Note: Descriptions are shown in the official language in which they were submitted.
ETHYLENE INTERPOLYMER PRODUCTS HAVING INTERMEDIATE BRANCHING
TECHNICAL FIELD
This disclosure relates to: copolymers of ethylene and a-olefins having
intermediate
branching; continuous polymerization processes to manufacture such copolymers;
analytical methods to characterize such copolymers; and the utility of such
copolymers in a myriad of manufactured articles.
BACKGROUND
The polymer industry is in constant need of improved ethylene interpolymer
products,
e.g. in flexible film applications such as food packaging, shrink films and
stretch films.
As disclosed hereinafter, ethylene interpolymer products having intermediate
branching have performance attributes that are advantageous in film
applications.
Relative to competitive ethylene interpolymer products of similar density and
melt
index, films produced from intermediately branched ethylene interpolymer
products
have, for example, higher dart impact, higher tensile strength and/or improved
optical
properties, such as higher film 45 gloss and lower film haze. The polymer
industry is
also in need of improved ethylene interpolymer products for rigid
applications,
including, but not limited to containers, lids, caps and toys, etc. Ethylene
interpolymer
products having intermediate branching also have utility in such rigid
applications.
Ethylene interpolymer products having intermediate branching were produced in
a
continuous solution polymerization process. Solution polymerization processes
are
typically carried out at temperatures above the melting point of the ethylene
interpolymer being synthesized. In a typical solution polymerization process,
catalyst
components, solvent, monomer(s) and hydrogen are fed under pressure to one or
more reactors. A wide variety of vessels (e.g. polymerization reactors, etc.)
and
vessel arrangements can be used under a wide range of process conditions
allowing
the production of a wide variety of ethylene interpolymer products. Post
reactor, the
polymerization reaction is typically quenched by adding a catalyst deactivator
and
passivated by adding an acid scavenger. Once passivated, the polymer solution
is
forwarded to polymer recovery operations where the ethylene interpolymer
product is
separated from process solvent, unreacted residual ethylene and unreacted
optional
a-olefin(s).
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SUMMARY OF THE DISCLOSURE
In this application, ethylene interpolymer products having intermediate
branching are
disclosed, as well as a process to manufacture such products and a method to
measure the Non-Comonomer Index Distribution (NCIDi) to quantify the amount of
intermediate branching in such products. Intermediate branching was defined as
branching that was longer than the branch length due to comonomer (e.g. C4 or
C6
branches from 1-hexene or 1-octene comonomers, respectively) and shorter than
the
entanglement molecular weight, Me (Me is a well-known concept in polymer
physics).
The amount of intermediate branching in the disclosed ethylene interpolymer
products
was characterized by the Non-Comonomer Index (NCI)', as well as the 'Non-
Comonomer Index Distribution (NCIDi), which was generated using triple
detection
cross fractionation chromatography (3D-CFC) techniques. Ethylene interpolymer
products, having intermediate branching, may, or may not contain long chain
branching as characterized by the Long Chain Branching Factor (LCBF). Long
chain
branches were branches that were greater than or equal to Me; long chain
branches
were macromolecular in nature and were evident in rheological measurements.
The
advantages of ethylene interpolymer products having intermediate branching in
films
applications is disclosed and compared with comparative ethylene interpolymer
.. product films that did not contain intermediate branching.
The following embodiments are provided for the purpose of a specific
disclosure for
the appended claims.
One embodiment of this disclosure, hereinafter embodiment [I], is fully
described
immediately below.
[1]-1. An ethylene interpolymer product comprising:
(i) a first ethylene interpolymer;
(ii) a second ethylene interpolymer, and;
(iii) optionally a third ethylene interpolymer;
wherein said second ethylene interpolymer is characterized by an
intermediate branching, wherein said intermediate branching is
characterized by a Non-Comonomer Index Distribution, NCIDi, having
a value characterized by Eq.(1a) and Eq.(1b);
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NCIDi < 1.000 ¨ 0.00201(1ogMi ¨ logM0 + 4.93) + 0.00137(/ogM1 ¨ logM0 +
4.93)2 ¨ 0.00034(/ogM1 ¨ logM0 + 4.93)3
Eq.(1a)
NCIDi> 0.730 ¨ 0.00388(/ogMi ¨ logM0 + 4.93) + 0.00313(/0gM1 ¨ logM0 +
4.93)2 ¨ 0.00069(/0gM1 ¨ logM0 + 4.93)3 Eq.(1b)
wherein, Mo is a peak molecular weight that characterizes a molecular
weight distribution of said second ethylene interpolymer when fit to a
log normal distribution;
wherein a first derivative of said NCIDi, dNCI191 dlogMi, Eq.(2);
dNCIDi
dlogMi = ,61+ 2132(logMi ¨ logM0 + 4.93) + 3,63(logMi ¨ logM0 + 4.93)2
Eq.(2)
has a value of 5 - 0.0001, coefficients f3o, 131, 32 and f33 are generated
by fitting said NCIDi of said second ethylene interpolymer to a third
order polynomial, Eq.(3),
NCIDi = fl o+ logMo+ 4.93) + /32(logMi¨ logM0 + 4.93)2 +
A(logMi ¨ logM0 + 4.93)3 Eq.(3)
wherein said NCID; may be experimentally measured or computer
simulated;
wherein said ethylene interpolymer product does not contain long
chain branching as characterized by a dimensionless Long Chain
Branching Factor, LCBF, having a value of < 0.001.
[1]-2. The ethylene interpolymer as described in [1]-1, wherein said
first
ethylene interpolymer is synthesized using a homogenous catalyst
formulation and said second ethylene interpolymer is synthesized
using an intermediate branching catalyst formulation.
[1]-3. The ethylene interpolymer product as described in [1]-2,
wherein said
homogeneous catalyst formulation is an unbridged single site catalyst
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formulation and said intermediate branching catalyst formulation is an
in-line intermediate branching catalyst formulation or a batch
intermediate branching catalyst formulation.
[1]-4. The ethylene interpolymer product as described in [1]-1
having a melt
index from about 0.3 to about 500 dg/minute and a density from about
0.858 to about 0.965 g/cc; wherein melt index is measured according
to ASTM D1238 (2.16 kg load and 190 C) and density is measured
according to ASTM D792.
[1]-5. The ethylene interpolymer product as described in [1]-1
having a
Mw/Mn from about 2 to about 25.
[1]-6. The ethylene interpolymer product as described in [1]-1
having a
CDB150 from about 10% to about 98%.
[1]-7. The ethylene interpolymer product as described in [1]-1;
wherein
(i) said first ethylene interpolymer has a melt index from about
0.001 to about 1000 dg/minute, a density from about 0.855
g/cm3 to about 0.975 g/cc and is from about 0 to 60 weight
percent of said ethylene interpolymer product;
(ii) said second ethylene interpolymer has melt index from about
0.001 to about 1000 dg/minute, a density from about 0.89
g/cm3 to about 0.965 g/cc and is from about 10 to 99 weight
percent of said ethylene interpolymer product;
(iii) optionally said third ethylene interpolymer has a melt index
from about 0.1 to about 10000 dg/minute, a density from
about 0.855 to about 0.975 g/cc and is from 0 to about 30
weight percent of said ethylene interpolymer product;
wherein melt index is measured according to ASTM D1238 (2.16 kg
load and 190 C), density is measured according to ASTM D792 and
weight percent is the weight of said first, said second or said optional
third ethylene interpolymer divided by the weight of said ethylene
interpolymer product.
[1]-8. The ethylene interpolymer product as described in [1]-1
synthesized
using a solution polymerization process.
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[1]-9. The ethylene interpolymer product as described in [1]-1
further
comprising from 0.001 to about 10 mole percent of one or more CC-
olefin.
[1]-10. The ethylene interpolymer product as described in [1]-9;
wherein said
one or more a-olefin are C3 to Cio a-olefins.
[1]-11. The ethylene interpolymer product as described in [1]-10;
wherein said
one or more a-olefin is 1-hexene, 1-octene or a mixture of 1-hexene
and 1-octene.
[1]-12. The ethylene interpolymer product as described in [1]-1
wherein said
third ethylene interpolymer is synthesized using a heterogeneous
catalyst formulation or a homogeneous catalyst formulation or an
intermediate branching catalyst formulation.
[1]-13. The ethylene interpolymer product as described in [1]-1;
wherein said
first ethylene interpolymer has a first CDB150 from about 20 to about
98%, said second ethylene interpolymer has a second CDB150 from
about 20 to about 70% and said optional third ethylene interpolymer
has a third CDB150from about 20 to about 98%.
[1]-14. The ethylene interpolymer product as described in [1]-13;
wherein said
first CDBI50 is higher than said second CDB150.
Another embodiment of this disclosure, hereinafter embodiment [11], is fully
described
immediately below.
[11]-1. An ethylene interpolymer product comprising:
(i) a first ethylene interpolymer;
(ii) a second ethylene interpolymer, and;
(iii) optionally a third ethylene interpolymer;
wherein said second ethylene interpolymer is characterized by an
intermediate branching, wherein said intermediate branching is
characterized by a Non-Comonomer Index Distribution, NCIDi, having
a value characterized by Eq.(1a) and Eq.(1b), wherein, Mo is a peak
molecular weight that characterizes a molecular weight distribution of
said second ethylene interpolymer when fit to a log normal
distribution;
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dNCIDi
wherein a first derivative of said NC1D dlogMi'
i, Eq.(2), has a value of
- 0.0001, coefficients 130,131, 132 and 133 are generated by fitting said
NCIDi of said second ethylene interpolymer to a third order
polynomial, Eq.(3),
wherein said NCIDI may be experimentally measured or computer
simulated;
wherein said ethylene interpolymer product contains long chain
branching as characterized by a dimensionless Long Chain Branching
Factor, LCBF, having a value 0.001.
[11]-2. The ethylene interpolymer as described in [11]-1, wherein said
first
ethylene interpolymer is synthesized using a homogenous catalyst
formulation and said second ethylene interpolymer is synthesized
using an intermediate branching catalyst formulation.
[11]-3. The ethylene interpolymer product as described in [11]-2,
wherein said
homogeneous catalyst formulation is a bridged single site catalyst
formulation and said intermediate branching catalyst formulation is an
in-line intermediate branching catalyst formulation or a batch
intermediate branching catalyst formulation.
[11]-4. The ethylene interpolymer product as described in [11]-1
having a melt
index from about 0.3 to about 500 dg/minute and a density from about
0.858 to about 0.965 g/cc; wherein melt index is measured according
to ASTM D1238 (2.16 kg load and 190 C) and density is measured
according to ASTM D792.
[11]-5. The ethylene interpolymer product as described in [11]-1
having a
Mw/Mn from about 2 to about 25.
[11]-6. The ethylene interpolymer product as described in [11]-1
having a
CDB150 from about 10% to about 98%.
[11]-7. The ethylene interpolymer product as described in [11]-1;
wherein
(i) said first ethylene interpolymer has a melt index from about
0.001 to about 1000 dg/minute, a density from about 0.855
g/cm3 to about 0.975 g/cc and is from about 0 to 60 weight
percent of said ethylene interpolymer product;
(ii) said second ethylene interpolymer has melt index from
about 0.001 to about 1000 dg/minute, a density from about
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0.89 g/cm3 to about 0.965 g/cc and is from about 10 to 99
weight percent of said ethylene interpolymer product;
(iii) optionally said third ethylene interpolymer has a
melt index
from about 0.1 to about 10000 dg/minute, a density from
about 0.855 to about 0.975 g/cc and is from 0 to about 30
weight percent of said ethylene interpolymer product;
wherein melt index is measured according to ASTM D1238 (2.16 kg
load and 190 C), density is measured according to ASTM D792 and
weight percent is the weight of said first, said second or said optional
third ethylene interpolymer divided by the weight of said ethylene
interpolymer product.
[11]-8. The ethylene interpolymer product as described in [11]-1
synthesized
using a solution polymerization process.
[11]-9. The ethylene interpolymer product as described in [11]-1
further
comprising from 0.001 to about 10 mole percent of one or more a-
olefin.
[11]-10. The ethylene interpolymer product as described in [11]-9; wherein
said
one or more a-olefin are C3 to C10 a-olefins.
[11]-11. The ethylene interpolymer product as described in [11]-10; wherein
said one or more a-olefin is 1-hexene, 1-octene or a mixture of 1-
hexene and 1-octene.
[11]-12. The ethylene interpolymer product as described in [11]-1 wherein said
third ethylene interpolymer is synthesized using a heterogeneous
catalyst formulation or a homogeneous catalyst formulation or an
intermediate branching catalyst formulation.
[11]-13. The ethylene interpolymer product as described in [11]-1; wherein
said
first ethylene interpolymer has a first CDB150 from about 20 to about
98%, said second ethylene interpolymer has a second CDB150 from
about 20 to about 70% and said optional third ethylene interpolymer
has a third CDB150from about 20 to about 98%.
[11]-14. The ethylene interpolymer product as described in [11]-13; wherein
said first CDB150 is higher than said second CDB15o.
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An additional embodiment of this disclosure, hereinafter embodiment [111], is
fully
described immediately below.
[111]-1 . An ethylene interpolymer product comprising at least one
ethylene
interpolymer; wherein said ethylene interpolymer is characterized by:
an intermediate branching wherein said intermediate branching is
characterized by a Non-Comonomer Index Distribution, NCID1, having
a value characterized by Eq.(1 a) and Eq.(1 b);
wherein, Mo is a peak molecular weight that characterizes a molecular
weight distribution of said ethylene interpolymer when fit to a log
normal distribution;
wherein a first derivative of said NC1Di, dNCIDi dlogMi, Eq.(2), has a value
of 5
- 0.0001, coefficients Po, 131, 132 and p3 are generated by fitting said
NCIDi of said ethylene interpolymer to a third order polynomial, Eq.(3),
wherein said NC1D, may be experimentally measured or computer
simulated.
[111]-2. The ethylene interpolymer product as described in [111]-1 ,
wherein said
ethylene interpolymer is synthesized using an intermediate branching
catalyst formulation.
[111]-3. The ethylene interpolymer product as described in [111]-2,
wherein said
intermediate branching catalyst formulation is an in-line intermediate
branching catalyst formulation or a batch intermediate catalyst
formulation.
[111]-4. The ethylene interpolymer product as described in [1111-1,
comprising a
first ethylene interpolymer, a second ethylene interpolymer and
optionally a third ethylene interpolymer;
wherein at least one of said first, said second and/or said third
ethylene interpolymer is characterized by said NCIDi having a value
characterized by Eq.(1 a) and Eq.(1 b) and said first derivative Eq.(2)
has a value -0.0001, wherein said NCIDi may be experimentally
measured or computer simulated.
[111]-5. The ethylene interpolymer product as described in [111]-4,
wherein said
first ethylene interpolymer is synthesized with a first heterogeneous
catalyst formulation, said second ethylene interpolymer is synthesized
with a second heterogeneous catalyst formulation and said optional
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third ethylene interpolymer is synthesized with a third heterogeneous
catalyst formulation; wherein said first, said second and said third
heterogeneous catalyst formulations may be the same formulation or
different formulations with the proviso that at least one of said first,
said second and said third heterogeneous catalyst formulations is an
intermediate branching catalyst formulation.
[111]-6. The ethylene interpolymer product as described in [111]-1, further
characterized by a dimensionless Long Chain Branching Factor,
LCBF, having a value <0.001.
[111]-7. The ethylene interpolymer product as described in [111]-1 having a
melt
index from about 0.3 to about 500 dg/minute and a density from about
0.890 to about 0.965 g/cc; wherein melt index is measured according
to ASTM D1238 (2.16 kg load and 190 C) and density is measured
according to ASTM D792.
[111]-8. The ethylene interpolymer product as described in [111]-1 having a
Mw/Mn from about 2.2 to about 25.
[111]-9. The ethylene interpolymer product as described in [111]-1 having a
CDB150 from about 10% to about 98%.
[111]-10. The ethylene interpolymer product as described in [111]-5; wherein
(i) said first ethylene interpolymer has a melt index from about 0.001
to about 1000 dg/minute, a density from about 0.890 g/cm3 to about
0.965 g/cc and is from about 0 to 60 weight percent of said ethylene
interpolymer product;
(ii) said second ethylene interpolymer has melt index from about
0.001 to about 1000 dg/minute, a density from about 0.89 g/cm3 to
about 0.965 g/cc and is from about 10 to 99 weight percent of said
ethylene interpolymer product; and
(iii) optionally said third ethylene interpolymer has a melt index from
about 0.1 to about 10000 dg/minute, a density from about 0.89 to
about 0.965 g/cc and is from 0 to about 30 weight percent of said
ethylene interpolymer product;
wherein melt index is measured according to ASTM D1238 (2.16 kg
load and 190 C), density is measured according to ASTM D792 and
weight percent is the weight of said first, said second or said optional
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third ethylene interpolymer divided by the weight of said ethylene
interpolymer product.
[111]-11. The ethylene interpolymer product as described in [111]-1
synthesized
using a solution polymerization process.
[111]-12. The ethylene interpolymer product as described in [111]-1 further
comprising from 0.001 to about 10 mole percent of one or more a-
olefin.
[111]-13. The ethylene interpolymer product as described in [111]-11; wherein
said one or more a-olefin are C3 to C10 a-olefins.
[111]-14. The ethylene interpolymer product as described in [111]-12; wherein
said one or more a-olefin is 1-hexene, 1-octene or a mixture of 1-
hexene and 1-octene.
One embodiment of this disclosure, hereinafter embodiment [IV], relates to a
method
to determine NCID, as fully described immediately below.
[IV]-1. A method to determine the Non-Comonomer Index Distribution,
NCIDi, of an ethylene interpolymer product, comprising:
a) placing from about 150 to about 300 mg of said ethylene
interpolymer product into a sample dissolution vessel of a
Polymer Char Crystaf-TREF unit;
b) dissolving said ethylene interpolymer product by adding 35 mL of
solvent to said dissolution vessel, heating said vessel to 140 C,
then stirring for about 2 to about 3 hours to form a polymer
solution; wherein said solvent is 1,2,4-trichlorobenzene containing
250 ppm of 2,6-di-tert-butyl-4-methylphenol;
C) transferring said polymer solution to a TREF column and
equilibrating said TREF column at 110 C for about 20 to about 45
minutes;
d) cooling said polymer solution by reducing the temperature of said
TREF column to 30 C, employing a cooling rate of 0.2 C/minute,
to form a crystallized ethylene interpolymer product and
equilibrating said TREF column at 30 C for 90 minutes;
e) heating said TREF column to a first dissolution temperature,
employing a heating rate of 1.0 C/min, and maintaining said
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TREF column at said first dissolution temperature for at least 50
minutes;
f) eluting a first TREF fraction from said TREF column using
said
solvent flowing at 1 mL/minute;
g) transferring said first TREF fraction through a heated transfer line
into a Size Exclusion Chromatography (SEC) unit operating at
140 C to produce an SEC effluent; wherein said heated transfer
line is maintained at 140 C;
h) passing said SEC effluent through a SEC detection system;
wherein said SEC detection system includes a differential
refractive index detector (DRI) to determine a polymer
concentration; a dual-angle (15 and 90 ) light scattering detector
to determine a viscosity average molecular weight, Mvf; and, a
differential viscometer to determine an intrinsic viscosity, [in of
said first TREF fraction; wherein superscript f represents the fh
TREF fraction, where f = 1 for said first TREF fraction;
i) calculating a Non-Comonomer Index, NCI, of said first TREF
fraction according to Eq.(4);
1000000(hjf/(4)0.725)
NC/f = ______________________________________________________ Eq.(4)
(391.98¨Ax (B x Tf+C )
wherein, A, B and C are constants that depend on the a¨olefin
comonomer in said ethylene interpolymer and Tf is a weight
average TREF elution temperature of said first TREF fraction
calculated based on the re-constructed analytical TREF profile of
said ethylene interpolymer product;
j) incrementally increasing the temperature of said TREF column
and repeat steps (e) through (i), such that said ethylene
interpolymer is fractionated into at least 5 TREF fractions to less
than 21 TREF fractions;
k) calculating said Non-Comonomer Index Distribution (NCIDi) of
said ethylene interpolymer according to Eq.(5)
NCIDi = Eli. (wt. fr.)f (wi Iog(Mi))f x NC/f Eq.(5)
wherein (wt.fr.)f represents the weight fraction of the fh TREF
fraction and (wilog(Mi))f represents the weight fraction of the fh
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TREF fraction having molar mass Mi and superscript f represents
the TREF fraction number.
[IV]-2. The method as described in [IV]-1; wherein said Polymer Char
Crystaf-TREF unit was programmed and controlled with Polymer Char
TREF software having step-elution capability.
[IV]-3. The method as described in [IV]-1; wherein said Size
Exclusion
Chromatography (SEC) unit comprised a PL 220 high-temperature
chromatography unit equipped with either four Shodex columns
(HT803, HT804, HT805 and HT806), or four PL Mixed ALS or BLS
columns; and SEC data was acquired and processed using Cirrus
GPC software and Excel spreadsheet to calculate said absolute molar
mass and said intrinsic viscosity.
[IV]-4. The method as described in [IV]-1, wherein said constant A is
2.1626,
said constant B is -0.6737 and said C is 63.6727, when the a-olefin is
1-octene.
An additional embodiment of this disclosure, hereinafter embodiment [V],
relates to
the manufacture an ethylene interpolymer product having intermediate
branching, as
fully described immediately below.
[V]-1. A continuous solution polymerization process wherein an ethylene
interpolymer product is produced, wherein said ethylene interpolymer
product is characterized as having an intermediate branching, wherein
said intermediate branching is characterized by a Non-Comonomer
Index Distribution, NCIDi, comprising:
a) injecting ethylene, a process solvent, a first catalyst
formulation, one or more a-olefins and optionally hydrogen
into a first reactor to produce a first exit stream containing a
first ethylene interpolymer in said process solvent;
b) passing said first exit stream into a second reactor and
injecting into said second reactor, ethylene, said process
solvent, an intermediate branching catalyst formulation, one
or more a-olefins and optionally hydrogen to produce a
second exit stream containing a second ethylene
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interpolymer and said first ethylene interpolymer in said
process solvent;
c) optionally adding a catalyst deactivator A to said second exit
stream, downstream of said second reactor, forming a
deactivated solution A;
d) passing said second exit stream, or optionally said
deactivated solution A, into a third reactor and optionally
injecting into said third reactor, ethylene, process solvent,
one or more a-olefins, hydrogen and a third catalyst
formulation to produce a third exit stream containing an
optional third ethylene interpolymer, said second ethylene
interpolymer and said first ethylene interpolymer in said
process solvent;
e) adding a catalyst deactivator B to said third exit stream,
downstream of said third reactor, forming a deactivated
solution B; with the proviso that e) is skipped if said catalyst
deactivator A was added in c);
optionally, b) through e) are skipped and replaced with f) through j),
with the proviso that if b) through e) are not skipped, e) is followed by
k);
f) injecting ethylene, said process solvent, an intermediate
branching catalyst formulation, one or more a-olefins and
optionally hydrogen into a second reactor to produce a
second exit stream containing a second ethylene
interpolymer in said process solvent;
g) combining said first and said second exit streams,
downstream of said second reactor, to form a third exit
stream;
h) optionally adding a catalyst deactivator A to said third exit
stream forming a deactivated solution A;
i) passing said third exit stream into a third reactor and
optionally injecting into said third reactor, ethylene, said
process solvent, one or more a-olefins, hydrogen and a third
catalyst formulation to produce a fourth exit stream containing
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an optional third ethylene interpolymer, said second ethylene
interpolymer and said first ethylene interpolymer in said
process solvent;
j) adding a catalyst deactivator B to said fourth exit stream,
downstream of said third reactor, forming a deactivated
solution B; with the proviso that j) is skipped if said catalyst
deactivator A was added in h);
k) adding a passivator to said deactivated solution A or said
deactivated solution B to form a passivated solution;
I) phase separating said passivated solution to recover said
ethylene interpolymer product;
wherein said ethylene interpolymer product is characterized by said
Non-Comonomer Index Distribution, NCIDi, having a value
characterized by Eq.(1a) and Eq.(1b);
wherein, Mo is a peak molecular weight that characterizes a molecular
weight distribution of said second ethylene interpolymer when fit to a
log normal distribution;
wherein a first derivative of said NOIR, dNCIDi dlogMi, Eq.(2), has a value of
s
- 0.0001, coefficients po, pi, 132 and 133 are generated by fitting said
NCIDI of said second ethylene interpolymer to a third order
polynomial, Eq.(3), wherein said NCIDI may be experimentally
measured or computer simulated.
