equipped with a stir bar. Cyclohexane (1L) was added to the
flask, and
the mixture was stirred at 450 rpm until the ARMEEN fully dissolved, forming a
clear
colourless solution. Using a dropping funnel hydrochloric acid (80mL, 1.0 M in
H20,
80mmol) was added dropwise to the stirring solution, turning it white and
opaque. The
solution was maintained at room temperature and stirred overnight,
approximately
22hr., during which the solution turned a lustrous white colour. Meanwhile,
lithium
tetrakis(pentafluorophenyl)borate ethyl etherate (62.421g, 82.122mmol) was
dissolved
in deionized water (500mL), forming a white cloudy gel, which was stirred
overnight,
approximately 20hr. The borate mixture was loaded into a dropping funnel and
added
slowly to the armeenium chloride slurry and stirred for 2hr. After 2hr., the
mixture was
poured into a 500mL separatory funnel in portions, and the organic and aqueous
layers were separated into 1L Erlenmeyer flasks. The organic fraction was
washed in
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3 portions, each with brine (4 x 100mL), and the combined organic fractions
were
collected in a 2L Erlenmeyer flask. The combined organic fractions were dried
overnight over magnesium sulfate. The solution was then filtered through a
glass frit
into a 1L 3-necked round-bottom flask and the volume reduced to approximately
250
mL under vacuum. The beige, transparent solution was then quantitatively
transferred
to a 500 mL Schlenk flask and dried under vacuum. The final compound was a
viscous caramel-coloured oil (77.523g, 64.542mmo1, 79% yield) and is referred
to as
"ammonium borate" in Table 2.
The comparative experiments 10-C and 11-C were conducted using the same
borate activator used in Example 1 and in the absence of any long chain amine
modifier. Experiments 10-C and 11-C show that both of the Cl2 and Me2 forms of
the
catalyst provide good productivity and a polymer having a satisfactory
molecular
weight under the reported polymerization conditions. The weight percent of the
(C16-
18)2NMe amine to total catalyst was 1.74%.
Inventive experiments 12, 13 and 14 were conducted using the borate/long
chain amine complex described above. The BM mole ratio was 1.2/1. As shown in
Table 2, these inventive experiments also provide good productivity and a
satisfactory
polymer under the reported polymerization conditions. In addition, the
polymerization
of experiments 12¨ 14 were completed in a stable manner (no reactor upsets)
and
did not produce any visual evidence of reactor fouling under the reported
polymerization conditions.
TABLE 2
Run Catalyst Cocatalyst Kp Productivity Q (%) Br./1000C MW Mw/Mn
Form Form (gPE/gTi)
10-C 012 Ph3CB(C6F5).4 2,727 1,978,893
89.66 7.9 51670 1.84
11-C Me2 Ph3CB(C6F5)4 2,561
1,802,838 89.97 8.4 50182 1.67
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12 C12
Ammonium 3,506 2,372,480 90.36 8.7 48918 1.93
borate
13 Me2 Ammonium 2,727 1,978,893 89.66 8.6 50162 1.74
borate
14 Me2 Ammonium 3,804 2,616,495 90.2 9.5 46977 1.68
borate
Kp units are L/(mmol . minute)
Polymer Analysis
Molecular weight information (Mw and Mn) and molecular weight distribution
(Mw/Mn) were analyzed by gel permeation chromatography (GPC), using an
instrument sold under the trade name "Waters 150c", with 1,2,4-
trichlorobenzene as
the mobile phase at 140 C. The samples were prepared by dissolving the polymer
in
this solvent and were run without filtration. Molecular weights are expressed
as
polyethylene equivalents with a relative standard deviation of 2.9% for the
number
average molecular weight ("Mn") and 5.0% for the weight average molecular
weight
("Mw"). Polymer sample solutions (1 to 2 mg/mL) were prepared by heating the
polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at
150 C
in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added
to the
mixture in order to stabilize the polymer against oxidative degradation. The
BHT
concentration was 250 ppm. Sample solutions were chromatographed at 140 C on a
PL 220 high-temperature chromatography unit equipped with four Shodex columns
(HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate
of 1.0 mL/minute, with a differential refractive index (DRI) as the
concentration
detector. BHT was added to the mobile phase at a concentration of 250 ppm to
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protect the columns from oxidative degradation. The sample injection volume
was
200 mL. The raw data were processed with Cirrus GPC software. The columns were
calibrated with narrow distribution polystyrene standards. The polystyrene
molecular
weights were converted to polyethylene molecular weights using the Mark-
Houwink
equation, as described in the ASTM standard test method D6474.
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