[V]-2. The process as described in [V]-1, wherein said first
catalyst
formulation is an unbridged single site catalyst formulation; wherein
said ethylene interpolymer product is further characterized by a
dimensionless Long Chain Branching Factor, LCBF, having a value <
0.001.
M-3. The process as described in M-1, wherein said first catalyst
formulation is a bridged metallocene catalyst formulation; wherein
said ethylene interpolymer product is further characterized by a
dimensionless Long Chain Branching Factor, LCBF, having a value
0.001.
M-4. The process as described in M-1, wherein said first catalyst
formulation is said intermediate branching catalyst formulation, or a
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second intermediate branching formulation, or a Ziegler-Natta catalyst
formulation.
[V]-5. The process as described in [V]-1, wherein said third
catalyst
formulation is one or more of: an unbridged single site catalyst
formulation; a bridged metallocene catalyst formulation; said
intermediate branching catalyst formulation; a second intermediate
branching catalyst formulation; a Ziegler-Natta catalyst formulation.
[V]-6. The process as described in [V]-1, wherein said ethylene,
said one or
more a-olefin, said hydrogen and said first catalyst formulation are not
injected into said first reactor and said first ethylene interpolymer is
not formed; optionally, said process solvent is not injected into said
first reactor.
[V]-7. The process as described in [V]-1, wherein said intermediate
branching catalyst formulation is an in-line intermediate branching
catalyst formulation formed in an in-line process comprising:
a) forming a first product mixture in a first heterogeneous
catalyst assembly by combining a stream Si and a stream S2
and allowing said first product mixture to equilibrate for a
HUT-1 seconds; wherein said stream Si comprises a
magnesium compound and an aluminum alkyl in said process
solvent and said stream S2 comprises a chloride compound
in said process solvent;
b) forming a second product mixture in said first heterogeneous
catalyst assembly by combining said first product mixture with
a stream S3 and allowing said second product mixture to
equilibrate for a HUT-2 seconds; wherein said stream S3
comprises a metal compound in said process solvent;
c) forming said in-line intermediate branching catalyst
formulation in said first heterogeneous catalyst assembly by
combining said second product mixture with a stream S4 and
allowing said in-line intermediate branching catalyst
formulation to equilibrate for a HUT-3 seconds prior to
injection into said second reactor and optional injection into
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said third reactor, wherein said stream S4 comprises an alkyl
aluminum co-catalyst in said process solvent;
d) optionally, c) is skipped and said in-line intermediate
branching catalyst formulation is formed inside said second
reactor and optionally inside said third reactor; wherein said
second product mixture is equilibrated for an additional HUT-
3 seconds and injected into said second reactor and
optionally into said third reactor, and said stream S4 is
independently injected into said second reactor and optionally
into said third reactor, and;
e) optionally, a second heterogeneous catalyst assembly is
employed wherein a) through c) are conducted to form a
second in-line intermediate branching catalyst formulation
that is injected into said third reactor; optionally said second
in-line intermediate branching catalyst formulation is formed
inside said third reactor according to d);
wherein said HUT-1 is from about 5 seconds to about 70 seconds,
said HUT-2 is from about 2 seconds to about 50 seconds and said
HUT-3 is from about 0.5 to about 15 seconds.
M-8. The process as described in M-7, wherein;
a) said magnesium compound is defined by the formula
Mg(R1)2, wherein the R1 groups may be the same or different;
b) said aluminum alkyl is defined by the formula Al(R3)3, wherein
the R3 groups may be the same or different;
c) said chloride compound is defined by the formula R2CI;
d) said metal compound is defined by the formulas M(X)n or
MO(X)n, wherein M represents titanium, zirconium, hafnium,
vanadium, niobium, tantalum, chromium, molybdenum,
tungsten, manganese, technetium, rhenium, iron, ruthenium,
osmium or mixtures thereof, 0 represents oxygen, X
represents a halogen atom and n is an integer that satisfies
the oxidation state of the metal M, and;
e) said alkyl aluminum co-catalyst is defined by the formula
Al(R4)p(0R5)q(X)r, wherein the R4 groups may be the same or
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different, the OR5 groups may be the same or different and
(p+q+r) = 3, with the proviso that p is greater than 0;
wherein R1, R2, R3, R4 and R5 represent hydrocarbyl groups having
from 1 to 10 carbon atoms; optionally R2 may be a hydrogen atom.
[V]-9. The process as described in M-7, wherein; a molar ratio of said
aluminum alkyl to said magnesium compound in said second and
optionally said third reactor is from about 3.0: 1 to about 70: 1; a
molar ratio of said chloride compound to said magnesium compound
in said second and optionally said third reactor is from about 1.0 : 1 to
about 4.0: 1; a molar ratio of said alkyl aluminum co-catalyst to said
metal compound in said second and optionally said third reactor is
from about 0 : 1 to about 10 : 1, and; a molar ratio of said aluminum
alkyl to said metal compound in said second and optionally said third
reactor is from about 0.05 : 1 to about 2 : 1.
[V]-10. The process as described in [V]-1, wherein said intermediate
branching catalyst formulation is a batch intermediate branching
catalyst formulation; wherein said batch intermediate branching
catalyst formulation is formed within said second reactor by injecting a
stream S5 and a stream S4 into said second reactor, wherein said
stream S4 comprises an alkyl aluminum co-catalyst in said process
solvent and said stream S5 comprises a batch intermediate branching
procatalyst in said process solvent; optionally said batch intermediate
branching catalyst formulation is employed in said third reactor by
independently injecting said stream S5 and said stream S4 into said
third reactor.
[V]-11. The process as described in [V]-10, wherein said alkyl aluminum co-
catalyst is defined by the formula Al(R4)p(0R5)q(X)r, wherein the R4
groups may be the same or different, the OR5 groups may be the
same or different and (p+q+r) = 3, with the proviso that p is greater
than 0; wherein R4 and R5 represent hydrocarbyl groups having from
1 to 10 carbon atoms.
[V]-12. The process as described in M-10; wherein said batch intermediate
branching procatalyst comprises:
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a) a magnesium compound defined by the formula Mg(R1)2,
wherein R1 may be the same or different;
b) a chloride compound defined by the formula R2CI;
c) optionally an aluminum alkyl halide defined by the formula
(R9vAIX3-v; wherein the R6 groups may be the same or
different, X represents a halogen atom, and v is 1 or 2;
d) a metal compound defined by the formulas M(X) n or MO(X)n,
wherein M represents titanium, zirconium, hafnium,
vanadium, niobium, tantalum, chromium, molybdenum,
tungsten, manganese, technetium, rhenium, iron, ruthenium,
osmium or mixtures thereof, 0 represents oxygen, X
represents a halogen atom and n is an integer that satisfies
the oxidation state of the metal M;
wherein R1, R2 and R6 represent hydrocarbyl groups having from 1 to
10 carbon atoms; optionally R2 may be a hydrogen atom.
[V]-13. The process as described in [V]-12 wherein a molar ratio of said
chloride compound to said magnesium compound in said batch
intermediate branching procatalyst is from about 2 : 1 to about 3 : 1;
wherein a molar ratio of said magnesium compound to said metal
compound in said procatalyst is from 5: 1 to about 10: 1; wherein a
molar ratio of said aluminum alkyl halide to said magnesium
compound in said procatalyst is from about 0 : 1 to about 0.5 : 1, and;
wherein a molar ratio of said alkyl aluminum co-catalyst to said metal
compound in said procatalyst is from about 0.5 : 1 to about 10 : 1.
Embodiments of this disclosure include articles of manufacture. Not to be
construed
as limiting, the ethylene interpolymer products disclosed herein may be
converted into
manufactured articles comprising a film. Non-limiting examples of processes to
manufacture such films include blown film processes, double bubble processes,
triple
bubble processes, cast film processes, tenter frame processes and machine
direction
orientation (MDO) processes. An embodiment of this disclosure, hereinafter
embodiment [VI], is fully described immediately below.
[VI]-1 . A film comprising at least one layer comprising an ethylene
interpolymer product comprising at least one ethylene interpolymer,
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wherein said ethylene interpolymer is characterized by an
intermediate branching,
wherein said intermediate branching is characterized by a Non-
Comonomer Index Distribution, NCIDi, having a value characterized
by Eq.(1a) and Eq.(1b), wherein, Mo is a peak molecular weight that
characterizes a molecular weight distribution of said ethylene
interpolymer when fit to a log normal distribution; wherein a first
dNCIDi
derivative of said NCIDi, ________________ Eq.(2), has a value of 5 -
0.0001,
dlogMi'
coefficients f3o, Pi, (32 and 133 are generated by fitting said NCID, of said
ethylene interpolymer to a third order polynomial, Eq.(3), and wherein
said NCIDi may be experimentally measured or computer simulated.
[VI]-2. The film as described in [VI]-1, wherein said ethylene
interpolymer is
synthesized using an intermediate branching catalyst formulation.
[VI]-3. The film as described in [VI]-2, wherein said intermediate
branching
catalyst formulation is an in-line intermediate branching catalyst
formulation or a batch intermediate catalyst formulation.
[VI]-4. The film as described in [VI]-1, wherein said ethylene
interpolymer
product comprises a first ethylene interpolymer, a second ethylene
interpolymer and optionally a third ethylene interpolymer;
wherein at least one of said first, said second and/or said third
ethylene interpolymer is characterized by said NCIDI having a value
characterized by Eq.(1a) and Eq.(1b) and said first derivative Eq.(2)
has a value 5-0.0001, wherein said NCIDi may be experimentally
measured or computer simulated.
[VI]-5. The film as described in [VI]-4, wherein said first ethylene
interpolymer is synthesized with a first heterogeneous catalyst
formulation, said second ethylene interpolymer is synthesized with a
second heterogeneous catalyst formulation and said optional third
ethylene interpolymer is synthesized with a third heterogeneous
catalyst formulation; wherein said first, said second and said third
heterogeneous catalyst formulations may be the same formulation or
different formulations with the proviso that at least one of said first,
said second and/or said third heterogeneous catalyst formulations is
an intermediate branching catalyst formulation.
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[VI]-6. The film as described in [VI]-1, wherein said ethylene
interpolymer is
further characterized by a dimensionless Long Chain Branching
Factor, LCBF, having a value < 0.001.
[VI]-7. The film as described in [VI]-1, wherein said ethylene
interpolymer
product has a melt index from about 0.3 to about 15 dg/minute and a
density from about 0.890 to about 0.965 g/cc; wherein melt index is
measured according to ASTM D1238 (2.16 kg load and 190 C) and
density is measured according to ASTM D792.
[VI]-8. The film as described in [VI]-1, wherein said ethylene
interpolymer
product has a Mw/Mn from about 2.2 to about 25 and a CDBI50 from
about 10% to about 98%.
[VI]-9. The film as described in [VI]-5, wherein:
(i) said first ethylene interpolymer has a melt index from about 0.001
to about 1000 dg/minute, a density from about 0.890 g/cm3 to about
0.965 g/cc and is from about 0 to 60 weight percent of said ethylene
interpolymer product;
(ii) said second ethylene interpolymer has melt index from about
0.001 to about 1000 dg/minute, a density from about 0.89 g/cm3 to
about 0.965 g/cc and is from about 10 to 99 weight percent of said
ethylene interpolymer product; and
(iii) optionally said third ethylene interpolymer has a melt index from
about 0.1 to about 10000 dg/minute, a density from about 0.890 to
about 0.965 g/cc and is from 0 to about 30 weight percent of said
ethylene interpolymer product;
wherein melt index is measured according to ASTM D1238 (2.16 kg
load and 190 C), density is measured according to ASTM D792 and
weight percent is the weight of said first, said second or said optional
third ethylene interpolymer divided by the weight of said ethylene
interpolymer product.
[VI]-10. The film as described in [VI]-1, wherein said ethylene interpolymer
product is manufactured using a solution polymerization process.
[VI]-11. The film as described in [VI]-1, wherein said ethylene interpolymer
product further comprises from 0.001 to about 10 mole percent of one
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or more a-olefin; wherein said one or more a-olefin are C3 to C10 11-
olefins.
[VI]-12. The film as described in [VI]-11, wherein said one or more a-olefin
is
1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.
[VI]-13. The film as described in [VI]-1 , wherein said film is a monolayer
film
having a dart impact that is from 10% to 110% higher, relative to a
comparative monolayer film; wherein said comparative monolayer film
contains a comparative ethylene interpolymer that has replaced said
ethylene interpolymer;
wherein said comparative ethylene interpolymer does not contain
intermediate branching, has a comparative Non-Comonomer Index
Distribution (NCIDi)c that does not satisfy Eq.(1a) and Eq.(1b), and
has a comparative first derivative (dNC1D1-)c dlogMi > 0.0001.-
[VI]-14. The film as described in [VI]-1, wherein said at least one layer
further
comprises one or more polyolefin.
[VI]-15. The film as described in [VI]-14, wherein said polyolefin is one or
more ethylene polymer, one or more propylene polymer or a mixture
of said ethylene polymer and said propylene polymer.
[VI]-16. The film as described in [VI]-1 , wherein said film has a thickness
from
0.5 mil to 10 mil.
[VI]-17. The film as described in [VI]-1, wherein said film comprises from 2
to
11 layers, wherein at least one or more layer comprises said ethylene
interpolymer product having intermediate branching.
A further embodiment of this disclosure, hereinafter embodiment [VII], is
fully
described immediately below.
[VII]-1. A film comprising at least one layer comprising an ethylene
interpolymer product comprising:
(i) a first ethylene interpolymer;
(ii) a second ethylene interpolymer, and;
(iii) optionally a third ethylene interpolymer;
wherein said second ethylene interpolymer is characterized by an
intermediate branching, wherein said intermediate branching is
characterized by a Non-Comonomer Index Distribution, NC ID, having
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a value characterized by Eq.(1a) and Eq.(1b); wherein, Mo is a peak
molecular weight that characterizes a molecular weight distribution of
said second ethylene interpolymer when fit to a log normal
distribution;
wherein a first derivative of said NCIDi, dNCIDi dlogMi, Eq.(2), has a value
of
- 0.0001, coefficients po, i31, 132 and f33 are generated by fitting said
NCIDi of said second ethylene interpolymer to a third order
polynomial, Eq.(3), and wherein said NCIDi may be experimentally
measured or computer simulated.
[VII]-2. The film as described in [VII]-1, wherein said first ethylene
interpolymer is synthesized using a homogenous catalyst formulation
and said second ethylene interpolymer is synthesized using an
intermediate branching catalyst formulation.
[VII]-3. The film as described in [VII]-2, wherein said homogeneous catalyst
formulation is an unbridged single site catalyst formulation or a
bridged metallocene catalyst formulation and said intermediate
branching catalyst formulation is an in-line intermediate branching
catalyst formulation or a batch intermediate branching catalyst
formulation.
[VII]-4. The film as described in [VII]-1, wherein said ethylene interpolymer
product has a melt index from about 0.3 to about 15 dg/minute and a
density from about 0.858 to about 0.965 g/cc; wherein melt index is
measured according to ASTM D1238 (2.16 kg load and 190 C) and
density is measured according to ASTM D792.
[VII]-5. The film as described in [VII]-1, wherein said ethylene interpolymer
product has a Mw/Mn from about 2 to about 25 and a CDBI50 from
about 10% to about 98%.
[VII]-6. The film as described in [VII]-1 wherein;
(i) said first ethylene interpolymer has a melt index from about
0.001 to about 1000 dg/minute, a density from about 0.855
g/cm3 to about 0.975 g/cc and is from about 0 to 60 weight
percent of said ethylene interpolymer product;
(ii) said second ethylene interpolymer has melt index from about
0.001 to about 1000 dg/minute, a density from about 0.89
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g/cm3 to about 0.965 g/cc and is from about 10 to 99 weight
percent of said ethylene interpolymer product
(iii) said third ethylene interpolymer has a melt index from about
0.1 to about 10000 dg/minute, a density from about 0.855 to
about 0.975 g/cc and is from 0 to about 30 weight percent of
said ethylene interpolymer product
wherein melt index is measured according to ASTM D1238 (2.16 kg
load and 190 C), density is measured according to ASTM D792 and
weight percent is the weight of said first, said second or said optional
third ethylene interpolymer divided by the weight of said ethylene
interpolymer product.
[VII]-7. The film as described in [VII]-1, wherein said ethylene interpolymer
product is manufactured using a solution polymerization process.
[VII]-8. The film as described in [VII]-1, wherein said ethylene interpolymer
product further comprises from 0.001 to about 10 mole percent of one
or more a-olefin; wherein said one or more a-olefin are C3 to Cio a-
olefins.
[VII]-9. The film as described in [VII]-8, wherein said one or more a-olefin
is
1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.
[VII]-10. The film as described in [VII]-1, wherein said film is a monolayer
film
having one or more of the following properties:
a) a dart impact from 10% to 110% higher;
b) a machine direction tensile strength from 10% to 20% higher;
c) a transverse direction tensile strength from 10% to 20%
higher;
d) a 45 gloss from 10% to 110% higher;
e) a haze from 10% to 50% lower;
relative to a comparative monolayer film, wherein said comparative
monolayer film contains a comparative second ethylene interpolymer
that has replaced said second ethylene interpolymer; wherein said
comparative second ethylene interpolymer does not contain
intermediate branching, has a comparative first derivative Eq.(2) value
> -0.0001.
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[VII]-11. The film as described in [VII]-1; wherein said at least one layer
further
comprises one or more polyolefin.
[VII]-12. The film as described in [VII]-11, wherein said polyolefin is one or
more ethylene polymer, one or more propylene polymer or a mixture
of said ethylene polymers and said propylene polymers.
[VII]-13. The film as described in [VII]-1, wherein said film has a thickness
from
0.5 mil to 10 mil.
[VII]-14. The film as described in [VII]-1, wherein said film comprises from 2
to
11 layers, wherein at least one or more layer comprises said ethylene
interpolymer product having intermediate branching.
Not to be construed as limiting, the ethylene interpolymer products disclosed
herein
may be converted into rigid manufactured articles such as containers, bottle
caps,
hinged closures, toys, recreational equipment, cable jacketing, tubing, pipe,
foamed
articles, truck bed liners, pallets and the like. Such rigid manufactured
articles may
contain one or more layers comprising the ethylene interpolymer products
described
in embodiments fully described above. Such rigid manufactured articles may be
fabricated using processes that are well-known in the art; non-limiting
examples
include injection molding, compression molding, blow molding, rotomolding,
profile
extrusion, pipe extrusion, sheet thermoforming and foaming processes employing
chemical or physical blowing agents.
Description of Figures
The following Figures are presented for the purpose of illustrating selected
features
and embodiments of this disclosure; it being understood that the embodiments
represented in these figures are not limiting.
Figure 1 compares the NCIDi (Non-Comonomer Index Distribution) of Examples 1
and
4 that have intermediate branching, relative to the NCIDi of Comparative 1
that does
not contain intermediate branching.
Figure 2 illustrates the NCIDi of Example 1 on the left axis generated from
nine TREF
fractions (F1 through F9); the right axis shows the normalized weight fraction
of each
TREF fraction as well as the cumulative weight fraction.
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Figure 3 illustrates the NCIDi of Example 4 on the left axis generated from
nine TREF
fractions (F1 through F9); the right axis shows the normalized weight fraction
of each
TREF fraction as well as the cumulative weight fraction.
Figure 4 illustrates the NCIDi of Comparative 1 on the left axis generated
from eight
TREF fractions (F1 through F8); the right axis shows the normalized weight
fraction of
each TREF fraction as well as the cumulative weight fraction.
Figure 5 plots the NCIDi of Example 1, Example 4, Component B of Example 5 and
Component B of Example 10 demonstrating that these ethylene interpolymer
products
contained intermediate branching; in contrast, Comparative 1 did not contain
intermediate branching; Equation (la) and Equation (1 b) are also plotted.
Note: For a
comparison purpose, data plotted in Figure 5 were horizontally shifted to a
same M.
value of 60000, i.e. the M. value from the component B of Example 10.
Figure 6 plots the first derivative of NCIDi, ddNiocgimpt , for Example 1,
Example 4,
io
Component B of Example 5 and Component B of Example 10 illustrating dn
-61cw gm, values
5 -0.0001; in contrast the dNCID, of Comparative 1 was > -0.0001. Note: Note:
For a
comparison purpose, data plotted in Figure 6 were horizontally shifted to a
same M.
value of 60000, i.e. the M. value from the component B of Example 10.
Figure 7 illustrates the NCIDi of Comparative 3 on the left axis generated
from nine
TREF fractions (F1 through F9); the right axis shows the normalized weight
fraction of
each TREF fraction as well as the cumulative weight fraction.
Figure 8 illustrates the NCIDi of Comparative 4 on the left axis generated
from nine
TREF fractions (Fl through F9); the right axis shows the normalized weight
fraction of
each TREF fraction as well as the cumulative weight fraction.
Figure 9 illustrates the NCIDi of Comparative 5 on the left axis generated
from six
TREF fractions (Fl through F6); the right axis shows the normalized weight
fraction of
each TREF fraction as well as the cumulative weight fraction.
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Figure 10 illustrates the NCIDi of Example 5 on the left axis generated from
eleven
TREF fractions (F1 through F11); the right axis shows the normalized weight
fraction
of each TREF fraction as well as the cumulative weight fraction.
Figure 11 compares NCIDivalues (left axis) of Example 5 (NCIDi Exptl, long
dashed
curve) with a computer simulated NCIDi (NCIDi Simulation, dotted curve).
Simulated
Example 5 was a binary blend of: i) 44.0 wt% component A having a constant
NCIDiA
of 0.997, Mr was 160000 and 9 was 0.850; and ii) 56.0 wt% component B having a
NCIDiB where po, 131, 132, and 133 were 0.97000, -0.00400, 0.00450 and -
0.00090,
respectively, and Mo was 65000 and 4 was 0.2620. The molecular weight
distributions
(right axis) of component A, component B and the combined (overall) were also
plotted.
Figure 12 illustrates the NC ID of Example 6 on the left axis generated from
eleven
TREF fractions (F1 through F11); the right axis shows the normalized weight
fraction
of each TREF fraction as well as the cumulative weight fraction.
Figure 13 illustrates the NCIDi of Example 7 on the left axis generated from
ten TREF
fractions (F1 through F10); the right axis shows the normalized weight
fraction of each
TREF fraction as well as the cumulative weight fraction.
Figure 14 illustrates the NCIDi of Comparative 6 on the left axis generated
from nine
TREF fractions (F1 through F9); the right axis shows the normalized weight
fraction of
each TREF fraction as well as the cumulative weight fraction.
Figure 15 illustrates the NCIDi of Example 10 on the left axis generated from
nine
TREF fractions (F1 through F9); the right axis shows the normalized weight
fraction of
each TREF fraction as well as the cumulative weight fraction.
Figure 16 compares NCID; values (left axis) of Example 10 (NCIDi Exptl, long
dashed
curve) with a computer simulated NCIDi (NCIDISimulation, dotted curve).
Simulated
Example 10 was a binary blend of: i) 50.0 wt% component A having a constant
NCIDiA
of 0.970, Mr of 120000 and 9 of 2.600; and ii) 50.0 wt% component B having a
NCIDiB
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where 130, 131, i32, and 133 were 1.0100, -0.0001, 0.0001 and -0.0011,
respectively, Mo of
60000 and 4 of 0.2400. The molecular weight distributions of component A,
component B and the combined (overall) were also plotted (right axis).
Figure 17 illustrates the NCIDi of Example 11 on the left axis generated from
eight
TREF fractions (F1 through F8); the right axis shows the normalized weight
fraction of
each TREF fraction as well as the cumulative weight fraction.
Figure 18 shows the determination of the Long Chain Branching Factor (LCBF).
The
abscissa plotted was the log of the corrected Zero Shear Viscosity (log(ZSVo))
and the
ordinate plotted was the log of the corrected Intrinsic Viscosity (log(IVc)).
Ethylene
interpolymer products that do not have LCB, or undetectable LCB, fall on the
'Linear
Reference Line'. Ethylene polymers having LCB deviate from the reference line
and
were characterized by the dimensionless Long Chain Branching Factor (LCBF).
LCBF = (Sh x Sv)/2; where Sh and Sv are horizontal and vertical shift factors,
respectively.
Figure 19 illustrates non-limiting embodiments of a continuous solution
polymerization
process employing two continuously stirred reactors (CSTR) wherein an ethylene
interpolymer product having intermediate branching may be produced.
Figure 20 illustrates non-limiting embodiments of a continuous solution
polymerization
process employing one continuously stirred reactor (CSTR) wherein an ethylene
interpolymer product having intermediate branching may be produced.
Definition of Terms
Other than in the examples or where otherwise indicated, all numbers or
expressions
referring to quantities of ingredients, extrusion conditions, etc., used in
the
specification and claims are to be understood as modified in all instances by
the term
"about." Accordingly, unless indicated to the contrary, the numerical
parameters set
forth in the following specification and attached claims are approximations
that can
vary depending upon the desired properties that the various embodiments desire
to
obtain. At the very least, and not as an attempt to limit the application of
the doctrine
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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.
In order to form a more complete understanding of this disclosure the
following terms
are defined and should be used with the accompanying figures and the
description of
the various embodiments throughout.
As used herein, the term "monomer" refers to a small molecule that may
chemically
react and become chemically bonded with itself or other monomers to form a
polymer.
As used herein, the term "a-olefin" is used to describe a monomer having a
linear
hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at
one
end of the chain; an equivalent term is "linear a-olefin".
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As used herein, the term "ethylene polymer", refers to macromolecules produced
from
ethylene and optionally one or more additional monomers; regardless of the
specific
catalyst or specific process used to make the ethylene polymer. In the
polyethylene
art, the one or more additional monomers are called "comonomer(s)" and often
include a-olefins. The term "homopolymer" refers to a polymer that contains
only one
type of monomer. Common ethylene polymers include high density polyethylene
(HDPE), medium density polyethylene (MDPE), linear low density polyethylene
(LLDPE), very low density polyethylene (VLDPE), ultralow density polyethylene
(ULDPE), plastomer and elastomers. The term ethylene polymer includes polymers
produced in high pressure polymerization processes; non-limiting examples
include
low density polyethylene (LDPE), ethylene vinyl acetate copolymers (EVA),
ethylene
alkyl acrylate copolymers, ethylene acrylic acid copolymers and metal salts of
ethylene acrylic acid (commonly referred to as ionomers). The term ethylene
polymer
includes block copolymers which may include 2 to 4 comonomers. The term
ethylene
polymer includes combinations of, or blends of, the ethylene polymers
described in
this paragraph.
The term "ethylene interpolymer" refers to a subset of polymers within the
"ethylene
polymer" group that excludes polymers produced in high pressure polymerization
processes; non-limiting examples of polymers produced in high pressure
processes
include LDPE and EVA.
The term "heterogeneous ethylene interpolymer" refers to a subset of polymers
in the
ethylene interpolymer group that are produced using heterogeneous catalyst
formulations; non-limiting examples of which include well-known Ziegler-Natta
or
chromium catalyst formulations. This disclosure introduces new heterogeneous
ethylene interpolymers, characterized as having intermediate branching and
synthesized with an intermediate branching catalyst formulation.
The term "homogeneous ethylene interpolymer" refers to a subset of polymers in
the
ethylene interpolymer group that are produced using homogeneous catalyst
formulations. Typically, homogeneous ethylene interpolymers have narrow
molecular
weight distributions, for example Size Exclusion Chromatography (SEC) Mw/Mn
values
of less than 2.8; Mw and Mn refer to weight and number average molecular
weights,
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respectively. In contrast, the Mw/Mn of heterogeneous ethylene interpolymers
are
typically greater than the Mw/Mn of homogeneous ethylene interpolymers. In
general,
homogeneous ethylene interpolymers also have a narrow comonomer distribution,
i.e.
each macromolecule within the molecular weight distribution has similar
comonomer
content. Frequently, the composition distribution breadth index "CDBI" is used
to
quantify how the comonomer is distributed within an ethylene interpolymer, as
well as
to differentiate ethylene interpolymers produced with different catalysts or
processes.
In this disclosure, "CDBI50" is defined as the percent of ethylene
interpolymer whose
composition is within 50% of the median comonomer composition; this definition
is
consistent with that described in U.S. Patent 5,206,075 assigned to Exxon
Chemical
Patents Inc. The CDBI50 of an ethylene interpolymer can be calculated from
TREF
curves (Temperature Rising Elution Fractionation); the TREF method is
described in
Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-
455.
Typically, the CDBI50 of homogeneous ethylene interpolymers are greater than
about
70%. In contrast, the CDBI50 of a-olefin containing heterogeneous ethylene
interpolymers are generally lower than the CDBI50 of homogeneous ethylene
interpolymers. A blend of two or more homogeneous ethylene interpolymers, that
differ in comonomer content, may have a CDBI50 less than 70%; in this
disclosure
such a blend was defined as a homogeneous blend or homogeneous composition.
Similarly, a blend of two or more homogeneous ethylene interpolymers, that
differ in
weight average molecular weight (Mw), may have a Mw/Mn 2.8; in this disclosure
such a blend was defined as a homogeneous blend or homogeneous composition.
In this disclosure, the term "homogeneous ethylene interpolymer" refers to
both linear
homogeneous ethylene interpolymers and substantially linear homogeneous
ethylene
interpolymers. In the art, linear homogeneous ethylene interpolymers are
generally
assumed to have no long chain branches or an undetectable amount of long chain
branches; while substantially linear ethylene interpolymers are generally
assumed to
have greater than about 0.01 to about 3.0 long chain branches per 1000 carbon
atoms. A long chain branch is macromolecular in nature, i.e. similar in length
to the
macromolecule that the long chain branch is attached to. In this disclosure
the
amount of long chain branching present in an ethylene interpolymer was
characterized
by the 'Long Chain Branching Factor (LCBF)'. The measurement of LCBF was fully
described in this disclosure.
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In this disclosure a new class of ethylene interpolymers are disclosed;
specifically,
ethylene interpolymers having "intermediate branching". Intermediate branching
was
defined as branching that was longer than the branch length resulting from
comonomer incorporation (e.g. C4 or C6 branches resulting from the
incorporation of
1-hexene or 1-octene comonomers into a propagating macromolecule,
respectively)
and shorter than the entanglement molecular weight, Me. Me is a well-known
concept
in polymer physics (for example reported to be about 1 kg/mol for
polyethylenes, see
Fetters et al., Macromolecules 1999, 32, 6847). The amount of intermediate
branching in ethylene interpolymers was characterized by the Non-Comonomer
Index
(NCI)', as well as the Non-Comonomer Index Distribution (NCIDi), which was
determined by triple detection cross fractionation chromatography (3D-CFC)
analysis,
as fully described in this specification.
In this disclosure the term 'ethylene interpolymer product' refers to the
final product
produced by a polymerization process; wherein the ethylene interpolymer
product has
intermediate branching, as characterized by the Non-Comonomer Index
Distribution
(NCI Di). The polymerization processes disclosed hereinafter include processes
employing one or more polymerization reactor(s). In the case of one reactor
employing one intermediate branching catalyst formulation, the final product
is an
ethylene interpolymer product containing one ethylene interpolymer containing
intermediate branching. In the case of two reactors employing the same
intermediate
branching catalyst formulation, the final product is an ethylene interpolymer
product
containing two ethylene interpolymers both containing intermediate branching.
In the
case of two reactors, employing two catalyst formulations where one is an
intermediate branching catalyst formulation, the final product is an ethylene
interpolymer product containing two ethylene interpolymers; wherein one
ethylene
interpolymer contains intermediate branching. In the case of a polymerization
processes employing three reactors, the ethylene interpolymer product
contained a
first, second and third ethylene interpolymer; wherein at least one of the
first, second
or third ethylene interpolymer contained intermediate branching. Intermediate
branching was produced by an intermediate branching catalyst formulation(s)
disclosed hereinafter.
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In this disclosure the term 'component' was also used; the term component
applies to
an ethylene interpolymer where the molecular weight distribution was defined
by a
mathematical function; i.e. a 'component A' synthesized employing one catalyst
formulation and one reactor. In this disclosure, the term component also
referred to
chemical compounds required to manufacture a catalyst formulation; e.g.
'component
Or.
In this disclosure the term 'homogeneous catalyst' refers to the chemical
compound
containing the catalytic metal which is frequently called a `metal-ligand
complex'. In
this disclosure, a homogeneous catalyst is defined by the characteristics of
the
resulting ethylene interpolymer. More specifically, a catalyst was a
homogeneous
catalyst if it produced a homogeneous ethylene interpolymer that has a narrow
molecular weight distribution (SEC Mw/Mn values of less than 2.8) and a narrow
comonomer distribution (CDBI50 > 70%). Homogeneous catalysts are well known in
the art. Two subsets of the homogeneous catalysts include unbridged
metallocene
catalysts and bridged metallocene catalysts. Unbridged metallocene catalysts
are
characterized by two bulky ligands bonded to the catalytic metal, a non-
limiting
example includes bis(isopropyl-cyclopentadienyl) titanium dichloride. In this
disclosure, an 'unbridged metallocene catalyst formulation' comprised an
unbridged
metallocene catalyst. In bridged metallocene catalysts the two bulky ligands
are
covalently bonded (bridged) together, a non-limiting example includes
diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfuorenyl) titanium
dichloride;
where the diphenylmethylene group bonds, or bridges, the cyclopentadienyl and
fluorenyl ligands together. In this disclosure, a 'bridged metallocene
catalyst
formulation' comprised an bridged metallocene catalyst. Two additional subsets
of
homogeneous catalysts include unbridged and bridged single site catalysts. In
this
disclosure, single site catalysts are characterized as having only one bulky
ligand
bonded to the catalytic metal. A non-limiting example of an unbridged single
site
catalyst includes cyclopentadienyl tri(tertiary butyl)phosphinimine titanium
dichloride;
wherein cyclopentadienyl was the bulky ligand. In this disclosure, an
'unbridged
single site catalyst formulation' comprised an unbridged single site catalyst.
A non-
limiting example of a bridged single site catalyst includes [C5(CH3)4 -
Si(CH3)2 -N(tBu)]
titanium dichloride, where the -Si(CH3)2- group functions as the bridging
group. In this
disclosure, a 'bridged single site catalyst formulation' comprised a bridged
single site
catalyst.
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Herein, the term "polyolefin" includes ethylene polymers and propylene
polymers; non-
limiting examples of "propylene polymers" include isotactic, syndiotactic and
atactic
propylene homopolymers, random propylene copolymers containing at least one
comonomer (e.g. a-olefins) and impact polypropylene copolymers or heterophasic
polypropylene copolymers.
The term "thermoplastic" refers to a polymer that becomes liquid when heated,
will
flow under pressure and solidify when cooled. Thermoplastic polymers include
ethylene polymers as well as other polymers used in the plastic industry; non-
limiting
.. examples of other polymers commonly used in film applications include
barrier resins
(EVOH), tie resins, polyethylene terephthalate (PET), polyamides and the like.
As used herein the term "monolayer film" refers to a film containing a single
layer of
one or more thermoplastics. The term "multilayer film" refers to a film
containing more
than one layer; non-limiting processes to produce such films include
coextrusion or
lamination.
As used herein, the terms "hydrocarbyl", "hydrocarbyl radical" or "hydrocarbyl
group"
refers to linear, branched, or cyclic, aliphatic, olefinic, acetylenic and
aryl (aromatic)
radicals comprising hydrogen and carbon that are deficient by one hydrogen.
As used herein, an "alkyl radical" includes linear, branched and cyclic
paraffin radicals
that are deficient by one hydrogen radical; non-limiting examples include
methyl (-
CH3) and ethyl (-CH2CH3) radicals. The term "alkenyl radical" refers to
linear,
branched and cyclic hydrocarbons containing at least one carbon-carbon double
bond
that is deficient by one hydrogen radical.
As used herein, the term "aryl" group includes phenyl, naphthyl, pyridyl and
other
radicals whose molecules have an aromatic ring structure; non-limiting
examples
include naphthylene, phenanthrene and anthracene. An "arylalkyl" group is an
alkyl
group having an aryl group pendant there from; non-limiting examples include
benzyl,
phenethyl and tolylmethyl; an "alkylaryl" is an aryl group having one or more
alkyl
groups pendant there from; non-limiting examples include tolyl, xylyl, mesityl
and
cumyl.
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As used herein, the phrase "heteroatom" includes any atom other than carbon
and
hydrogen that can be bound to carbon. A "heteroatom-containing group" is a
hydrocarbon radical that contains a heteroatom and may contain one or more of
the
same or different heteroatoms. In one embodiment, a heteroatom-containing
group is
a hydrocarbyl group containing from 1 to 3 atoms selected from the group
consisting
of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and
sulfur.
Non-limiting examples of heteroatom-containing groups include radicals of
imines,
amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics,
oxazolines,
thioethers, and the like. The term "heterocyclic" refers to ring systems
having a
carbon backbone that comprise from 1 to 3 atoms selected from the group
consisting
of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and
sulfur.
As used herein the term "unsubstituted" means that hydrogen radicals are
bounded to
the molecular group that follows the term unsubstituted. The term
"substituted" means
that the group following this term possesses one or more moieties that have
replaced
one or more hydrogen radicals in any position within the group; non-limiting
examples
of moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl
groups,
carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups,
naphthyl groups, Ci to Cio alkyl groups, C2 to Cio alkenyl groups, and
combinations
thereof. Non-limiting examples of substituted alkyls and aryls include: acyl
radicals,
alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,
dialkylamino
radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl
radicals, alkyl-
and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,
arylamino
radicals and combinations thereof.
Herein the term "R1" and its superscript form "Rl" refers to a first
polymerization
reactor in a continuous solution polymerization process; it being understood
that R1 is
distinctly different from the symbol R1; the latter is used in chemical
formula, e.g.
representing a hydrocarbyl group. Similarly, the term "R2" and it's
superscript form
"R2" refers to a second reactor, and; the term "R3" and it's superscript form
"R3" refers
to a third reactor.
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DETAILED DESCRIPTION
Non-Comonomer Index (NCI) and Non-Comonomer Index Distribution (NCIDi)
Figure 1 compared the Non-Comonomer Index Distribution (NCIDi) of Examples 1
and
4 with Comparative 1. Examples 1 and 4 as well as Comparative 1 did not
contain
long chain branching (LCB) (or contained an undetectable level of LCB) as
evidenced
by the Long Chain Branching Factor (LCBF) discussed below. Examples 1 and 4
contained intermediate branching as evidenced by NC1Di values less than or
equal to
0.99. In contrast, Comparative 1 did not contain intermediate branching as
evidenced
by NCIDi values greater than 0.99. Examples 1 and 4 were ethylene/l-octene
interpolymer products (about 0.92 g/cm3 and about 1.0 12 (melt index, ASTM
1239,
2.16 kg load, 190 C) produced in a continuous solution polymerization process
using
different embodiments of intermediate branching catalyst formulations. The
solution
process conditions required to manufacture Examples 1 and 4 are discussed
below
and disclosed in Tables la and lb. Comparative 1 was an ethylene/l-octene
interpolymer (about 0.92 g/cm3 and about 1.0 12) produced in a competitive
solution
polymerization process using a comparative batch Ziegler-Natta catalyst
formulation;
Comparative 1 was Dowlex 2045G available from The Dow Chemical Company
(Midland, Michigan, USA). The physical properties of Examples 1, 2 and 4 and
Comparatives 1 and 2 were summarized in Table 2. In this disclosure
Comparative 2
was also Dowlex 2045; however, a different lot (or batch) relative to
Comparative 1.
In this disclosure, Triple Detection Cross Fractionation Chromatography (3D-
CFC)
was used to measure NCI and NCIDi. NCI and NC ID were dimensionless
parameters. The testing methods section of this disclosure fully described the
3D-
CFC technique. NCI was defined as the measured Mark-Houwink constant (Km) of
the sample under test (measured in 1,2,4-trichlorobenzene (TCB) at 140 C)
divided by
the short chain branching (SCB) corrected Mark-Houwink constant (Kco) for
linear
ethylene/a-olefin interpolymers, as defined by Eq.(6).
Km 1000000([171/4725)
NCI = ¨ = ____________________________________ Eq.(6)
Kco (391.98¨Ax SCB )
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In Eq.(6), [ri] was the experimentally measured intrinsic viscosity (dL/g) as
determined
by 3D-SEC, Mv was the viscosity average molar mass (g/mol) as determined by 3D-
SEC; SCB was the short chain branching content (number of CH3 groups per 1000
carbon atoms [CH3#/1000C]) as determined by FTIR; and A was a constant that
depended on the a-olefin present in the ethylene/a-olefin interpolymer under
test; A
was 2.1626 for 1-octene. In the case of an ethylene homopolymer no correction
was
required for the Mark-Houwink constant, i.e. SCB is zero.
Using a Polymer Char Crystaf-TREF unit an ethylene/ix-olefin interpolymer
sample
under test was fractionated into a number of fractions (typically from 5 to 20
fractions,
in this disclosure superscript f, i.e. f, represents the fraction number) and
the Non-
Comonomer Index Distribution (NCIDi) was determined. Specifically: (i) the NCI
of
each fraction (NCI) was calculated using Eq.(4) (Equation (4) was introduced
previously and was reproduced below);
Kin 1000000adf l(Mt)(1725)
NCIf Eq.(4)
Km (391.98¨Ax (B x Tf+C )
where A, B and C were constants determined experimentally and V was the weight
average TREF elution temperature of fraction f (see testing methods section
for
additional detail), and; (ii) the Non-Comonomer Index Distribution (NCIDi) was
calculated using Eq.(5) (introduced previously);
NCIDi = (wt. fr.)f (wi log(Mi))f x NC/f Eq.(5)
where (wt.fr.)f represented the weight fraction of -Ph TREF fraction, and;
(wilog(Mi))f
represented the weight fraction of the fth TREF fraction having molar mass M.
Clarifying with an example, 3D-CFC results for Example 1 were disclosed in
Table 3.
As shown in Table 3, Example 1 was fractionated into nine fractions (F1
through F9),
the NCI f of each fraction was calculated using Eq.(4). TREF fraction 1 (F1)
was eluted
from 30 C to 60 C and was 0.1699 weight fraction {(wt.fr)1} of Example 1.
Again,
(wilog(Mi))1 was the weight fraction of Fl having molar mass Mi; further, (wi
log(Mi))1
summed over all i characterized the molecular weight distribution of Fl.
Typically, the
molecular weight distribution of each fraction contained about 300 data
points,
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employing log(M) increments of 0.01. As shown in Table 3, fraction Fl (of
Example 1)
had a weight average molecular weight (Mw) of 72,300 g/mol, a viscosity
average
molecular weight (My) of 63,700 g/mol, an intrinsic viscosity [i] of 0.98
dL/g, the
amount of short chain branching (SCI3f) was 29.03 CH3/1000C and the Non-
Comonomer Index of Fraction 1 (NCI1) was 0.983. The 3D-CFC TREF fractions
isolated from Example 1 had Non-Comonomer Index values (NCI) that varied from
0.983 to 0.902.
Graphically, Figure 2 shows the Non-Comonomer Index Distribution (NCIDi) of
Example 1 (left y-axis), and; the molecular weight distributions of the nine
3D-CFC
TREF fractions and cumulative (overall) molecular weight distribution (right y-
axis).
Example 1 was an ethylene/1 -octene interpolymer containing intermediate
branching
as evidenced by NCIDi values 0.99. As shown in Tables 1 a and lb, Example 1
was
produced by injecting an in-line intermediate branching catalyst formulation
into
.. reactor 2 (R2); 80% of the ethylene and 100% of the 1-octene was injected
into R2;
20% of the ethylene was injected into reactor 3 (R3); a catalyst formulation
was not
injected into R3.
As shown in Tables la and 1 b, Example 4 was produced using a batch
intermediate
branching catalyst formulation; Table 2 summarized the physical
characteristics of
Example 4. The 3D-CFC analysis of Example 4 was summarized in Table 4. Nine
3D-CFC TREF fractions were collected; fraction 1 (F1) was collected at TREF
elution
temperatures from 30 C to 60 C and was 0.1666 weight fraction (wt.fr.)1 of
Example
4. Fl had a weight average molecular weight (Mw) of 61,600 g/mol, a viscosity
average molecular weight (My) of 54,400 g/mol, an intrinsic viscosity [i] of
0.88 dL/g,
the amount of short chain branching (SCBt) was 29.42 CH3/1000C and the Non-
Comonomer Index of Fraction 1 (NCO) was 0.985. The 3D-CFC TREF fractions
isolated from Example 4 had Non-Comonomer Index values (NCI) that varied from
0.985 to 0.938. Figure 3 showed the NCIDi of Example 4 as a function of
Log(Molar
Mass), as well as the molecular weight distributions of the nine 3D-CFC TREF
fractions and the cumulative (overall) molecular weight distribution. Example
4
contained intermediate branching as evidenced by NCIDi values 0.99.
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Table 5 summarized 3D-CFC analysis of Comparative 1 and physical
characteristics
were summarized in Table 2. Comparative 1 was fractionated into eight 3D-CFC
TREF fractions; fraction 1 (F1) collected from 30 C to 65 C was 0.1921 weight
fraction
((wt.fr.)1) of Comparative 1. Fl had a weight average molecular weight (Mw) of
60,400
g/mol, a viscosity average molecular weight (Mu) of 51,700 g/mol, an intrinsic
viscosity
[ri] of 0.87 dL/g, the amount of short chain branching (SCBf) was 26.63
CH3/1000C
and the Non-Comonomer Index value of Fraction 1 (NCI1) was 1.00. Comparative 1
fractions had an average NCI of 0.998 0.005. Figure 4 plotted the Non-
Comonomer
Index Distribution (NCIDi) of Comparative 1 as a function of Log(Molar Mass),
the
molecular weight distributions of the eight 3D-CFC TREF fractions and the
cumulative
molecular weight distribution; NCIDi values were consistently greater than
0.99.
Comparative 1 did not contain intermediate branching as evidenced by NCIDI
values >
0.99.
Using various embodiments of intermediate branching catalyst formulations,
ethylene
interpolymer products having a range of intermediate branching were produced.
This
range in intermediate branching was characterized by the Non-Comonomer Index
Distribution (NCIDi) as shown in Figure 5 (again, Comparative 1 in Figure 5
(long
dash-dot line) did not contain intermediate branching, i.e. NCIDI values
>0.99). The
experimentally measured NCIDi of Example 1 was fit to the following third
order
polynomial, Eq.(3) (introduced previously);
NCIDi = fl o+ A(logMi ¨ logM0 + 4.93) + /32(logMi ¨ logM0 + 4.93)2 +
/33(logM1 ¨ logM0 + 4.93)3 Eq.(3)
and this fit produced the Example 1 curve (dotted curve) plotted in Figure 5;
where 13o,
pi, 132 and 133 were 0.98658, -0.00388, 0.00313 and -0.00069, respectively,
and Mo
was 85000. Mo was the peak molecular weight that characterized the molecular
weight distribution of Example 1 when fit to the log normal distribution
(described
below). Similarly, the experimentally measured NCIDi of Example 4 was fit to
Eq.(3)
producing the short dash ¨ dot curve plotted in Figure 5; where po, 131, 132
and 133 were
0.98945, -0.00201, 0.00137 and -0.00034, respectively, and Mo was 82000.
Figure 5
also plotted the computer simulated NCIDI of component B of Example 5 (short
dashed curved); where 130, 131, 132 and 133 were 0.97000, -0.00400 0.00450 and
-
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0.00090, respectively, and Mo was 65000. Example 5 was fully described below,
in
brief, Example 5 (manufactured in a dual reactor solution process) contained a
first
and a second ethylene interpolymer, i.e. components A and B, respectively.
Example
5's component B contained intermediate branching and component A did not
contain
.. intermediate branching. The term 'computer simulated' means the NCIDi of
component B (in Example 5) was generated by deconvolution (fully described
below).
Figure 5 also plotted the computer simulated NCID, of component B in Example
10
(long dash-dot-dot curve); where 130, pi, 132 and 133 were 1.0100, -0.0001,
0.0001 and -
0.0011, respectively, and Mo was 60000.
Given these examples, intermediately branched ethylene interpolymer products
had
NCIDi values characterized by Eq.(1a) and Eq.(1b) (both introduced
previously):
NCIDi < 1.000 ¨ 0.00201(/ogM1 ¨ logM, + 4.93) + 0.00137(/ogM1 ¨ logM, +
4.93)2 ¨ 0.00034(/ogM1 ¨ logM, + 4.93)3 Eq.(1a)
NCIDE > 0.730 ¨ 0.00388(/ogM1 ¨ logM, + 4.93) + 0.00313(/ogM1 ¨ logM, +
4.93)2 ¨ 0.00069(/ogM1 ¨ logM, + 4.93)3 Eq.(1b)
Eq.(1a) was plotted in Figures (solid curve), as was Eq.(1b) (long dash
curve); where
Mo was 60000. In alternative words, ethylene interpolymer products having
intermediate branching had NCIDi values characterized as follows: Eq.(1b)
NCID;
Eq. (1a).
An additional feature that characterized intermediately branched ethylene
interpolymer
products was the first derivative of Eq.(3), i.e. Eq.(2) (introduced
previously):
dNCID,
dlogM, = A + 2132(logMi¨ 10g M0 + 4.93) + 3)33 (logMi¨ 10g M0 + 4.93)2
Eq.(2)
Figure 6 compares the ddNiocgim ' values of Example 1 (dotted curve),
Example 4 (dash-
dot curve), component B of Example 5 (dash curve), component B of Example 10
D,
(solid curve) with comparative 1 (dash-dot-dot line). Evidently, dNCI was
negative for
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intermediately branched ethylene interpolymer products. In contrast,
ddNiocgrAiD, of
Comparative 1 was zero; more specifically, statistically the NCIDi values of
Comparative 1 shown in Figure 5 were best represented by a one parameter
intercept
dNCID,
model (i.e. a constant, the mean 0.998), thus of Comparative 1 was zero. As
dlogM,
__________________ shown in Figure 6, ddNiocgim 1 of the disclosed ethylene
interpolymer products was
consistently - 0.0001; in contrast, Comparative 1 had ddrviocgimp,
values > -0.0001.
Table 6 summarized the 3D-CFC analysis of Comparative 3 and additional
physical
and molecular characteristics were shown in Table 7. Comparative 3 was a dual
reactor ethylene/1-octene interpolymer manufactured in a dual reactor solution
polymerization process using an unbridged single site catalyst formulation
comprising
cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride, i.e.
SURPASS
FPs117-C available from NOVA Chemicals Company (Calgary, Alberta, Canada). In
Comparative 3 the comonomer was randomly distributed and Comparative 3 did not
contain long chain branching (LCB) (or contained an undetectable level of LCB)
as
evidenced by the Long Chain Branching Factor (LCBF) (discussed below).
Comparative 3 was fractionated into nine 3D-CFC TREF fractions; fraction 1
(F1) was
collected from 30 C to 65 C and was 0.1527 weight fraction (wt.fr.)1. Fraction
Fl had
a weight average molecular weight (Mw) of 23,800 g/mol, a viscosity average
molecular weight (Mv) of 22,200 g/mol, an intrinsic viscosity [i] of 0.48
dL/g, the
amount of short chain branching (SCBf) was 24.98 CH3/1000C and the Non-
Comonomer Index value of Fraction 1 (NC 11) was 0.998. The 3D-CFC TREF
fractions
isolated from Comparative 3 had NCI f values that varied from 1.00 to 0.994.
Figure 7
plotted Comparative 3's NCIDi values as a function of Log(Molar Mass). The
NCIDi of
.. Comparative 3 was characterized by a constant (i.e. the mean 0.997); thus
Nd dCm1D, of
Comparative 3 was zero. Comparative 3 did not contain intermediate branching
as
evidenced by NCIDi values > 0.99.
Table 8 summarizes 3D-CFC analysis of Comparative 4 and physical
characteristics
were summarized in Table 7. Comparative 4 was a competitive ethylene/1-octene
interpolymer produced using a single-site catalyst formation in a single
reactor
solution process, i.e. AFFINITY PL1880 available from The Dow Chemical Company
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(Midland, Michigan, USA). In addition to short chain branching (i.e. C6
branching from
the 1-octene comonomer), Comparative 4 also contained long chain branching
(LCB);
as evidenced by the Long Chain Branching Factor (LCBF) (discussed below). The
Non-Comonomer Index (NCI), as defined by Eq.(6), was influenced by the amount
of
long chain branching; with NCI decreasing as LCB increased. As shown in Table
8,
Comparative 4 was fractionated into nine 3D-CFC TREF fractions; fraction 1
(F1)
collected from 30 C to 50 C was 0.1123 weight fraction (wt.fr.)1. Fraction Fl
had a
weight average molecular weight (Mw) of 45,900 g/mol, a viscosity average
molecular
weight (My) of 43,900 g/mol, an intrinsic viscosity [n] of 0.70 dL/g, the
amount of short
chain branching (SCBf) was 33.91 CH3/1000C and the Non-Comonomer Index value
of Fraction 1 (NC') was 0.944. The 3D-CFC TREF fractions isolated from
Comparative 4 had consistent NCI f values, i.e. 0.945 0.003. Figure 8
plotted
Comparative 4's NCIDi values as a function of Log(Molar Mass); statistically
these
NCIDi values were best represented by a one parameter (the mean, 0.945)
intercept
,
model thus dNC1D was zero.
dlog111,
Table 9 summarizes 3D-CFC analysis of Comparative 5 and physical
characteristics
were summarized in Table 7. Comparative 5 was an ethylene/1-octene
interpolymer
produced in the solution pilot plant disclosed herein using one reactor and a
bridged
.. metallocene catalyst formulation comprising diphenylmethylene
(cyclopentadienyl)
(2,7-di-t-butylfuorenyl) hafnium dimethyl. Comparative 5 contained long chain
branching (LCB); as evidenced by LCBF data (discussed below). Comparative 5
was
fractionated into six 3D-CFC TREF fractions; fraction 1 (F1) collected from 30
C to
55 C was 0.1153 weight fraction (wt.fr.)1. Fraction F1 had a weight average
molecular
weight (Mw) of 37,700 g/mol, a viscosity average molecular weight (My) of
35,900
g/mol, an intrinsic viscosity [rd of 0.64 dL/g, the amount of short chain
branching
(SCBf) was 30.95 CH3/1000C and the Non-Comonomer Index value of Fraction 1
(NCI1) was 0.976. The 3D-CFC TREF fractions isolated from Comparative 5 had
consistent NCI f values, i.e. 0.975 0.002. The flat (constant) Non-Comonomer
Index
Distribution (NCIDi) of Comparative 5 was plotted in Figure 9; statistically
these NCIDi
values were best represented by a one parameter (the mean, 0.975) intercept
model
thus Comparative 5's dNCID,was zero.
dlogM,
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In some cases the polymer sample under test contained one component. The term
'component' referred to an ethylene interpolymer having a distribution of
molecular
weights produced by one catalyst system injected into one reactor. In other
cases,
the polymer sample contained more than one component; for example, a polymer
sample produced by injecting more than one catalyst formulation into one
reactor, or a
polymer sample produced using more than one reactor (where the same or
different
catalyst(s) are used in the multiple reactors).
Tables 10a and 10b summarized the solution process conditions used to
manufacture
Example 5 and Table 11 disclosed the physical characteristics. Example 5 was a
dual
reactor and dual catalyst ethylene/1-octene interpolymer product containing:
about
44% of a component A produced in a first reactor (R1) using an unbridged
single site
catalyst formulation, and; about 56% of a component B produced in a second
reactor
(R2) using an embodiment of an in-line intermediate branching catalyst
formulation.
In Example 5, the two reactors (R1 and R2) were operated in series mode. Table
12
summarized 3D-CFC analysis of Example 5. Example 5 was fractionated into
eleven
3D-CFC TREF fractions; fraction 5 (F5) collected from 71 C to 73 C was 0.0992
weight fraction (wt.fr.)5. Fraction F5 had a weight average molecular weight
(Mw) of
140,600 g/mol, a viscosity average molecular weight (Mu) of 132,100 g/mol, an
intrinsic viscosity [IA of 1.84 dL/g, the amount of short chain branching
(SCBf) was
15.10 CH3/10000 and the Non-Comonomer Index value of Fraction 5 (NCI5) was
0.992. The NCIDI of Example 5 was plotted in Figure 10 (left vertical axis),
as well as
the molecular weight distributions of eleven 3D-CFC TREF fractions and
cumulative
(overall) molecular weight distribution (right vertical axis). Component B in
Example 5
contained intermediate branching produced by an embodiment of an in-line
intermediate branching catalyst formulation. The shape of the NCIDi in Figure
10
reflected the following facts: (1) component B's intermediate branching tended
to
reduce NCI values monotonically as Log (Molar Mass) increased as shown in
Figure 5
and ,of
component B was 5 -0.0001 as shown in Figure 6, and; (2) the NCIDI of
dlogM,
dNCID,
_________________________________________________________________ component A
was a constant 0.997 and of component A was zero (>-0.0001).
dlogilli
In Figure 10 the peak in Example 5's NCIDi at about 5.5 Log(Molar Mass)
reflected
the fact that component A was higher molecular weight than component B; as
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supported by Figure 11. Figure 11 illustrated a computer simulation of Example
5
showing the NCIDI distribution of a binary blend of: i) 44.0 wt% component A
having a
constant NCIDiA of 0.997, and, ii) 56.0 wt% component B having a NCID,B
defined by
Eq.(3), where po, [31, 132, and 133 were 0.97000, -0.00400, 0.00450 and -
0.00090,
dNCIDi
respectively, and M. was 65000; component B was also characterized by dlogMi
values - 0.0001. The computer simulation was a good representation of Example
5
as evidenced by the similarity between the experimentally measured NCIDi
values
(long dash curve) and the simulated NCIDi values (dotted curve) in Figure 11.
The simulated NCIDi values shown in Figure 11 were generated using Eq.(7)
NCIDi =1(wt. fr.)A (w1llI)ANCID1.4 + (wt. fr.)B (wiMi)B NCIDP
Eq.(7)
where (wt.fr.)A and (wt.fr.)8 represented the weight fractions of components A
and B,
respectively, with the proviso that ((wt.fr.)A + (wt.fr.)B = 1.0); (wiMi)A was
the weight
fraction of component A having molecular weight Mi defined by a modified Flory-
Schultz distribution Eq.(8); NCIRA was the Non-Comonomer Index Distribution of
component A (in the case of Example 5's component A, NCIDI was a constant
0.997);
(wiMi)B was the weight fraction of component B having molecular weight Mi
defined by
a log normal distribution Eq.(9) and; NCID,B was the Non-Comonomer Index
Distribution of component B as defined above.
The modified Flory-Shultz distribution was defined as follows:
(wiMi)A = ln(10) x (-dm exp( ¨ i1.71:1") Ed.(8)
where Mr and 9 were fitting parameters, i.e. Mr was a reference molecular
weight and
9 a breadth parameter. In the case of Example 5's component A, Mr was 160000
and
9 was 0.850.
The log-normal distribution was defined as follows:
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(wiMi)B = 1 exp(¨ ((logMi ¨ 1ogM0)k)2) Eq.(9)
(2 r)
where M. and 4 were fitting parameters, i.e. M. was the peak molecular weight
and 4
was a breadth parameter. In the case of Example 5's component B, Mo was 65000
and 4 was 0.2620.
In this disclosure the NCIDi of an ethylene interpolymer product may be
'experimentally measured' or 'computer simulated'. Figure 2 and Table 3
demonstrated how to determine the 'experimentally measured' NCIDi for Example
1; in
this case, NCIDi could be measured directly (i.e. experimentally measured)
because
Example 1 contained only one ethylene interpolymer. However, in the case of an
ethylene interpolymer product containing more than one ethylene interpolymer,
the
NCIDI was determined by computer simulation, or deconvolution, as demonstrated
by
Example 5 in Figure 11; i.e. a computer was used to fit Eq.(7) to the
experimentally
measured NCIDi of Example 5 to determine the Po, 131, 132 and 133 values of
Example
5's component B for use in Eq.(2) and Eq.(3).
The 3D-CFC analysis of Example 6 was summarized in Table 13 and Figure 12; the
physical characteristics of Example 6 were summarized in Table 11. Example 6
was
a dual reactor ethylene/1-octene interpolymer produced in a commercial
solution
polymerization plant. Example 6 contained about 40 wt% of a component A and
about 60 wt% of a component B; component A was produced in a first reactor
(R1)
using an unbridged single site catalyst formulation and component B was
produced in
a second reactor (R2) using an embodiment of an in-line intermediate branching
catalyst formulation; R1 and R2 were operated in series mode. As shown in
Table 13,
Example 6 was fractionated into eleven 3D-CFC TREF fractions; fraction 1 (F1)
collected at TREF elution temperatures from 30 C to 51 C was 0.0993 weight
fraction
(wt.fr.)1. Fraction Fl had a weight average molecular weight (Mw) of 61,800
g/mol, a
viscosity average molecular weight (Mv) of 56,400 g/mol, an intrinsic
viscosity [1] of
0.88 dL/g, the amount of short chain branching (SCBf) was 33.39 CH3/10000 and
the
Non-Comonomer Index value of Fraction 1 (NCli) was 0.983. The NCIDi of Example
6
was plotted in Figure 12, as well as the molecular weight distributions of
eleven 3D-
CFC TREF fractions and cumulative (overall) molecular weight distribution. The
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component B portion of Example 6 contained intermediate branching produced by
the
in-line intermediate branching catalyst formulation. As shown in Figure 12,
Example
6's Non-Comonomer Index Distribution (NCIDi) was similar to Example 5 (Figure
11);
which reflected the similarity in the design of these two examples.
The 3D-CFC analysis of Example 7 was summarized in Table 14 and Figure 13; and
physical characteristics were summarized in Table 11. Example 7 was a dual
reactor
ethylene/1-octene interpolymer produced in a commercial solution
polymerization
plant; containing about 40 wt% of a component A and about 60 wt% of a
component
B. Component A was produced in a first reactor (R1) using an unbridged single
site
catalyst formulation and component B was produced in a second reactor (R2)
using
an in-line intermediate branching catalyst formulation; R1 and R2 were
operated in
series mode. Given similar product design, the shape of Example 7's Non-
Comonomer Index Distribution (NCIDi), shown in Figure 13, was similar relative
to
Examples 5 and 6 shown in Figures 10 and 12, respectively.
Table 15 and Figure 14 summarized the 3D-CFC analysis of Comparative 6; and
physical characteristics were disclosed in Table 11. Comparative 6 was a multi-
component ethylene interpolymer product produced using a single site catalyst
formation in a first reactor (producing a component A) and a comparative batch
Ziegler-Natta catalyst formulation in a second reactor (producing a component
B).
Comparative 6 was Elite 5100G available from The Dow Chemical Company
(Midland, Michigan, USA). Component A in Comparative 6 was believed to be
produced by the same single site catalyst formulation used to manufacture
Comparative 4; further, the component A portion of Example 6 contained long
chain
branching as evidenced by the Long Chain Branching Factor (LCBF) discussion
(below). The component B portion of Comparative 6 was believed to be produced
by
the same comparative batch ZN catalyst formulation used to manufacture
Comparatives 1 and 2; further, component B does not contain intermediate
branching
as evidenced by Figures 1, 4 and 6 and did not contain LCB (see LCBF
discussion).
As shown in Table 15, Comparative 6 was fractionated into nine 3D-CFC TREF
fractions; fraction 1 (F1) collected from 30 C to 55 C was 0.1268 weight
fraction
(wt.fr.)1. Fraction Fl had a weight average molecular weight (Mw) of 97,400
g/mol, a
viscosity average molecular weight (Mv) of 91,100 g/mol, an intrinsic
viscosity [n] of
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1.216 dL/g, the amount of short chain branching (SCBf) was 31.02 CH3/1000C and
the
Non-Comonomer Index value of Fraction 1 (NCI1) was 0.950. Comparative 6's
NCIDi
plotted in Figure 14 showed a monotonically decreasing NCIDI.
Tables 10a and 10b summarized the solution process conditions used to
manufacture
Examples 10 and 11; and the resulting physical characteristics were summarized
in
Table 16. Example 10 was a dual reactor and dual catalyst ethylene/1-octene
interpolymer product containing: about 50% of a component A produced in a
first
reactor (R1) using a bridged metallocene catalyst formulation, and; about 50%
of a
component B produced in a second reactor (R2) using an in-line intermediate
branching catalyst formulation that produced intermediate branching. Example
10
was produced with R1 and R2 operated in series mode. Example 11 was a dual
reactor and dual catalyst ethylene/1-octene interpolymer product containing:
about
60% of a component A produced in a first reactor (R1) using a bridged
metallocene
catalyst formulation, and; about 40% of a component B produced in a second
reactor
(R2) using and an in-line intermediate branching catalyst formulation that
produced
intermediate branching. Example 11 was manufactured with R1 and R2 operated in
parallel mode.
.. Table 17 summarized 3D-CFC analysis of Example 10. Example 10 was
fractionated
into nine 3D-CFC TREF fractions; fraction 1 (F1) collected from 30 C to 50 C
was
0.0812 weight fraction (wt.fr.)1. Fraction Fl had a weight average molecular
weight
(Mw) of 98,300 g/mol, a viscosity average molecular weight (My) of 93,200
g/mol, an
intrinsic viscosity [II] of 1.23 dL/g, the amount of short chain branching
(SCBf) was
33.60 CI-13/1000C and the Non-Comonomer Index value of Fraction 1 (NCI1) was
0.961. The NCIDi of Example 10 was plotted in Figure 15, as well as the
molecular
weight distributions of nine 3D-CFC TREF fractions and cumulative (overall)
molecular
weight distribution. Component B in Example 10 contained intermediate
branching
produced by an in-line intermediate branching catalyst formulation. The shape
of the
NCIDi in Figure 15 reflected the following facts: (1) component B's
intermediate
branching reduced NCIDiB values monotonically as Log(Molar Mass) increased as
dNCID,
shown in Figure 5 and the ____ of component B was 5 -0.0001 as shown in
Figure 6,
dlogM,
and; (2) component A contained long chain branching and had a constant NCIDiA
and
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dNCID,
the _______ of component A was zero, or > -0.0001. These facts were supported
by
dlogl
Figure 16. Figure 16 illustrated a simulation of Example 10 showing the NCIDi
distribution of a binary blend of: i) 50 wt% of long chain branched component
A having
a constant NCIDiA of 0.970, and, ii) 50 wt% component B having a NCIDiB
defined by
Eq.(3), where 130, I3-1, 132, and 133 were 1.0100, -0.0001, 0.0001 and -
0.0011,
dNCIDi
respectively, and Mo was 60000; component B was also characterized by dlogMi
values s - 0.0001. The computer simulation was a reasonable representation of
Example 10 as evidenced by the similarity between the experimentally measured
NCIDi values (long dash curve) and the simulated NCIDi values (dotted curve)
in
Figure 16.
The 3D-CFC analysis of Example 11 is summarized in Table 18 and Figure 17.
Example 11 was produced in parallel reactor mode and contained about 40 wt% of
a
component A and about 60 wt% of a component B. The shape of Example 11's NCIDi
(Figure 17) reflected intermediate branching in component B and long chain
branching
in component A.
Comparatives 7 and 8 were dual reactor products produced using the solution
pilot
plant (disclosed herein) employing the bridged metallocene catalyst
formulation
comprising diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfuorenyl)
hafnium
dimethyl in both reactors. Similar to Comparative 5 (Figure 9 and Table 9),
the NCIDi
values of Comparatives 7 and 8 were best represented by one parameter (i.e.
the
mean, 0.954 and 0.929, respectively) intercept models; thus Comparative 7 and
Comparative 8 had dNcID` values of zero.
dlogM,
Long Chain Branching Factor (LCBF)
The Long Chain Branching Factor, hereinafter LCBF, was used to quantify the
amount
of Long Chain Branching (LCB) in ethylene/a-olefin interpolymers. Some
embodiments of the disclosed ethylene/a-olefin interpolymer products did not
contain
LCB (or an undetectable level of LCB). Other embodiments of the disclosed
ethylene/a-olefin interpolymer products contained LCB.
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LCB is a structural phenomenon in polyethylenes and well-known to those of
ordinary
skill. In this disclosure, a long chain branch was equal to, or greater than,
the
entanglement molecular weight, Me. Me is a well-known concept in polymer
physics
(e.g. reported to be about 1 kg/mol for polyethylenes, see Fetters et al.,
.. Macromolecules 1999, 32, 6847). In this disclosure, long chain branches
were
characterized as 'rheologically active'; the term rheologically active means
the
presence of long chain branches in a sample was evident after comparing
rheological
test results with a comparative sample that did not contain long chain
branches. Non-
limiting examples of rheological test results include, flow activation energy
(Eact),
shear thinning or viscosity ratios, melt flow ratios (121/12, 1102, etc.),
melt strength and
long chain branching factor (LCBF), etc.
Typically, in the art, three methods have been used for LCB analysis, i.e.:
nuclear
magnetic resonance spectroscopy (NMR), for example see J.C. Randall, J
Macromol.
Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equipped
with
a DRI, a viscometer and a low-angle laser light scattering detector, for
example see
W.W. Yau and D.R. Hill, Int. J. Polym. Anal. Charact. 1996; 2:151; and
rheology, for
example see W.W. Graessley, Acc. Chem. Res. 1977, 10, 332-339.
A limitation with LCB analysis via NMR is that it cannot distinguish branch
length for
branches equal to or longer than six carbon atoms (thus, NMR cannot be used to
characterize LCB in ethylene/1-octene copolymers, which have hexyl groups as
side
branches).
The triple detection SEC method measures the intrinsic viscosity (N) (see
W.W. Yau, D. Gillespie, Analytical and Polymer Science, TAPPI Polymers,
Laminations, and Coatings Conference Proceedings, Chicago 2000; 2: 699 or F.
Beer,
G. Capaccio, L.J. Rose, J. Appl. Polym. Sci. 1999, 73: 2807 or P.M. Wood-
Adams,
J.M. Dealy, A.W. deGroot, O.D. Redwine, Macromolecules 2000; 33: 7489). By
referencing the intrinsic viscosity of a branched polymer (Nib) to that of a
linear one
(No, at the same molecular weight, the viscosity branching index factor g'
(g'=[q]b/[ri])
was used for branching characterization. However, both short chain branching
(SCB)
and long chain branching (LCB) make contribution to the intrinsic viscosity
([0, effort
was made to isolate the SCB contribution for ethylene/1-butene and ethylene/1-
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hexene copolymers but not ethylene/1-octene copolymers (see Lue et al., US
6,870,010). In this disclosure, a systematical investigation was performed to
look at
the SCB impact on the Mark-Houwink constant K for three types of ethylene/1-
olefin
interpolymers, i.e. octene, hexene and butene interpolymers. After correction
for
SCB, triple detection SEC data was used to calculate the Long Chain Branching
Factor (LCBF).
In the art, rheology has been an effective method to measure the amount of
LCB, or
lack of, in ethylene interpolymers. Several rheological methods to quantify
LCB have
been disclosed. One commonly-used method was based on zero-shear viscosity
(no)
and weight average molar mass (Mw) data. The 3.41 power dependence (no =
KxMw3.41) has been established for monodisperse polyethylene solely composed
of
linear chains, for example see R.L. Arnett and C.P. Thomas, J. Phys. Chem.
1980, 84,
649-652. An ethylene polymer with a rjo exceeding what was expected for a
linear
ethylene polymer, with the same Mw, was considered to contain long-chain
branches.
However, there is a debate in the field regarding the influence of
polydispersity, e.g.
Mw/Mn. A dependence on polydispersity was observed in some cases (see M.
Ansari
et al., Rheol. Acta, 2011, 5017-27) but not in others (see T.P. Karjala et
at., Journal of
Applied Polymer Science 2011, 636-646).
Another example of LCB analysis via rheology was based on zero-shear viscosity
(go)
and intrinsic viscosity (ND data, for example see R.N. Shroff and H. Mavridis,
Macromolecules 1999, 32, 8454; which is applicable for essentially linear
polyethylenes (i.e. polyethylenes with very low levels of LCB). A limitation
of this
method is the contribution of the SCB to the intrinsic viscosity. It is well
known that [r]
decreases with increasing SCB content.
In this disclosure, a systematical investigation was performed to look at the
impact of
both SCB and molar mass distribution on LCB characterization. After the
deduction of
the contribution of both SCB and molar mass distribution (polydispersity), a
Long
Chain Branching Factor (LCBF) was introduced to characterize the amount of LCB
in
ethylene/a-olefin interpolymers, as described in the following paragraphs.
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Figure 18 illustrated the calculation of LCBF. The solid 'Linear Reference
Line' shown
in Figure 18 characterized ethylene/a-olefin interpolymers that did not
contain LCB (or
undetectable LCB). Ethylene/a-olefin interpolymers containing LCB deviate from
this
Reference Line. For example, Example 10 and Comparatives 4, 5 and 6 deviated
horizontally and vertically from the Reference Line.
LCBF calculation requires the polydispersity corrected Zero Shear Viscosity
(ZSVc)
and the SCB corrected Intrinsic Viscosity (IV).
The correction to the Zero Shear Viscosity, ZSVc, having dimensions of poise,
was
performed as shown in equation Eq.(10),
1.8389 X 770
ZSV = Eq. (10)
2.4noLn(Pd)
where no, the zero shear viscosity (poise), was measured by DMA as described
in the
Testing Methods section of this disclosure; Pd was the dimensionless
polydispersity
(i.e. Mw/Mn) as measured using conventional SEC (see Testing Methods) and
1.8389
and 2.4110 are dimensionless constants.
The correction to the Intrinsic Viscosity, IVc, having dimensions of dL/g, was
performed as shown in equation Eq.(11),
A X SCB X 4725
/VC = [17] + Eq.(11)
1000000
where the intrinsic viscosity [n] (dL/g) was measured using 3D-SEC (see
Testing
Methods); SCB having dimensions of (CH3#/1000C) was determined using FTIR (see
Testing Methods), and; Mv, the viscosity average molar mass (g/mole), was
determined using 3D-SEC (see Testing Methods). The comonomer dependent
constant A was defined above. In the case of an ethylene homopolymer no
correction
is required for the Mark-Houwink constant, i.e. SCB is zero.
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As shown in Figure 18, linear ethylene/a-olefin interpolymers (which do not
contain
LCB or undetectable levels of LCB) fall on the Reference Line, e.g. Examples
1, 4 and
and Comparatives 1 and 3, as defined by Eq.(12).
5 Log(IV) = 0.2100 x Log(ZSV)¨ 0.7879 Eq.(12)
Tables 19a and 19b disclosed Reference Resins having Mw/Mn (Pd) values that
ranged from 1.68 to 9.23 containing 1-octene, 1-hexene or 1-butene a-olefins.
Reference Resins included ethylene interpolymers produced in solution, gas
phase or
slurry processes with comparative Ziegler-Natta, homogeneous and mixed
(comparative Ziegler-Natta + homogeneous) catalyst formulations. Reference
resins,
having no LCB (or undetectable LCB), were characterized by LCBF values less
than
0.001 (dimensionless), as supported by the LCBF values reported in Table 19b
where
LCBF values ranged from 0.000426 to 1.47x10-9.
As shown in Figure 18, the calculation of the LCBF was based on the Horizontal-
Shift
(Sn) and Vertical-Shift (Sv) from the linear reference line, as defined by the
following
equations:
Sh= Log(ZS17,)¨ 4.7619 x Log(IV,)¨ 3.7519 Eq.(13)
= 0.2100 x Log(ZSV,)¨ Log(IV) ¨ 0.7879 Eq.(14)
In Eq.(13) and Eq.(14), it was required that ZSVc and IVc have dimensions of
poise
and dL/g, respectively. The Horizontal-Shift (Sn) was a shift in ZSVc at
constant
Intrinsic Viscosity (IVc), if one removes the Log function its physical
meaning is
apparent, i.e. a ratio of two Zero Shear Viscosities, the ZSVc of the sample
under test
relative to the ZSVc of a linear ethylene polymer having the same IVc. The
Horizontal-
Shift (Sn) was dimensionless. The Vertical-Shift (Sv) was a shift in IVc at
constant Zero
Shear Viscosity (ZSVc), if one removes the Log function its physical meaning
is
apparent, i.e. a ratio of two Intrinsic Viscosities, the IVc of a linear
ethylene polymer
having the same ZSVc relative to the IVc of the sample under test. The
Vertical-Shift
(Sv) was dimensionless.
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In this disclosure a dimensionless Long Chain Branching Factor (LCBF) was
defined
by Eq.(15):
LCBF = shxsv - Eq.(15)
2
Given the data in Table 20 the LCBF of Examples 1, 4, 5-7, 10 and 11 were
calculated. To be more clear: the Sh and Sv of Example 1 were -0.0487 and -
0.0102,
respectively, thus the LCBF was 0.000249 ((-0.0487 x -0.0102)/2), i.e. Example
1 did
not contain LCB; in contrast, Examples 10 and 11 contained LCB given the LCBF
values of 0.0291 and 0.0205, respectively.
Examples 1 and 4-7, having LCBF values less than 0.001, did not contain LCB
(or
undetectable LCB); but did contain intermediate branching (as discussed
above).
Figure 18 showed Examples 1, 4 and 5 falling on the Reference Line defined by
Eq.(12), i.e. no LCB. Examples 1 and 4 were manufactured as disclosed in
Tables la
and lb using embodiments of an intermediate branching catalyst formulation;
physical
characteristics of Examples 1 and 4 were disclosed in Table 2.
Examples 5-7 contained two components: component A was produced in a first
reactor using an unbridged single site catalyst formulation that produced
interpolymer
that did not contain LCB or intermediate branching, and; component B was
produced
in a second reactor using an in-line intermediate branching catalyst
formulation that
produced interpolymer that did not contain LCB but did contain intermediate
branching. The solution process conditions required to manufacture Example 5
were
summarized in Tables 10a and 10b and the physical characteristics were
summarized
in Table 11.
As shown in Table 20, Examples 10 and 11 contained LCB as evidenced by LCBF
values of 0.0291 and 0.0205, respectively; i.e. LCBF ?_ 0.001. Figure 18
showed the
significant deviation of Example 10 from the Linear Reference Line. Examples
10 and
11 contained two components: LCB containing component A was produced in a
first
reactor employing a bridged metallocene catalyst formulation; and; component B
was
produced in a second reactor using an in-line intermediate branching catalyst
formulation producing an interpolymer that did not contain LCB but did contain
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intermediate branching. The solution process conditions required to
manufacture
Examples 10 and 11 were summarized in Tables 10a and 10b and physical
characteristics were summarized in Table 16.
As shown in Table 21, Comparatives 1 and 3 did not contain LCB (LCBF was <
0.001). Comparatives 1 and 3 did not contain intermediate branching.
Comparative 1
was produced in a solution process using a comparative batch Ziegler-Natta
catalyst
formulation, physical properties were summarized in Table 2. Comparative 3 was
produced in a solution process using an unbridged single site catalyst
formulation;
physical properties were summarized in Table 7.
As evidenced by the LCBF values shown in Table 21, Comparatives 4 through 8
contained LCB. To be more clear: Comparative 4 contained LCB as evidenced by
the
LCBF value of 0.0406 disclosed in Table 21 (LCBF 0.001), as well as the
significant
deviation from the Linear Reference Line shown in Figure 18. Comparative 4 was
an
ethylene/1-octene copolymer produced in a solution polymerization process
employing a constrained geometry catalyst; physical characteristics were
summarized
in Table 7. Comparative 5 contained LCB as evidenced by the LCBF value of
0.0563.
Comparative 5 was an ethylene/1-octene copolymer produced in the solution
pilot
plant (disclosed herein) employing a bridged metallocene catalyst formulation;
physical characteristics were disclosed in Table 7.
Comparative 6 was a competitive ethylene/1-octene interpolymer produced in a
dual
reactor solution process. Comparative 6 contained two components: long chain
branched component A was produced in a first reactor using a constrained
geometry
catalyst formulation, and; component B was produced in a second reactor using
a
comparative batch ZN catalyst formulation that produced an interpolymer that
did not
contain LCB or intermediate branching. Comparative 6 contained LCB as
evidenced
by the LCBF value of 0.00883 disclosed in Table 21 (LCBF 0.001). Further:
component A in Comparative 6 was believed to be produced by the same
constrained
geometry catalyst that was used to manufacture Comparative 4 (Comparative 4
contained LCB), and; component B in Comparative 6 was believed to be produced
by
the same comparative batch ZN catalyst formulation used to manufacture
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Comparative 1 (Comparative 1 did not contain LCB or intermediate branching).
The
physical characteristics of Comparative 6 were summarized in Table 11.
Comparatives 7 and 8 were dual reactor products produced using the solution
pilot
plant (disclosed herein) and the same catalyst formulation was employed in
both
reactors; more specifically, the bridged metallocene catalyst formulation,
containing
diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium
dimethyl, was
injected into both reactors 1 and 2. As shown in Table 21, Comparatives 7 and
8
contained long chain branching, i.e. the dimensionless LCBF was 0.0438 and
0.0541,
respectively. The physical characteristics of Comparatives 7 and 8 were
summarized
in Table 16, these interpolymers had a melt index (12) of about 1.0 dg/min;
polydispersities (Mw/Mn) were 3.32 and 2.51, respectively.
In this disclosure, resins having LCB were characterized by a LCBF of 0.001
(dimensionless); and resins having no LCB (or undetectable LCB) were
characterized
by a LCBF of less than 0.001.
Solution Polymerization Process
Non-limiting embodiments of continuous solution polymerization processes
wherein
ethylene interpolymer products having intermediate branching may be produced
are
shown in Figures 19 and 20. These Figures are not to be construed as limiting,
it
being understood that embodiments are not limited to the precise arrangement
of, or
number of, vessels shown.
Intermediate Branching Catalyst Formulations
Embodiments are described where an in-line intermediate branching catalyst
.. formulation and a batch intermediate branching catalyst formation were
used. The
term 'in-line' referred to the continuous synthesis of a small quantity of
catalyst and
immediately injecting this catalyst into at least one continuously operating
reactor
wherein an ethylene interpolymer was formed. The terms 'batch' referred to the
synthesis of a much larger quantity of catalyst or procatalyst in one or more
mixing
vessels that are external to, or isolated from, the continuously operating
solution
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polymerization process. Once prepared, the batch catalyst formulation, or
batch
procatalyst, was transferred to a catalyst storage tank. The term `procatalyst
referred
to an inactive catalyst formulation (inactive with respect to ethylene
polymerization);
procatalyst was converted to an active catalyst by adding an alkyl aluminum co-
catalyst. As needed, the procatalyst was pumped from the storage tank to at
least
one continuously operating reactor wherein an ethylene interpolymer was
formed.
The procatalyst may be converted into an active catalyst in the reactor or
external to
the reactor.
As described in the following paragraph a wide variety of chemical compounds
can be
used to synthesize an in-line intermediate branching catalyst formulation; it
being
understood that disclosed embodiments were not limited to the specific
chemical
compounds disclosed.
An in-line intermediate branching catalyst formulation may be formed from:
component (v), a magnesium compound; component (vi), a chloride compound;
component (vii), a metal compound; component (viii), an alkyl aluminum co-
catalyst;
and component (ix), an aluminum alkyl. A non-limiting example of an
intermediate
branching catalyst formulation may be prepared as follows. In the first step,
a solution
of a magnesium compound (component (v)) was reacted with a solution of
chloride
compound (component (vi)) forming a magnesium chloride support suspended in
solution. Non-limiting examples of magnesium compounds included Mg(R1)2;
wherein
the R1 groups may be the same or different, linear, branched or cyclic
hydrocarbyl
radicals containing 1 to 10 carbon atoms. Non-limiting examples of chloride
compounds include R2CI; where R2 represents a hydrogen atom, or a linear,
branched
or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. In the first
step, the
solution of magnesium compound may also contain an aluminum alkyl (component
(ix)). Non-limiting examples of aluminum alkyl include Al(R3)3, wherein the R3
groups
may be the same or different, linear, branched or cyclic hydrocarbyl radicals
containing from 1 to 10 carbon atoms. In the second step a solution of the
metal
compound (component (vii)) was added to the solution of magnesium chloride and
the
metal compound was supported on the magnesium chloride. Non-limiting examples
of suitable metal compounds included M(X) n or MO(X)n; where M represents a
metal
selected from Group 4 through Group 8 of the Periodic Table, or mixtures of
metals
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selected from Group 4 through Group 8; 0 represents oxygen, and; X represents
chloride or bromide; n is an integer from 3 to 6 that satisfies the oxidation
state of the
metal. Additional non-limiting examples of suitable metal compounds include
Group 4
to Group 8 metal alkyls, metal alkoxides (which may be prepared by reacting a
metal
alkyl with an alcohol) and mixed-ligand metal compounds that contain a mixture
of
halide, alkyl and alkoxide ligands. In the third step a solution of an alkyl
aluminum co-
catalyst (component (viii)) was added to the metal compound supported on the
magnesium chloride. A wide variety of alkyl aluminum co-catalysts were
suitable, as
expressed by Formula (I):
Al(R4)p(0R5)q(X)r (I)
wherein R4 groups may be the same or different, hydrocarbyl groups having from
1 to
10 carbon atoms; OR5 groups may be the same or different, alkoxy or aryloxy
groups
wherein R5 is a hydrocarbyl group having from 1 to 10 carbon atoms bonded to
oxygen; X is chloride or bromide, and; (p+q+r) = 3, with the proviso that p is
greater
than 0. Non-limiting examples of suitable 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. Further, to produce a
highly
active in-line intermediate branching catalyst formulation the quantity and
mole ratios
of components (v) through (ix) were optimized as described below; where the
term
'highly active' means the catalyst formulation was very efficient in
converting olefins to
an ethylene interpolymer having intermediate branching, i.e. maximizing the
following
ratio: (pounds of ethylene interpolymer product produced) per (pounds of
catalyst
consumed).
In-line intermediate branching catalyst formulation synthesis may be carried
out in a
variety of solvents; non-limiting examples of solvents include linear or
branched C5 to
C12 alkanes or mixtures thereof.
A batch intermediate branching procatalyst may be prepared by sequentially
added
the following components to a stirred mixing vessel: (a) a solution of a
magnesium
compound (component (v)); (b) a solution of a chloride compound (component
(vi));
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(c) optionally a solution of an aluminum alkyl halide, and; (d) a solution of
a metal
compound (component (vii)). Suitable, non-limiting examples of aluminum alkyl
halides are defined by the formula (R6)vAIX3-v; where R6 groups may be the
same or
different hydrocarbyl group having from 1 to 10 carbon atoms, X represents
chloride
or bromide, and; v is 1 or 2. Suitable, non-limiting examples of the magnesium
compound, the chloride compound and the metal compound were described earlier
in
this disclosure. Suitable solvents within which to prepare the procatalyst
include linear
or branched C5 to C12 alkanes or mixtures thereof.
Individual mixing times and mixing temperatures may be used in each of steps
(a)
through (d). The upper limit on mixing temperatures for steps (a) through (d)
in some
case may be 160 C, in other cases 130 C and in still other cases 100 C. The
lower
limit on mixing temperatures for steps (a) through (d) in some cases may be 10
C, in
other cases 20 C and in still other cases 30 C. The upper limit on mixing time
for
steps (a) through (d) in some case may be 6 hours, in other cases 3 hours and
in still
other cases 1 hour. The lower limit on mixing times for steps (a) through (d)
in some
cases may be 1 minute, in other cases 10 minutes and in still other cases 30
minutes.
Batch intermediate branching procatalyst formulations can have various
catalyst
component mole ratios. The upper limit on the (chloride compound)/(magnesium
compound) molar ratio in some cases may be about 3, in other cases about 2.7
and is
still other cases about 2.5; the lower limit in some cases may be about 2.0,
in other
cases about 2.1 and in still other cases about 2.2. The upper limit on the
(magnesium
compound)/(metal compound) molar ratio in some cases may be about 10, in other
cases about 9 and in still other cases about 8; the lower limit in some cases
may be
about 5, in other cases about 6 and in still other cases about 7. The upper
limit on the
(aluminum alkyl halide)/(magnesium compound) molar ratio in some cases may be
about 0.5, in other cases about 0.4 and in still other cases about 0.3; the
lower limit in
some cases may be 0, in other cases about 0.1 and in still other cases about
0.2. A
batch intermediate branching catalyst formulation was formed when the
procatalyst
was combined with an alkyl aluminum co-catalyst. Suitable co-catalysts were
described earlier in this disclosure. The procatalyst may be activated
external to the
reactor or in the reactor; in the latter case, the procatalyst and an
effective amount of
alkyl aluminum co-catalyst were independently injected at least one reactor.
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Homogeneous Catalyst Formulations
This disclosure is not limited to any specific genus of bulky ligand-metal
complex;
.. rather, a wide variety of bulky ligand-metal complexes may be used to form
a
homogeneous ethylene interpolymer that may comprise a portion of the ethylene
interpolymer product having intermediate branching. Homogeneous catalyst
formulations produce a homogeneous ethylene interpolymer characterized by a
narrow molecular weight distribution (Mw/Mn < 2.8), a narrow comonomer
distribution
(CDBI50 > 70%) and devoid of intermediate branching. The following paragraphs
disclose two examples of homogeneous catalyst formulations; specifically, an
unbridged single site catalyst formulation and a bridged metallocene catalyst
formulation; these examples are not to be construed as limiting.
.. The unbridged single site catalyst formulation employed the following bulky
ligand-
metal complex Formula (II);
(LA)aM(PI)b(Q)n (II)
wherein (LA) represents a bulky ligand; M represents a metal atom; PI
represents a
phosphinimine ligand; Q represents a leaving group; a is 0 or 1; b is 1 or 2;
(a+b) = 2;
n is 1 or 2, and; the sum of (a+b+n) equals the valance of the metal M.
Non-limiting examples of the bulky ligand LA in Formula (II) include
unsubstituted or
.. substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands,
heteroatom
substituted and/or heteroatom containing cyclopentadienyl-type ligands.
Additional
non-limiting examples include, cyclopentaphenanthreneyl ligands, unsubstituted
or
substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted
fluorenyl
ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,
cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene
ligands,
phosphoyl ligands, phosphinimine, pyrrolyl ligands, pyrozolyl ligands,
carbazolyl
ligands, borabenzene ligands and the like, including hydrogenated versions
thereof,
for example tetrahydroindenyl ligands. In other embodiments, LA may be any
other
ligand structure capable of rl-bonding to the metal M, such embodiments
include both
q3-bonding and r15-bonding to the metal M. In other embodiments, LA may
comprise
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one or more heteroatoms, for example, nitrogen, silicon, boron, germanium,
sulfur and
phosphorous, in combination with carbon atoms to form an open, acyclic, or a
fused
ring, or ring system, for example, a heterocyclopentadienyl ancillary ligand.
Other
non-
limiting embodiments for LA include bulky amides, phosphides, alkoxides,
aryloxides,
imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other
polyazomacrocycles.
Non-limiting examples of metal M in Formula (II) include Group 4 metals,
titanium,
zirconium and hafnium.
The 'leaving group' Q in Formula (II) is any ligand that can be abstracted
forming a
catalyst species capable of polymerizing one or more olefin(s). An equivalent
term for
Q is an `activatable ligand', i.e. equivalent to the term "leaving group". In
some
embodiments, Q is a monoanionic labile ligand having a sigma bond to M.
Depending
on the oxidation state of the metal, the value for n is 1 or 2 such that
Formula (II)
represents a neutral bulky ligand-metal complex. Non-limiting examples of Q
ligands
include a hydrogen atom, halogens, C1-20 hydrocarbyl radicals, C1-20 alkoxy
radicals,
05-10 aryl oxide radicals; these radicals may be linear, branched or cyclic or
further
.. substituted by halogen atoms, Ci-io alkyl radicals, Ci-io alkoxy radicals,
06-10 arly or
aryloxy radicals. Further non-limiting examples of Q ligands include weak
bases such
as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals
having from
1 to 20 carbon atoms. In another embodiment, two Q ligands may form part of a
fused ring or ring system.
The phosphinimine ligand, PI, is defined by Formula (III):
(RP)3 P N - (III)
.. wherein the RP groups are independently selected from: a hydrogen atom; a
halogen
atom; 01-20 hydrocarbyl radicals which are unsubstituted or substituted with
one or
more halogen atom(s); a 01-8 alkoxy radical; a C6-10 aryl radical; a 06-10
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 01-8 alkyl or alkoxy radical,
a C6-10
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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.
Further embodiments of Formula (II) include structural, optical or
enantiomeric
isomers (meso and racemic isomers) and mixtures thereof. While not to be
construed
as limiting, the species of Formula (II) employed in this disclosure was
cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride, (Cp[(t-
Bu)3PN]TiC12); abbreviated PIC-1 in this disclosure.
The non-limiting example of the bridged metallocene catalyst formulation
employed in
this disclosure employed the following bulky ligand-metal complex Formula
(IV);
X(R)
R4
M¨X(R6)
R5
FoR
..3
(IV)
R2
In Formula (IV): non-limiting examples of M include Group 4 metals, i.e.
titanium,
zirconium and hafnium; non-limiting examples of G include Group 14 elements,
carbon, silicon, germanium, tin and lead; X represents a halogen atom,
fluorine,
chlorine, bromine or iodine; the R6 groups are independently selected from a
hydrogen atom, a C1-20 hydrocarbyl radical, a 01-20 alkoxy radical or a 06-10
aryl oxide
radical (these radicals may be linear, branched or cyclic or further
substituted with
halogen atoms, Cm() alkyl radicals, Cm alkoxy radicals, C6-10 aryl or aryloxy
radicals);
Ri represents a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy
radical, a
C6-10 aryl oxide radical or alkylsilyl radicals containing at least one
silicon atom and C3-
carbon atoms; R2 and R3 are independently selected from a hydrogen atom, a 01-
20
30 hydrocarbyl radical, a C1-20 alkoxy radical, a 06-10 aryl oxide radical
or alkylsilyl
radicals containing at least one silicon atom and C3-30 carbon atoms, and; R4
and R5
are independently selected from a hydrogen atom, a C1-20 hydrocarbyl radical,
a 01-20
alkoxy radical a 06-10 aryl oxide radical, or alkylsilyl radicals containing
at least one
silicon atom and C3-30 carbon atoms.
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In Formula (IV) the X(R6) group was a 'leaving group' or `activatable ligand';
as
described above in Formula (II), i.e. equivalent to the group Q illustrated in
Formula
(II).
Further embodiments of Formula (IV) include structural, optical or
enantiomeric
isomers (meso and racemic isomers) and mixtures thereof. While not to be
construed
as limiting, the species of Formula (IV) employed in this disclosure was
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dimethyl,
[(2,7-
tBu2Flu)Ph2C(Cp)HfMe2]; abbreviated CpF-2 in this disclosure.
The catalyst components required to fabricate a homogeneous catalyst
formulation
are not particularly limited, i.e. a wide variety of catalyst components can
be used.
One non-limiting example of a homogeneous catalyst formulation comprises the
following components: component (i), a bulky ligand-metal complex; component
(ii),
an alumoxane co-catalyst; 'component (iii), an ionic activator; and optionally
component (iv), a hindered phenol. In this disclosure: if a species of Formula
(II) was
employed as component (i) an unbridged single site catalyst formulation
results; in
contrast, if a species of Formula (IV) was employed as component (i) a bridged
metallocene catalyst formulation results.
A non-limiting example of component (ii) in the homogeneous catalyst
formulation was
an alumoxane co-catalyst that activates component (i) to a cationic complex.
An
equivalent term for "alumoxane" is "aluminoxane"; although the exact structure
of this
co-catalyst is uncertain, subject matter experts generally agree that it is an
oligomeric
species that contain repeating units of the general Formula N):
(R)2A10-(Al(R)-0)n-Al(R)2 (V)
where the R groups may be the same or different linear, branched or cyclic
hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about
50. A
non-limiting example of an alumoxane is methyl aluminoxane (or MAO) wherein
each
R group in formula (V) is a methyl radical.
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A non-limiting example of component (iii) of the homogeneous catalyst
formulation
was 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 (VI) and (VII) shown below;
[R5y[B(R7)4]- (VI)
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,
C14 alkyl or alkoxy radicals which are unsubstituted or substituted by
fluorine atoms;
and a silyl radical of formula -Si(R9)3, where each R9 is independently
selected from
hydrogen atoms and C1-4 alkyl radicals, and; compounds of Formula (VII);
[(R8)tZH][B(R7)4- (VII)
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 01-4 alkyl radicals, or one R8
taken together
with the nitrogen atom may form an anilinium radical and R7 is as defined
above in
Formula (VI).
In both Formula (VI) and (VII), a non-limiting example of R7 is a
pentafluorophenyl
radical. In general, boron ionic activators may be described as salts of
tetra(perfluorophenyl) boron; non-limiting examples include anilinium,
carbonium,
oxonium, phosphonium and sulfonium salts of tetra(perfluorophenyl)boron with
anilinium and trityl (or triphenylmethylium). Additional non-limiting examples
of ionic
activators include: triethylammonium tetra(phenyl)boron, tripropylammonium
tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium
tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-
dimethylphenyl)boron,
tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra (p-
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trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron,
tri(n-
butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron,
N,N-
diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-
butylboron,
N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium
tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron,
triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium
tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron,
tropillium
tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl
borate,
benzene(diazonium)tetrakispentafluorophenyl borate, tropillium
tetrakis(2,3,5,6-
tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-
tetrafluorophenyl)borate,
benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium
tetrakis(3,4,5 -
trifluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-
trifluorophenyl)borate,
tropillium tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium
tetrakis(1 ,2,2-
trifluoroethenyl)borate, benzene(diazonium) tetrakis(1,2,2-
trifluoroethenyl)borate,
tropillium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylium
tetrakis(2,3,4,5-
tetrafluorophenyl)borate, and benzene(diazonium) tetrakis(2,3,4,5
tetrafluorophenyl)borate. Readily available commercial ionic activators
include N,N-
dimethylanilinium tetrakispentafluorophenyl borate, and triphenylmethylium
tetrakispentafluorophenyl borate.
A non-limiting example of optional component (iv) of the homogeneous catalyst
formulation was a hindered phenol. Non-limiting example of hindered phenols
include
butylated phenolic antioxidants, butylated hydroxytoluene, 2,4-di-
tertiarybuty1-6-ethyl
phenol, 4,4'-methylenebis (2,6-di-tertiary-butylphenol), 1,3, 5-trimethy1-
2,4,6-tris (3,5-
di-tert-butyl-4-hydroxybenzyl) benzene and octadecy1-3-(3',5'-di-tert-buty1-4'-
hydroxyphenyl) propionate.
An active homogeneous catalyst formulation was produced by optimizing the
proportion of each of the four catalyst components: component (i), component
(ii),
component (iii) and component (iv). In the case of one reactor (R1), the
quantity of
component (i) added to the reactor was expressed as the parts per million
(ppm) of
component (i) in the total mass of reactor solution, i.e. `R1 (i) catalyst
(ppm)' as recited
in Table 10a. The upper limit on R1 (i) catalyst (ppm) may be 5 ppm, in some
cases 3
ppm and in other cases 2 ppm. The lower limit on R1 (i) catalyst (ppm) may be
0.02
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ppm, in some cases 0.05 ppm and in other cases 0.1 ppm. An effective
proportion of
component (iii) to prepare a homogeneous catalyst formulation was determined
by
optimizing the [component(iii)]/[(component (i)] molar ratio in the reactor
solution, e.g.
R1 (iii)/(i) as recited in Table 10a. The upper limit on R1 (iii)/(i) may be
10, in some
cases 5 and in other cases 2. The lower limit on R1 (iii)/(i) may be 0.3, in
some cases
0.5 and in other cases 1Ø An effective proportion of component (ii) to
prepare a
homogeneous catalyst formulation was determined by optimizing the [component
(ii)]/[component (i)] molar ratio, e.g. R1 (ii)/(i) as recited in Table 10a.
Alumoxane was
generally added in a molar excess relative to component (i). The upper limit
on R1
.. (ii)/(i) may be 1000, in some cases 500 and is other cases 200. The lower
limit on R1
(ii)/(i) may be 1, in some cases 10 and in other cases 30. An effective
proportion of
component (iv) to prepare a homogeneous catalyst formulation was determined by
optimizing the [component (iv)]/[component (ii)] molar ratio, e.g. R1
(iv)/(ii) as recited
in Table 10a. The upper limit on R1 (iv)/(ii) may be 1, in some cases 0.75 and
in other
cases 0.5. The lower limit on R1 (iv)/(ii) may be 0.0, in some cases 0.1 and
in other
cases 0.2.
In embodiments employing two CSTR's and two homogeneous catalyst assemblies a
second bridged metallocene catalyst formulation may be prepared independently
of
the first bridged metallocene catalyst formulation and optimized as described
above.
Optionally, a bridged metallocene catalyst formulation may be employed in the
tubular
reactor and optimized as described above.
Embodiments in this disclosure include the use of one or more homogeneous
catalyst
formulations in more than one reactor.
Solution Polymerization Process In-Line Catalyst Formulation
Figure 19 illustrates several embodiments were two or three reactors may be
__ employed to produce an ethylene interpolymer product having intermediate
branching.
Figure 19 illustrates a first reactor 11a; in this disclosure an equivalent
term for the
first reactor was `R1'. Figure 19 also showed a second reactor 12a; an
equivalent
term for the second reactor was `R2'. R1 was a continuously stirred tank
reactor
(CSTR) agitated by stirring assembly llb which includes a motor external to
the
reactor and an agitator within the reactor. Similarly, R2 was agitated by
stirring
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assembly 12b. Figure 19 also showed an optional tubular reactor 17; in this
disclosure, equivalent terms for the tubular reactor were 'the third reactor'
or 113'. The
third reactor need not be tubular, i.e. a wide variety of reactor designs may
be
employed. The embodiment shown in Figure 19 may be used to produce a first
ethylene interpolymer in R1, a second ethylene interpolymer in R2 and a third
ethylene interpolymer in R3. Optionally, polymerization may be terminated
prior to
R3; in this case a third ethylene interpolymer was not produced. Figure 19
illustrates
an embodiment where an in-line intermediate branching catalyst formulation was
employed in R2 producing a second ethylene interpolymer having intermediate
branching. Optionally, the in-line intermediate branching catalyst formulation
may also
be employed in R3 producing a third ethylene interpolymer having intermediate
branching. In an alternative embodiment, a second in-line intermediate
branching
catalyst formulation may be employed in R3 producing a third ethylene
interpolymer
having intermediate branching. In an alternative embodiment, a comparative
Ziegler-
Natta catalyst formulation may be employed in R3 producing a third ethylene
interpolymer that did not contain intermediate branching.
In this disclosure, a variety of catalysts may be employed in the first
reactor; for
example, a homogeneous catalyst formulation, a heterogeneous catalyst
formulation,
a ZN catalyst formulation or an intermediate branching catalyst formulation;
the latter
produces a first ethylene interpolymer having intermediate branching.
Not to be construed as limiting, Figure 19 illustrates an embodiment where a
homogeneous catalyst formulation was employed in the first reactor R1. In
Figure 19,
process solvent 1, ethylene 2 and a-olefin 3 were combined to produce reactor
feed
stream RF1 which was injected into reactor 11a, or R1. In Figure 19 optional
streams,
or optional embodiments, were denoted with dotted lines. It was not
particularly
important that combined reactor feed stream RF1 be formed; i.e. reactor feed
streams
can be combined in all possible combinations, including an embodiment where
streams 1 through 3 were independently injected into reactor 11a. Optionally
hydrogen may be injected into reactor lla through stream 4; hydrogen was
generally
added to control the molecular weight of the first ethylene interpolymer.
Figure 19 illustrated an embodiment where a homogeneous catalyst formulation
was
injected into reactor 11 a through stream 5e. Homogeneous catalyst component
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streams 5d, 5c, 5b and optional 5a refer to an ionic activator (component
(iii)), a bulky
ligand-metal complex (component (i)), an alumoxane co-catalyst (component
(ii)) and
an optional hindered phenol (component (iv)), respectively. Homogeneous
catalyst
component streams can be arranged in all possible configurations, including an
embodiment where streams 5a through 5d were independently injected into
reactor
11a. Each homogeneous catalyst component was dissolved in a catalyst component
solvent. Catalyst component solvents, for component (i) through (iv), may be
the
same or different. Catalyst component solvents were selected such that the
combination of catalyst components did not produce a precipitate in any
process
stream; for example, precipitation of a portion of the homogeneous catalyst
formulation in the conduit or stream 5e. The optimization of the homogeneous
catalyst formulation was described below. Reactor lla produced a first exit
stream,
stream 11c, that contained the first ethylene interpolymer dissolved in
process solvent,
as well as unreacted ethylene, unreacted a-olefins (if present), unreacted
hydrogen (if
present), active homogeneous catalyst, deactivated homogeneous catalyst,
residual
catalyst components and other impurities (if present). Melt index ranges and
density
ranges of the first ethylene interpolymer produced were described below.
Figure 19 illustrated embodiments where reactors 11a and 12a can be operated
in
series or parallel modes. In series mode 100% of stream 11c (a first exit
stream)
passes through flow controller 11d forming stream 11e which enters reactor
12a. In
contrast, in parallel mode 100% of stream 11c passes through flow controller
11f
forming stream 11g. Stream llg by-passes reactor 12a and is combined with
stream
12c (the second exit stream) forming stream 12d (the third exit stream).
Fresh reactor feeds were injected into R2, reactor 12a, i.e.; process solvent
6,
ethylene 7 and a-olefin 8 were combined to produce reactor feed stream RF2. It
was
not important that stream RF2 be formed; i.e. reactor feed streams can be
combined
in all possible combinations, including independently injecting each stream
into the
reactor. Optionally hydrogen may be injected into reactor 12a through stream 9
to
control the molecular weight of the second ethylene interpolymer having
intermediate
branching.
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Figure 19 illustrated an embodiment where an in-line intermediate branching
catalyst
formulation (capable of producing a second ethylene interpolymer having
intermediate
branching) was injected into reactor 12a through stream 10f. The catalyst
components that comprised the in-line intermediate branching catalyst
formulation
were introduced through streams 10a, 10b, 10c and 10d; streams 10a', 10b',
10c'
represent streams containing process solvent for diluting the respective
catalyst
components and controlling stream temperatures. In this disclosure, the term
'a first
heterogeneous catalyst assembly', defined by the conduits and flow controllers
associated with streams 10a through 10h, was operated as described in this
paragraph. The first heterogeneous catalyst assembly produced an in-line
intermediate branching catalyst formulation by optimizing feed flow rates,
temperatures and the following molar ratios: (aluminum alkyl)/(magnesium
compound)
or (ix)/(v); (chloride compound)/(magnesium compound) or (vi)/(v); (alkyl
aluminum co-
catalyst)/(metal compound) or (viii)/(vii), and; (aluminum alkyl)/(metal
compound) or
(ix)/(vii); as well as the time these compounds have to react and equilibrate.
Stream
10a contained a binary blend of a magnesium compound, component (v) and an
aluminum alkyl, component (ix), in process solvent. The upper limit on the
(aluminum
alkyl)/(magnesium compound) molar ratio in stream 10a may be 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. Stream 10b contained a solution of a chloride
compound, component (vi), in process solvent. Stream 10b (and associated
solvent
stream 10b') were combined with stream 10a (and associated solvent stream
10a')
and the intermixing of these streams produced a magnesium chloride catalyst
support.
The in-line intermediate branching catalyst formulation was produced by
optimizing
the (chloride compound)/(magnesium compound) molar ratio. 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 time between the addition of the
chloride
compound and the addition of the metal compound (component (vii)) via stream
10c
was controlled; hereafter HUT-1 (the first Hold-Up-Time). HUT-1 was the time
for
streams 10a and 10b to form a magnesium chloride support and equilibrate. The
upper limit on HUT-1 may be about 70 seconds, in some cases about 60 seconds
and
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is other cases about 50 seconds. The lower limit on HUT-1 may be about 5
seconds,
in some cases about 10 seconds and in other cases about 20 seconds. HUT-1 was
controlled by adjusting the length of the conduit between the combination of
streams
10a and 10b and the downstream injection of stream 10c (plus 100 injection, as
well
.. as controlling the flow rates of these streams. The temperature of the
solution during
HUT-1, i.e. " THuT-1", was controlled; the upper limit on ruT-1 may be about
100 C, in
some cases about 90 C and is other cases about 80 C; the lower limit on THuT-1
may
be about 30 C, in some cases about 40 C and in other cases about 50 C.
Following
HUT-1, stream 10c containing component (vii) (and associated solvent stream
10c')
was injected into the solution containing the magnesium chloride support. The
time
between the addition of component (vii) and the addition of the alkyl aluminum
co-
catalyst, component (viii), via stream 10d was controlled; hereafter HUT-2
(the second
Hold-Up-Time). HUT-2 was the time for the magnesium chloride support and the
component (vii) in stream 10c to react and equilibrate. The upper limit on HUT-
2 may
be about 50 seconds, in some cases about 35 seconds and is other cases about
25
seconds. The lower limit on HUT-2 may be about 2 seconds, in some cases about
6
seconds and in other cases about 10 seconds. HUT-2 was controlled by adjusting
the
length of the conduit between stream 10c (plus 10c') injection and stream 10d
injection, as well as controlling the flow rates of these streams. The
temperature of
the solution during HUT-2, i.e.., THUT-2 u, was also controlled; the upper
limit on THUT-2
may be about 100 C, in some cases about 90 C and is other cases about 80 C;
the
lower limit on TH1T-2 may be about 30 C, in some cases about 40 C and in other
cases about 50 C. The quantity of the alkyl aluminum co-catalyst added was
optimized to produce an efficient catalyst; this was accomplished by adjusting
the
(alkyl aluminum co-catalyst)/(metal compound) molar ratio, or (viii)/(vii)
molar ratio.
The upper limit on the (alkyl aluminum co-catalyst)/(metal compound) molar
ratio may
be 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 In addition, the time between
the
addition of the alkyl aluminum co-catalyst and the injection of the in-line
intermediate
branching catalyst formulation into reactor 12a via stream 10f was controlled;
hereafter HUT-3 (the third Hold-Up-Time). HUT-3 was the time for stream 10d to
intermix and equilibrate to form the in-line intermediate branching catalyst
formulation.
Prior to reactor injection, additional process solvent may be added to stream
10f via
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stream 10f. The upper limit on HUT-3 may be about 15 seconds, in some cases
about 10 seconds and is other cases about 8 seconds. The lower limit on HUT-3
may
be about 0.5 seconds, in some cases about 1 seconds and in other cases about 2
seconds. HUT-3 was controlled by adjusting the length of the conduit between
stream
.. 10d injection and the catalyst injection port on reactor 12a, and by
controlling the flow
rates of associated streams. The R2 catalyst inlet temperature was controlled,
the
upper limit on R2 catalyst inlet temperature may be about 70 C, in some cases
about
60 C and is other cases about 50 C; and the lower limit on R2 catalyst inlet
temperature may be about 10 C, in some cases about 20 C and in other cases
about
30 C. As shown in Figure 19, optionally, 100% of stream 10d, the alkyl
aluminum co-
catalyst, may be injected directly into reactor 12a via stream 10h.
Optionally, a portion
of stream 10d may be injected directly into reactor 12a via stream 10h and the
remaining portion of stream 10d injected into reactor 12a via stream 10f. The
quantity
of in-line intermediate branching catalyst formulation added to R2 is
expressed as the
parts-per-million (ppm) of metal compound (component (vii)) in the reactor
solution,
hereafter "R2 (vii) (ppm)". The upper limit on R2 (vii) (ppm) may be about 10
ppm, in
some cases about 8 ppm and in other cases about 6 ppm. The lower limit on R2
(vii)
(ppm) in some cases may be about 0.5 ppm, in other cases about 1 ppm and in
still
other cases about 2 ppm. The (aluminum alkyl)/(metal compound) molar ratio in
reactor 12a, or the (ix)/(vii) molar ratio, is also controlled. The upper
limit on the
(aluminum alkyl)/(metal compound) molar ratio in the reactor may be about 2,
in some
cases about 1.5 and is other cases about 1Ø The lower limit on the (aluminum
alkyl)/(metal compound) molar ratio may be about 0.05, in some cases about
0.075
and in other cases about 0.1. Any combination of the streams employed to
prepare
and deliver the in-line intermediate branching catalyst formulation to R2 may
be
heated or cooled, i.e. streams 10a through 10h (including stream lOg (optional
R3
delivery) discussed below); in some cases the upper temperature limit of
streams 10a
through 10g may be about 90 C, in other cases about 80 C and in still other
cases
about 70 C and; in some cases the lower temperature limit may be about 10 C;
in
.. other cases about 20 C and in still other cases about 30 C.
As shown in Figure 19, if reactors 11a and 12a were operated in a series mode,
the
second exit stream 12c contains the second ethylene interpolymer having
intermediate branching and the first ethylene interpolymer dissolved in
process
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solvent; as well as unreacted ethylene, unreacted a-olefins (if present),
unreacted
hydrogen (if present), active catalysts, deactivated catalysts, catalyst
components and
other impurities (if present). Optionally the second exit stream 12c was
deactivated by
adding a catalyst deactivator A from catalyst deactivator tank 18A forming a
deactivated solution A, stream 12e; in this case, Figure 19 defaults to a dual
reactor
solution process. If the second exit stream 12c was not deactivated the second
exit
stream enters tubular reactor 17. Catalyst deactivator A is discussed below.
If reactors lla and 12a were operated in parallel mode, the second exit stream
12c
contains the second ethylene interpolymer having intermediate branching
dissolved in
process solvent. The second exit stream 12c was combined with stream llg
forming
a third exit stream 12d, the latter contains the second ethylene interpolymer
and the
first ethylene interpolymer dissolved in process solvent; as well as unreacted
ethylene,
unreacted a-olefins (if present), unreacted hydrogen (if present), active
catalyst,
deactivated catalyst, catalyst components and other impurities (if present).
Optionally
the third exit stream 12d was deactivated by adding catalyst deactivator A
from
catalyst deactivator tank 18A forming deactivated solution A, stream 12e; in
this case,
Figure 19 defaults to a dual reactor solution process. If the third exit
stream 12d was
not deactivated the third exit stream 12d enters tubular reactor 17.
The term "tubular reactor" was meant to convey its conventional meaning,
namely a
simple tube; wherein the length/diameter (L/D) ratio is at least 10/1.
Optionally, one or
more of the following reactor feed streams may be injected into tubular
reactor 17;
process solvent 13, ethylene 14 and optional a-olefin 15. As shown in Figure
19,
.. streams 13, 14 and 15 may be combined forming reactor feed stream RF3 and
the
latter was injected into reactor 17. It is not particularly important that
stream RF3 be
formed; i.e. reactor feed streams can be combined in all possible
combinations.
Optionally hydrogen may be injected into reactor 17 through stream 16.
Optionally,
the in-line intermediate branching catalyst formulation may be injected into
reactor 17
via stream10g; i.e. a portion of the in-line intermediate branching catalyst
formulation
enters reactor 12a through stream 10f and the remaining portion enters reactor
17
through stream 10g. Although not shown in Figure 19, an optional process may
be
the injection of stream lOg upstream of reactor 17.
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Figure 19 shows an optional embodiment where reactor 17 was supplied with a
second in-line intermediate branching catalyst formulation produced in a
second
heterogeneous catalyst assembly. The second heterogeneous catalyst assembly
refers to the combination of conduits and flow controllers that include
streams 34a ¨
34f and 34h. The chemical composition of the first and second in-line
intermediate
branching catalyst formulations may be the same, or different. For example,
the
catalyst components ((v) through (ix)) mole ratios and hold-up-times may
differ in the
first and second heterogeneous catalyst assemblies. Relative to the first
heterogeneous catalyst assembly, the second heterogeneous catalyst assembly
was
operated in a similar manner, i.e. the second heterogeneous catalyst assembly
may
be employed to produce a second in-line intermediate branching catalyst
formulation
capable of producing a third ethylene interpolymer having intermediate
branching by
optimizing feed flow rates, feed temperatures and the molar ratios of the
catalyst
components, i.e.: (aluminum alkyl)/(magnesium compound), (chloride compound)/-
(magnesium compound), (alkyl aluminum co-catalyst/(metal compound, and
(aluminum alkyl)/(metal compound). To be more clear: stream 34a contained a
binary
blend of magnesium compound (component (v)) and aluminum alkyl (component
(ix))
in process solvent; stream 34b contained a chloride compound (component (vi))
in
process solvent; stream 34c contained a metal compound (component (vii)) in
process
solvent; stream 34d contained an alkyl aluminum co-catalyst (component (viii))
in
process solvent; and streams stream 34a', 34b', 34c' and 34f' contained
process
solvent. Once prepared, the second in-line intermediate branching catalyst
formulation was injected into reactor 17 through stream 34f; optionally,
additional alkyl
aluminum co-catalyst may be injected into reactor 17 through stream 34h. As
shown
in Figure 19, optionally, 100% of stream 34d, the alkyl aluminum co-catalyst,
was
injected directly into reactor 17 via stream 34h. Optionally, a portion of
stream 34d
was injected directly into reactor 17 via stream 34h and the remaining portion
of
stream 34d injected into reactor 17 via stream 34f. In Figure 19, the first or
the
second heterogeneous catalyst assembly supplies 100% of the catalyst to
reactor 17.
.. Any combination of the streams that comprise the second heterogeneous
catalyst
assembly may be heated or cooled, i.e. streams 34a through 34h; in some cases,
the
upper temperature limit of streams 34a through 34h may be about 90 C, in other
cases about 80 C and in still other cases about 70 C and; in some cases the
lower
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temperature limit may be about 10 C; in other cases about 20 C and in still
other
cases about 30 C.
In reactor 17 a third ethylene interpolymer may, or may not, form. If
embodiments of
the in-line, or batch intermediate branching catalyst formulations disclosed
herein
were employed in reactor 17, the third ethylene interpolymer was characterized
as
having intermediate branching. If a comparative Ziegler-Natta catalyst
formulation
was injected into reactor 17, the third ethylene interpolymer did not contain
intermediate branching. A third ethylene interpolymer will not form if
catalyst
deactivator A was added upstream of reactor 17 via catalyst deactivator tank
18A. A
third ethylene interpolymer will be formed if catalyst deactivator B is added
downstream of reactor 17 via catalyst deactivator tank 18B.
The optional third ethylene interpolymer produced in reactor 17 may be formed
using
a variety of operational modes; with the proviso that catalyst deactivator A
was not
added upstream of reactor 17. Non-limiting examples of operational modes
include:
(a) residual ethylene, residual optional a-olefin and residual active catalyst
entering
reactor 17 via stream 12e react to form the optional third ethylene
interpolymer having
intermediate branching, or; (b) a fresh portion of the first in-line
intermediate branching
catalyst formulation was added to reactor 17 via stream lOg to polymerize
residual
ethylene forming a third ethylene interpolymer having intermediate branching,
or; (c)
fresh ethylene 14, optional process solvent 13 and optional a-olefin 15 were
added to
reactor 17 and the residual active catalyst entering reactor 17 forms the
third ethylene
interpolymer having intermediate branching, or; (d) a fresh portion of the
first in-line
intermediate branching catalyst formulation was added to reactor 17 via stream
10g to
polymerize freshly injected ethylene and optional a-olefin forming the third
ethylene
interpolymer having intermediate branching. Further, in operational modes (b)
and
(d), the first in-line intermediate branching catalyst formulation may be
replaced with a
second in-line intermediate branching catalyst formulation injected into
reactor 17 via
stream 34f. In any one of these operational modes, fresh hydrogen 16 may be
injected into reactor 17 to reduce the molecular weight of the optional third
optional
ethylene interpolymer.
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In series mode, reactor 17 produced a third exit stream 17b containing the
first
ethylene interpolymer, the second ethylene interpolymer and optionally the
third
ethylene interpolymer. As shown in Figure 19, catalyst deactivator B may be
added to
the third exit stream 17b via catalyst deactivator tank 18B producing a
deactivated
solution B, stream 19; with the proviso that catalyst deactivator B was not
added if
catalyst deactivator A was added upstream of reactor 17. Deactivated solution
B may
also contain unreacted ethylene, unreacted a-olefin, unreacted hydrogen and
impurities if present. As indicated above, if catalyst deactivator A was
added,
deactivated solution A (stream 12e) exits tubular reactor 17 as shown in
Figure 19.
In parallel mode operation, reactor 17 produced a fourth exit stream 17b
containing
the first ethylene interpolymer, the second ethylene interpolymer and
optionally a third
ethylene interpolymer. As indicated above, in parallel mode, stream 12d was
the third
exit stream. As shown in Figure 19, in parallel mode, catalyst deactivator B
was
added to the fourth exit stream 17b via catalyst deactivator tank 18B
producing a
deactivated solution B, stream 19; with the proviso that catalyst deactivator
B was not
added if catalyst deactivator A was added upstream of reactor 17.
In Figure 19, deactivated solution A (stream 12e) or B (stream 19) passed
through
pressure let down device 20, heat exchanger 21 and a passivator was added via
tank
22 forming a passivated solution 23; the passivator was described below. The
passivated solution passed through pressure let down device 24 and entered a
first
vapor/liquid separator 25. Hereinafter, "V/L" is equivalent to vapor/liquid.
Two
streams were formed in the first V/L separator: a first bottom stream 27
comprising a
solution rich in ethylene interpolymers and; a first gaseous overhead stream
26
comprising ethylene, process solvent, optional a-olefins, optional hydrogen,
oligomers
and light-end impurities if present.
The first bottom stream entered a second V/L separator 28. In the second V/L
separator two streams were formed: a second bottom stream 30 comprising a
solution
that was richer in ethylene interpolymer and leaner in process solvent
relative to the
first bottom stream 27, and; a second gaseous overhead stream 29 comprising
process solvent, optional a-olefins, ethylene, oligomers and light-end
impurities if
present.
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The second bottom stream 30 flowed into a third V/L separator 31. In the third
V/L
separator two streams were formed: a product stream 33 comprising an ethylene
interpolymer product, deactivated catalyst residues and less than 5 weight %
of
residual process solvent, and; a third gaseous overhead stream 32 comprised
essentially of process solvent, optional a-olefins and light-end impurities if
present.
Embodiments also include the use of one or more V/L separators operating at
reduced pressure, i.e. the operating pressure is lower than atmospheric
pressure
and/or embodiments where heat is added during the devolitization process, i.e.
one or
more heat exchangers are employed upstream of, or within, one or more of the
V/L
separators. Such embodiments facilitate the removal of residual process
solvent and
comonomer such that the residual volatiles in ethylene interpolymer products
are less
than 500 ppm.
Product stream 33 proceeded to polymer recovery operations. Non-limiting
examples
of polymer recovery operations included one or more gear pump, single screw
extruder or twin screw extruder that forced the molten ethylene interpolymer
product
through a device to form pellets. Embodiments include the use of a
devolatilizing
extruder, where residual process solvent and optional a-olefin may be removed
such
that the volatiles in the ethylene interpolymer product is less than 500 ppm.
Once
pelletized the solidified ethylene interpolymer product is typically
transported to a
product silo.
The first, second and third gaseous overhead streams shown in Figure 19
(streams
26, 29 and 32, respectively) may be sent to a distillation operation where
solvent,
ethylene and optional a-olefin were separated for recycling, or; the first,
second and
third gaseous overhead streams may be recycled to the reactors, or; a portion
of the
first, second and third gaseous overhead streams may be recycled to the
reactors and
the remaining portion sent to the distillation operation.
Solution Polymerization Process Batch Catalyst Formulation
An additional embodiment includes a process to manufacture an ethylene
interpolymer product having intermediate branching, wherein a batch
intermediate
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branching catalyst formulation was employed as illustrated in Figure 20. It
being
understood that the arrangement of, or number of vessels shown in Figure 20
are not
limiting. To maintain a consistent lexicon in this disclosure CSTR reactor 112
in
Figure 20 was referred to as the second reactor, or R2, and this reactor
produced a
.. second ethylene interpolymer; and tubular reactor 117 was referred to as
the third
reactor or R3 and this reactor produced an optional third ethylene
interpolymer.
Referring to Figure 20: process solvent was injected into reactor 112 (reactor
R2) and
tubular reactor 117 (reactor R3) via streams 106 and 113, respectively;
ethylene was
injected into reactors 112 and 117 via streams 107 and 114, respectively; cc-
olefin(s)
were injected into reactors 112 and 117 via streams 108 and 115, respectively;
and
optional hydrogen was injected into reactors 112 and 117 via streams 109 and
116,
respectively. Figure 20 shows a reactor 112 with stirring assembly 112b. In
Figure
20, a first batch heterogeneous catalyst assembly, i.e. vessels and streams
60a
through 60e, was employed to produce a first batch intermediate branching
catalyst
formulation within reactor 112. Vessel 60a contained a solution or slurry of a
first
batch intermediate branching procatalyst in process solvent and vessel 60c
contained
a solution of alkyl aluminum co-catalyst in process solvent. A batch
intermediate
branching catalyst formulation or a batch intermediate branching procatalyst
.. formulation was injected into reactor 112 via stream 60e and a second
ethylene
interpolymer having intermediate branching was formed in reactor 112. The
synthesis
of an embodiment of the batch intermediate branching procatalyst formulation
was
fully described below; process solvent was used to pump the batch intermediate
branching procatalyst formulation to procatalyst storage tank 60a. Tank 60a
may, or
may not, be agitated. Storage tank 60c contained an alkyl aluminum co-
catalyst; non-
limiting examples of suitable alkyl aluminum co-catalysts were described in
this
disclosure. A batch intermediate branching catalyst formulation stream 60e was
formed by mixing the batch intermediate branching procatalyst formulation
stream 60b
with alkyl aluminum co-catalyst stream 60d; optionally, prior to reactor
injection
.. additional process solvent may be added via stream 60e'. Stream 60e was
injected
into reactor 112 where the second ethylene interpolymer having intermediate
branching was formed; Embodiments include the following operational modes: (a)
100% of the alkyl aluminum co-catalyst was injected directly into reactor 112
through
stream 60g and the batch intermediate branching procatalyst formulation was
injected
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directly into reactor 112 through stream 60e, or; (b) a portion of the alkyl
aluminum co-
catalyst was injected into reactor 12a via stream 60g and the remaining
portion
passing through stream 60d was combined with stream 60b to form the batch
intermediate branching catalyst formulation in stream 60e.
As shown in Figure 20, additional optional embodiments include: (a) injecting
the
batch intermediate branching procatalyst formulation into tubular reactor 117
through
stream 60f, or; (b) injecting the batch intermediate branching catalyst
formulation into
tubular reactor 117 through stream 60f. In the case of option (a), 100% of the
alkyl
aluminum co-catalyst was injected directly into reactor 117 via stream 60h. An
additional embodiment included the injection of a portion of the alkyl
aluminum co-
catalyst through stream 60f and the remaining portion flows through stream
60h. Any
combination of vessels or streams 60a through 60h may be heated or cooled.
Employing the first batch intermediate branching catalyst formulation in
reactor 117
produced a third ethylene interpolymer characterized as having intermediate
branching.
Figure 20 illustrates further embodiments were a second heterogeneous catalyst
assembly, i.e. vessels and streams 90a through 90f, may be employed. The
second
heterogeneous catalyst assembly allows one to: employ a second batch
intermediate
catalyst formulation in reactor 117 to synthesize a third ethylene
interpolymer having
intermediate branching; or employ a comparative batch ZN catalyst formulation
in
reactor 117 to synthesize a third ethylene interpolymer that does not have
intermediate branching. This disclosure also contemplates the use of a
heterogeneous catalyst formulation in reactor 117 that produces a third
ethylene
interpolymer that does not contain intermediate branching; for example by
loading a
comparative batch Ziegler-Natta catalyst formulation into vessel 90a.
Once prepared the second batch intermediate branching procatalyst was pumped
to
procatalyst storage tank 90a using process solvent. Tank 90a may, or may not,
be
agitated. Storage tank 90c contained an alkyl aluminum co-catalyst. A batch
intermediate branching catalyst formulation stream 90e was formed by combining
the
second batch intermediate branching procatalyst stream 90b with alkyl aluminum
co-
catalyst stream 90d; optionally additional process solvent may be added to
stream
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90e via stream 90e'. Stream 90e was injected into reactor 117, wherein a third
ethylene interpolymer having intermediate branching was formed. Figure 20
includes
additional embodiments where: (a) the batch intermediate branching procatalyst
was
injected directly into reactor 117 through stream 90e and the procatalyst was
activated
-- inside reactor 117 by injecting 100% of the aluminum co-catalyst directly
into rector
117 via stream 90f, or; (b) a portion of the aluminum co-catalyst flowed
through
stream 90e with the remaining portion flowing through stream 90f. Any
combination of
tanks or streams 90a through 90f may be heated or cooled. The first and second
intermediate branching procatalyst formulations may be the same, or different.
The time between the addition of the alkyl aluminum co-catalyst and the
injection of
the first batch intermediate branching catalyst formulation into reactor 112
was
controlled; i.e. HUT-4 (the fourth Hold-Up-Time). Referring to Figure 20, HUT-
4 was
the time for stream 60d to intermix and equilibrate with stream 60b to form
the first
batch intermediate branching catalyst formulation prior to injection into
reactor 112 via
in stream 60e; optionally this batch intermediate branching catalyst
formulation may
be injected into reactor 117 via stream 60f. The upper limit on HUT-4 may be
about
300 seconds, in some cases about 200 seconds and in other cases about 100
seconds. The lower limit on HUT-4 may be about 0.1 seconds, in some cases
about
lseconds and in other cases about 10 seconds. The second heterogeneous
catalyst
assembly was operated in a similar manner, i.e. the HUT-4 (time for stream 90d
to
intermix and equilibrate with stream 90b to form the second batch intermediate
branching catalyst formulation prior to injection into reactor 112 via in
stream 90e) was
controlled; where HUT-4 varied from about 0.1 to 300 seconds.
The quantity of batch intermediate branching procatalyst formulation or batch
intermediate branching catalyst formulation added to reactor 112 was expressed
as
132 batch (vii) (ppm)', i.e. the parts-per-million (ppm) of metal compound, or
component (vii), in the reactor solution, as shown in Table la. The upper
limit on R2
batch (vii) may be about 10 ppm, in some cases about 8 ppm and in other cases
about 6 ppm. The lower limit on R2 batch (vii) may be about 0.1 ppm, in some
cases
about 0.2 ppm and in other cases about 0.5 ppm. The quantity of the alkyl
aluminum
co-catalyst added to reactor 112 was optimized to produce an efficient
catalyst; this
was accomplished by adjusting the (alkyl aluminum co-catalyst)/(metal
compound)
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molar ratio, i.e. `R2 batch (viii)/(vii) (mol ratio)' as shown in Table la.
The upper limit
on R2 batch (viii)/(vii) may be about 10, in some cases about 8.0 and is other
cases
about 6Ø The lower limit on R2 batch (viii)/(vii) may be 0.5, in some cases
about
0.75 and in other cases about 1.
Referring to Figure 20, the batch intermediate branching catalyst formulation
in exit
stream 112c may be deactivated upstream of reactor 117 by adding a catalyst
deactivator A via deactivator storage tank 118A to form a deactivated solution
A
(stream 112e); in this case deactivated solution A exits reactor 17 and
proceeds to
pressure let down device 120. Optionally, exit stream 112c enters reactor 117
(i.e.
catalyst deactivator A was not added): in this case, a wide variety of
catalyst
formulation may, or may not, be added to reactor 117 and stream 117b exits
reactor
117; stream 117b was then deactivated downstream of reactor 117 by adding a
catalyst deactivator B via deactivator storage tank 118B to form a deactivated
solution
B (stream 119). Deactivated solution B then enters pressure let down device
120.
Deactivated solution A or B was then passed through heat exchanger 121 and a
passivator was added via passivator tank 122 forming a passivated solution
123. The
remaining vessels 124, 125, 128 and 131 and streams 126, 127, 129, 130, 132
and
133 and associated process conditions have been described previously; to be
more
clear, these vessels and streams were equivalent to vessels 24, 25, 28 and 31,
respectively, and the streams 26, 27, 29, 30, 32 and 33, respectively,
described
above. Ethylene interpolymer product stream 133 proceeded to polymer recovery
and
was processed as described above.
The quantity of batch intermediate branching procatalyst produced and/or the
size of
procatalyst storage tanks 60a and 90a was not particularly important. However,
a
large quantity of procatalyst allows one to operate the continuous solution
polymerization plant for an extended period: the upper limit on this time in
some cases
may be about 3 months, in other cases for about 2 months and in still other
cases for
about 1 month; the lower limit on this time in some cases may be about 1 day,
in other
cases about 1 week and in still other cases about 2 weeks.
Additional Solution Polymerization Parameters
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In embodiments of the continuous solution polymerization process that produced
an
intermediately branched ethylene interpolymer a variety of solvents may be
used as
the 'process solvent'; non-limiting examples include linear, branched or
cyclic C5 to
C12 alkanes. Non-limiting examples of a-olefins include 1-propene, 1-butene, 1-
pentene, 1-hexene, 1-octene, 1-nonene and 1-decene. Suitable catalyst
component
solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of
aliphatic catalyst component solvents include linear, branched or cyclic C5-12
aliphatic
hydrocarbons, e.g. pentane, methyl pentane, hexane, heptane, octane,
cyclohexane,
methylcyclohexane, hydrogenated naphtha or combinations thereof. Non-limiting
examples of aromatic catalyst component solvents include benzene, toluene
(methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-
dinnethylbenzene), 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.
Reactor feed streams (solvent, monomer, a-olefin, hydrogen, catalyst
formulation etc.)
must be essentially free of catalyst deactivating poisons; non-limiting
examples of
poisons include trace amounts of oxygenates such as water, fatty acids,
alcohols,
ketones and aldehydes. Such poisons are removed from reactor feed streams
using
standard purification practices; non-limiting examples include molecular sieve
beds,
alumina beds and oxygen removal catalysts for the purification of solvents,
ethylene
and a-olefins, etc.
Referring to Figures 19 and 20 any combination of the reactor feed streams may
be
heated or cooled: for example, reactor lla feed streams 1 ¨ 4 (in Figure 19).
The
upper limit on reactor feed stream temperatures may be 90 C; in other cases 80
C
and in still other cases 70 C. The lower limit on reactor feed stream
temperatures
may be 20 C; in other cases 35 C and in still other cases 50 C. Any
combination of
the streams feeding tubular reactors 17 and 117 may be heated or cooled; i.e.
streams 13 ¨ 16 and 113-116, respectively. In some cases, tubular reactor feed
streams were tempered, i.e. the tubular reactor feed streams were heated to at
least
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above ambient temperature. The upper temperature limit on the tubular reactor
feed
streams in some cases was 200 C, in other cases 170 C and in still other cases
140 C; the lower temperature limit on the tubular reactor feed streams in some
cases
was 60 C, in other cases 90 C and in still other cases 120 C; with the proviso
that the
temperature of the tubular reactor feed streams are lower than the temperature
of the
process stream that enters the tubular reactor.
The operating temperature of the polymerization reactors can vary over a wide
range.
For example, the upper limit on reactor temperatures in some cases was 300 C,
in
other cases 280 C and in still other cases 260 C; and the lower limit in some
cases
was 80 C, in other cases 100 C and in still other cases 125 C. In Figure 19,
the
second reactor, reactor 12a (R2), was operated at a higher temperature than
the first
reactor lla (R1). The maximum temperature difference between these two
reactors
TRix
) in some cases was 120 C, in other cases 100 C and in still other cases
80 C; the minimum (TR2 - TR1) in some cases was 1 C, in other cases 5 C and in
still
other cases 10 C. The optional tubular reactor, reactors 17 and 117 (also
referred to
as R3) in Figure 19 and 20, respectively, was operated in some cases 100 C
higher
than R2; in other cases 60 C higher than R2, in still other cases 10 C higher
than R2
and in alternative cases 0 C higher, i.e. the same temperature as R2. The
temperature within optional R3 may increase along its length. The maximum
temperature difference between the inlet and outlet of R3 in some cases was
100 C,
in other cases 60 C and in still other cases 40 C. The minimum temperature
difference between the inlet and outlet of R3 was in some cases may be 0 C, in
other
cases 3 C and in still other cases 10 C. In some cases R3 was operated an
adiabatic
fashion and in other cases R3 was heated.
The pressure in the polymerization reactors should be high enough to maintain
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. 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
was 45 MPag, in other cases 30 MPag and in still other cases 20 MPag; and the
lower
limit in some cases was 3 MPag, in other some cases 5 MPag and in still other
cases
7 MPag. Prior to entering the first V/L separator, deactivated solution A or
deactivated
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solution B may have a maximum temperature in some cases of 300 C, in other
cases
290 C and in still other cases 280 C; the minimum temperature may be in some
cases
150 C, in other cases 200 C and in still other cases 220 C. Immediately prior
to
entering the first V/L separator, deactivated solution A, deactivated solution
B or the
passivated solution in some cases may have a maximum pressure of 40 MPag, in
other cases 25 MPag and in still cases 15 MPag; the minimum pressure in some
cases may be 1.5 MPag, in other cases 5 MPag and in still other cases 6 MPag.
The first V/L separator (vessels 25 and 125 in Figures 19 and 20,
respectively) may
be operated over a relatively broad range of temperatures and pressures. For
example, the maximum operating temperature of the first V/L separator in some
cases
was 300 C, in other cases 285 C and in still other cases 270 C; the minimum
operating temperature in some cases was 100 C, in other cases 140 C and in
still
other cases 170 C. The maximum operating pressure of the first V/L separator
in
some cases was 20 MPag, in other cases 10 MPag and in still other cases 5
MPag;
the minimum operating pressure in some cases was 1 MPag, in other cases 2 MPag
and in still other cases 3 MPag.
The second V/L separator (vessels 28 and 128 in Figures 19 and 20,
respectively)
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 was 300 C, in other cases 250 C and in still other cases 200 C; the
minimum
operating temperature in some cases was 100 C, in other cases 125 C and in
still
other cases 150 C. The maximum operating pressure of the second V/L separator
in
some cases was 1000 kPag, in other cases 900 kPag and in still other cases
800kPag; the minimum operating pressure in some cases was 10 kPag, in other
cases 20 kPag and in still other cases 30 kPag.
The third V/L separator (vessels 31 and 131 in Figures 19 and 20,
respectively) may
be operated over a relatively broad range of temperatures and pressures. For
example, the maximum operating temperature of the third V/L separator in some
cases was 300 C, in other cases 250 C, and in still other cases 200 C; the
minimum
operating temperature in some cases may be 100 C, in other cases 125 C and in
still
other cases 150 C. The maximum operating pressure of the third V/L separator
in
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some cases was 500 kPag, in other cases 150 kPag and in still other cases 100
kPag;
the minimum operating pressure in some cases was 1 kPag, in other cases 10
kPag
and in still other cases 25 kPag.
Embodiments of the continuous solution polymerization process shown in Figures
19
and 20 show three V/L separators. However, continuous solution polymerization
embodiments may include configurations comprising at least one V/L separator.
Any reactor shape or design may be used for solution polymerization reactors,
i.e.
reactors 1 1 a (R1), 12a (R2) and 17 (R3) in Figure 19; and reactors 112 (R2)
and 117
(R3) in Figure 20; non-limiting examples include unstirred or stirred
spherical,
cylindrical or tank-like vessels, as well as tubular reactors or recirculating
loop
reactors. At commercial scale the maximum volume of R1 in some cases may be
about 20,000 gallons (about 75,710 L), in other cases about 10,000 gallons
(about
37,850 L) and in still other cases about 5,000 gallons (about 18,930 L). At
commercial
scale the minimum volume of R1 in some cases may be about 100 gallons (about
379
L), in other cases about 500 gallons (about 1,893 L) and in still other cases
about
1,000 gallons (about 3,785 L). At commercial scale the maximum volume of R2 in
some cases may be about 120,000 gallons (about 454,000 L), in other cases
about
60,000 gallons (about 227,000 L) and in still other cases about 30,000 gallons
(about
114,000 L).
At commercial scale the minimum volume of R2 in some cases may be about 6000
gallons (about 22,700 L), in other cases about 2,000 gallons (about 7,570 L)
and in
still other cases about 200 gallons (about 757 L). At pilot plant scales
reactor volumes
were typically much smaller, for example the volume of R1 at pilot scale could
be less
than about 2 gallons (less than about 7.6 L). In the case of continuously
stirred tank
reactors the stirring rate may vary over a wide range; in some cases from
about 10
rpm to about 2000 rpm, in other cases from about 100 to about 1500 rpm and in
still
other cases from about 200 to about 1300 rpm. In this disclosure the volume of
R3,
the tubular reactor, was 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.
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The 'average reactor residence time', a well-known parameter in the chemical
engineering art, was defined by the first moment of the reactor residence time
distribution; the reactor residence time distribution was a probability
distribution
function that describes the amount of time that a fluid element spends inside
the
reactor. The average reactor residence time varied widely depending on process
flow
rates and reactor mixing, design and capacity. The upper limit on the average
reactor
residence time of the solution in R1 in some cases may be 600 seconds, in
other
cases 360 seconds and in still other cases 180 seconds. The lower limit on the
average reactor residence time of the solution in R1 in some cases may be 10
seconds, in other cases 20 seconds and in still other cases 40 seconds. The
upper
limit on the average reactor residence time of the solution in R2 in some
cases may
be 720 seconds, in other cases 480 seconds and in still other cases 240
seconds.
The lower limit on the average reactor residence time of the solution in R2 in
some
cases may be 10 seconds, in other cases 30 seconds and in still other cases 60
seconds. The upper limit on the average reactor residence time of the solution
in R3
in some cases may be 600 seconds, in other cases 360 seconds and in still
other
cases 180 seconds. The lower limit on the average reactor residence time of
the
solution in R3 in some cases may be 1 second, in other cases 5 seconds and in
still
other cases 10 seconds.
Optionally, additional reactors (e.g. CSTRs, loops or tubes, etc.) could be
added to the
continuous solution polymerization process embodiments shown in Figure 19. In
this
disclosure, the number of reactors was not particularly important; with the
proviso that
the continuous solution polymerization process comprises at least one reactor
that
employs an intermediate branching catalyst formulation that produces an
ethylene
interpolymer product having intermediate branching.
In operating the continuous solution polymerization process embodiments shown
in
Figure 19 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 was
called
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 ESR1+
ESR2+
ESR3 = 100%. This was accomplished by adjusting the ethylene flow rates in the
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following streams: stream 2 (R1), stream 7 (R2) and stream 14 (R3). The upper
limit
on ESR1 in some cases was about 60%, in other cases about 55% and in still
other
cases about 50%; the lower limit on ESR1 in some cases was about 5%, in other
cases
about 10% and in still other cases about 20%. The upper limit on ESR2 in some
cases
was about 90%, in other cases about 80% and in still other cases about 70%;
the
lower limit on ESR2 in some cases was about 20%, in other cases about 30% and
in
still other cases about 40%. The upper limit on ESR3 in some cases was about
30%,
in other cases about 25% and in still other cases about 20%; the lower limit
on ESR3 in
some cases was 0%, in other cases about 5% and in still other cases about 10%.
Similarly, in Figure 20 the ethylene may be apportioned between R2 (reactor
112) and
R3 (reactor 117); where ESR2+ ESR3 = 100%.
In operating the continuous solution polymerization process embodiments shown
in
Figures 19 and 20 the ethylene concentration in each reactor was also
controlled.
The ethylene concentration in R1, i.e. ECR1, was defined as the weight of
ethylene in
reactor 1 divided by the total weight of everything added to reactor 1; ECR2
and ECR3
were defined similarly. Ethylene concentrations in the reactors (EC R1 or ECR2
or
ECR3) in some cases varied from about 7 weight percent (wt %) to about 25 wt
%, in
other cases from about 8 wt % to about 20 wt % and in still other cases from
about 9
.. wt % to about 17 wt %.
In operating the continuous solution polymerization process embodiments shown
in
Figures 19 and 20 the total amount of ethylene converted in each reactor was
monitored. The term `0R1' referred to the percent of the ethylene added to R1
that
was converted into a first ethylene interpolymer by the catalyst formulation.
Similarly,
QR2 and QR3 represented the percent of the ethylene added to R2 and R3 that
was
converted into the second and third ethylene interpolymer, respectively.
Ethylene
conversions varied significantly depending on a variety of process conditions,
e.g.
catalyst concentration, catalyst formulation, impurities and poisons. The
upper limit on
both QR1 and QR2 in some cases was about 99%, in other cases about 95% and in
still
other cases about 90%; the lower limit on both QR1 and 0R2 in some cases was
about
65%, in other cases about 70% and in still other cases about 75%. The upper
limit on
QR3 in some cases was about 99%, in other cases about 95% and in still other
cases
about 90%; the lower limit on 0R3 in some cases was 0%, in other cases about
5%
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and in still other cases about 10%. The term "QT" represented the total or
overall
ethylene conversion across the entire continuous solution polymerization
plant; i.e. QT
= 100 x [weight of ethylene in the interpolymer product]/gweight of ethylene
in the
interpolymer productMweight of unreacted ethylene]). The upper limit on QT in
some
cases was about 99%, in other cases about 95% and in still other cases about
90%;
the lower limit on QT in some cases was about 75%, in other cases about 80%
and in
still other cases about 85%.
Referring to Figures 19, a-olefin was added to the continuous solution
polymerization
process; and was proportioned or split between R1, R2 and R3. This operational
variable was called the Comonomer (a-olefin) Split (CS), i.e. 'CSR1', `CSR2'
and `CSR3'
referred to the weight percent of a-olefin comonomer that was injected in R1,
R2 and
R3, respectively; with the proviso that CSR1+ csR2 CSR3 = 100%. This was
accomplished by adjusting a-olefin flow rates in the following streams: stream
3 (R1),
stream 8 (R2) and stream 15 (R3). The upper limit on CSR1 in some cases was
100%
(i.e. 100% of the a-olefin was injected into R1), in other cases about 95% and
in still
other cases about 90%. The lower limit on CSR1 in some cases was 0% (i.e. the
first
ethylene interpolymer was an ethylene homopolymer), in other cases about 5%
and in
still other cases about 10%. The upper limit on CSR2 in some cases was about
100%
(i.e. 100% of the a-olefin was injected into reactor 2), in other cases about
95% and in
still other cases about 90%. The lower limit on CSR2 in some cases was 0%, in
other
cases about 5% and in still other cases about 10%. The upper limit on CSR3 in
some
cases was 100%, in other cases about 95% and in still other cases about 90%.
The
lower limit on CSR3 in some cases was 0%, in other cases about 5% and in still
other
cases about 10%. Similarly, in Figure 20 the comonomer may be apportioned
between R2 (reactor 112) and R3 (reactor 117); where CSR2+ CSR3 = 100%.
In the continuous polymerization processes described in this disclosure,
polymerization was terminated by adding a catalyst deactivator. Embodiments in
Figure 19 shows catalyst deactivation occurring either: (a) upstream of
tubular reactor
17 by adding a catalyst deactivator A from catalyst deactivator tank 18A, or;
(b)
downstream of tubular reactor 17 by adding a catalyst deactivator B from
catalyst
deactivator tank 18B. Similarly, Figure 20 shows catalyst deactivation
occurring
either: (a) upstream of tubular reactor 117 by adding a catalyst deactivator A
from
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catalyst deactivator tank 118A, or; (b) downstream of tubular reactor 117 by
adding a
catalyst deactivator B from catalyst deactivator tank 118B. Catalyst
deactivator tanks
may contain neat (100%) catalyst deactivator, a solution of catalyst
deactivator in a
solvent, or a slurry of catalyst deactivator in a solvent. The chemical
composition of
catalyst deactivator A and B may be the same, or different. Non-limiting
examples of
suitable solvents included linear or branched C5 to C12 alkanes. In this
disclosure,
how the catalyst deactivator was added was not particularly important. Once
added,
the catalyst deactivator substantially stopped the polymerization reaction by
changing
active catalyst species to inactive forms. Suitable deactivators are well
known in the
art, non-limiting examples include: amines (e.g. U.S. Pat. No. 4,803,259 to
Zboril et
al.); alkali or alkaline earth metal salts of carboxylic acid (e.g. U.S. Pat.
No. 4,105,609
to Machan et al.); water (e.g. U.S. Pat. No. 4,731,438 to Bernier et al.);
hydrotalcites,
alcohols and carboxylic acids (e.g. U.S. Pat. No. 4,379,882 to Miyata); or a
combination thereof (U.S. Pat No. 6,180,730 to Sibtain et al.). In this
disclosure the
quantify of catalyst deactivator added was determined by the following
catalyst
deactivator molar ratio: 0.3 (catalyst deactivator)/((total catalytic
metal)+(alkyl
aluminum co-catalyst)+(aluminum alkyl)) 5. 2.0; where the total catalytic
metal was the
total moles of catalytic metal added to the solution process. The upper limit
on the
catalyst deactivator molar ratio was 2, in some cases 1.5 and in other cases
0.75. The
lower limit on the catalyst deactivator molar ratio was 0.3, in some cases
0.35 and in
still other cases 0.4. In general, the catalyst deactivator was added in a
minimal
amount such that the catalyst was deactivated and the polymerization reaction
was
quenched.
Prior to entering the first V/L separator, a passivator or acid scavenger was
added to
deactivated solution A or B forming a passivated solution, i.e. passivated
solution
streams 23 and 123 shown in Figures 19 and 20, respectively. Passivator tanks
22
and 122 may contain neat (100%) passivator, a solution of passivator in a
solvent, or
a slurry of passivator in a solvent. Non-limiting examples of suitable
solvents include
linear or branched C5 to C12 alkanes. In this disclosure, how the passivator
was
added was not particularly important. Suitable passivators are well-known in
the art,
non-limiting examples included alkali or alkaline earth metal salts of
carboxylic acids
or hydrotalcites. The quantity of passivator added varied over a wide range.
The
quantity of passivator added was determined by the total moles of chloride
compounds added to the solution process, i.e. the chloride compound "compound
(vi)"
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plus the metal compound "compound (vii)" that was used to manufacture the
catalyst
formulation. The upper limit on the (passivator)/(total chlorides) molar ratio
was 15, in
some cases 13 and in other cases 11. The lower limit on the
(passivator)/(total
chlorides) molar ratio was about 5, in some cases about 7 and in still other
cases
about 9. In general, the passivator was added in the minimal amount to
substantially
passivate the deactivated solution.
Ethylene Interpolymer Products
The intermediately branched ethylene interpolymer products of this disclosure
were
characterized by a Non-Comonomer Index Distribution, NCIDI, having values
characterized by Eq.(1a) and Eq.(1b), i.e. Eq.(1b) .s NCIDI s Eq.(1a); and a
first
derivative of NCIDI, dNCIDi , Eq.(2), having values s - 0.0001.
dlogMi
To maintain a consistent lexicon and avoid confusion between various
embodiments
(e.g. Figures 19 and 20) the 'second ethylene interpolymer' in the ethylene
interpolymer product was consistently characterized as having intermediate
branching. It being understood that, in the case of one reactor running one
intermediate branching catalyst formulation, the ethylene interpolymer product
consists of a solitary ethylene interpolymer, i.e. the second ethylene
interpolymer
having intermediate branching.
The disclosed ethylene interpolymer products may consist of two ethylene
interpolymers, i.e. a first and a second ethylene interpolymer where the
second
interpolymer contains intermediate branching and the first ethylene
interpolymer may
or may not contain intermediate branching. The first ethylene interpolymer may
be
produced with a variety of catalyst formulations; including, homogeneous
catalyst
formulations, heterogeneous catalyst formulations or intermediate branching
catalyst
formulations.
The disclosed ethylene interpolymer products may consist of three ethylene
interpolymers, i.e. a first, a second and a third ethylene interpolymer; the
second
ethylene interpolymer contains intermediate branching; while the first and
third
ethylene interpolymers may or may not contain intermediate branching. The
first and
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third ethylene interpolymers were independently synthesized using a variety of
catalyst formulations; including homogeneous catalyst formulations,
heterogeneous
catalyst formulations or an intermediate branching catalyst formulations.
The disclosed ethylene interpolymer products may consist of more than three
ethylene
interpolymers, e.g. a first, a second, a third and a fourth ethylene
interpolymer (etc.);
again, the second interpolymer contains intermediate branching; while the
first, third
and fourth (etc.) ethylene interpolymers may or may not contain intermediate
branching. The first, third and fourth (etc.) ethylene interpolymers were
independently
synthesized using a variety of catalyst formulations; including homogeneous
catalyst
formulations, heterogeneous catalyst formulations or intermediately branching
catalyst
formulations.
The second ethylene interpolymer was also characterized as having no long
chain
branching (or an undetectable level) as characterized by a Long Chain
Branching
Factor (LCBF) value <0.001. The first, the third, the fourth (etc.) ethylene
interpolymers may or may not contain long chain branching; if present, long
chain
branching was characterized by a LCBF value 0.001.
Ethylene interpolymer products have a density (al); where the superscript f '
refers to
the 'final' density, i.e. the final product may comprise several ethylene
interpolymers.
In some cases, the upper limit on density (Gf) may be about 0.965 g/cm3, in
other
cases about 0.955 g/cm3 and in still other cases about 0.945 g/cm3; while the
lower
density limit (Gf) may be about 0.862 g/cm3, in other cases about 0.875 g/cm3,
and; in
still other cases about 0.885 g/cm3. In this disclosure, the symbol '(52'
refers to the
density of the second ethylene interpolymer. The lower limit on the density of
the
second ethylene interpolymer (G2) may be 0.890 g/cm3, in other cases 0.900
g/cm3
and in still other cases 0.910 g/cm3; and upper limit on density of the second
ethylene
interpolymer may be about 0.965 g/cm3, in other cases about 0.955 g/cm3 and in
still
other cases about 0.945 g/cm3.
The comonomer to ethylene mole ratio in the second reactor (R2) was used to
control
density, i.e. ((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; while the
lower limit
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on ((a-olefin)/(ethylene))R2 may be 0; in other cases about 0.25 and in still
other cases
about 0.5.
Ethylene interpolymer products having intermediate branching may have an upper
limit on melt index (I2f) of 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 ethylene interpolymer products (12f) 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 blends the upper limit on the melt index of the second ethylene
interpolymer (122)
having intermediate branching may be about 1000 dg/min, in some cases about
750
dg/min, in other cases about 500 dg/min and in still other cases about 200
dg/min; the
lower limit on the melt index of the second ethylene interpolymer (122) having
intermediate branching may be about 0.001 dg/min; in some cases about 0.005
dg/min, in other cases about 0.01 dg/min and in still other cases about 0.05
dg/min.
The hydrogen content in R2 was used to control melt index of the second
ethylene
interpolymer, i.e. H2R2 (ppm); H2R2 (ppm) may range from about 50 ppm to 0
ppm, in
other cases from about 25 ppm to 0 ppm, in still other cases from about 10 to
0 and or
from about 2 ppm to 0 ppm.
Methods to determine the CDBI50 (Composition Distribution Branching Index) of
an
ethylene interpolymer are well known to those skilled in the art. The CDBI50,
expressed as a percent, is defined as the percent of the ethylene interpolymer
whose
.. comonomer composition is within 50% of the median comonomer composition.
Ethylene interpolymer products having intermediate branching may have an upper
limit on CDBI50 of about 98%, in other cases about 90% and in still other
cases about
85%; while the lower limit on the CDBI50 of an ethylene interpolymer product
may be
about 10%, in other cases about 15% and in still other cases about 20%. The
second
ethylene interpolymer having intermediate branching may have a CDB150that
ranges
from: an upper CDBI5olimit of about 70%, in other cases about 65% and in still
other
cases about 60%; and a lower CDBI50 limit of about 20%, in other cases about
45%
and in still other cases about 55%.
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The upper limit on the Mw/Mn of the ethylene interpolymer product having
intermediate
branching 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 ethylene interpolymer product may be 2.0,
in other
cases about 2.2 and in still other cases about 2.4. The Mw/Mn of second
ethylene
interpolymer having intermediate branching may be characterized by: an upper
Mw/Mn
limit of about 5.0, in other cases about 4.5 and in still other cases about
4.0; and a
lower Mw/Mn limit of about 2.2, in other cases about 2.4 and in still other
cases about
2.6.
In the case of ethylene interpolymer products containing more than one
ethylene
interpolymer; the upper limit on the weight percent (wt%) of the second
ethylene
interpolymer having intermediate branching in the ethylene interpolymer
product may
be about 99 wt%, in other cases about 95 wt% and in still other cases about 90
wt%.
The lower limit on the wt % of the second ethylene interpolymer in the
ethylene
interpolymer product may be about 10 wt%; in other cases about 15 wt% and in
still
other cases about 20 wt%. The specific volume blending rule was used to
calculate
the final density (af) of a multicomponent ethylene interpolymer product; e.g.
in the
case of a blend of two ethylene interpolymers the final blend density (01) was
af =
Awti /co +wt2//)a2k ,=
where wti and wt2 represent weight fractions of the first and second
ethylene interpolymer, respectively, and the following melt index blending
rule was
used to the calculate blend melt index, log(I2f ). wt1log(121)+wt2log(122).
Ethylene interpolymer products containing intermediate branching contain
catalyst
residues that reflect the chemical compositions of the catalyst formulation
used. In the
case of the second ethylene interpolymer having intermediate branching,
catalyst
residues were quantified by the parts per million of catalytic metal
originating from
'component (vii)' in the second ethylene interpolymer; in this disclosure this
metal was
referred to as "metal B". Non-limiting examples of metal B include metals
selected
from Group 4 through Group 8 of the Periodic Table, or mixtures of metals
selected
from Group 4 through Group 8. The upper limit on the ppm of metal B in the
second
ethylene interpolymer having intermediate branching may be about 12 ppm, in
other
cases about 10 ppm and in still other cases about 8 ppm. The lower limit on
the ppm
of metal B in the ethylene interpolymer having intermediate branching may be
about
0.5 ppm, in other cases about 1 ppm and in still other cases about 2 ppm.
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The ethylene interpolymer product may also contain (optionally) additional
catalytic
metals. For example, as described below, a metal A used to synthesize a first
ethylene interpolymer and/or a metal C used to synthesize a third ethylene
interpolymer. Catalytic metals A, B and C may be the same or different. In
this
disclosure the term "total catalytic metal" was equivalent to the sum of
catalytic metals
A+B+C. The upper and lower limits on catalytic metal A, or metal B or metal C
in the
ethylene interpolymer product can be calculated from the weight fractions of
the first,
the second and the third ethylene interpolymer, respectively, in the ethylene
interpolymer product; given the disclosed upper and lower limits on the
respective
catalytic metal in the first, second and third ethylene interpolymer.
First Ethylene Interpolymer
In this disclosure, the term 'first ethylene interpolymer' refers to an
ethylene
interpolymer synthesized in a first reactor. This disclosure described several
embodiments of intermediately branched ethylene interpolymer products; and the
first
ethylene interpolymer may, or may not, be present in the product. If present,
the first
ethylene interpolymer may be an intermediately branched ethylene interpolymer
and
characterized as described above (e.g. via Eq.(1a), Eq.(1b) and Eq.(2), etc.).
If
present, the first ethylene interpolymer may also be produced using a
heterogeneous
catalyst formulation, e.g. a comparative batch Ziegler-Natta catalyst
formulation that
does not produce intermediate branching. If present, the first ethylene
interpolymer
may also be produced using a homogeneous catalyst formulation that does not
produce intermediate branching and may, or may not, produce long chain
branching.
The first ethylene interpolymer may have an upper density limit of about 0.975
g/cm3,
in other cases about 0.965 g/cm3 and in still other cases about 0.955 g/cm3;
while the
lower density may be about 0.855 g/cm3, in other cases about 0.865 g/cm3, and;
in still
.. other cases about 0.875 g/cm3. In this disclosure the symbol `cyl' refers
to the density
of the first ethylene interpolymer. The ((a-olefin)/(ethylene)) ratio in the
first reactor
(R1) was used to control the density of the first ethylene interpolymer.
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The upper limit on the melt index of the first ethylene interpolymer, (121)
may be about
1000 dg/min, in some cases about 750 dg/min; in other cases about 500 dg/min,
and;
in still other cases about 200 dg/min; and the lower limit on the melt index
of the
homogeneous first ethylene interpolymer may be about 0.001 dg/min, in some
cases
about 0.005 dg/min; in other cases about 0.01 dg/min, and; in still other
cases about
0.05 dg/min. The melt index of the first ethylene interpolymer was controlled
by the
amount of hydrogen in R1, i.e. H2R1 (ppm).
The first ethylene interpolymer may, or may not, contain long chain branching
as
characterized by LCBF values. The upper limit on the LCBF of the first
ethylene
interpolymer may be 0.5, in other cases 0.4 and in still other cases 0.3
(dimensionless). The lower limit on LCBF was a homogenous first ethylene
interpolymer that did not chain long chain branching or an undetectable level
of long
chain branching, as characterized by LCBF values < 0.001.
The first ethylene interpolymer may have a CDB150that ranges from: an upper
CDB150
of about 98%, in other cases 95% and in still other cases about 90%; and a
lower
CDB150 of about 20%, in other cases about 45% and in still other cases about
55%.
The upper limit on the Mw/Mn of the first ethylene interpolymer may be about
5.0, in
other cases about 4.5 and in still other cases about 4.0; and the lower limit
on the
Mw/Mn the first ethylene interpolymer may be about 1.7, in other cases about
1.8 and
in still other cases about 1.9.
The first ethylene interpolymer contains catalyst residues that reflect the
chemical
composition of the catalyst formulation used. Catalyst residues were
quantified by the
parts per million of catalytic metal in the first ethylene interpolymer;
hereinafter 'metal
A'. Non-limiting examples of metal A include metals selected from Group 4
through
Group 8 of the Periodic Table, or mixtures of metals selected from Group 4
through
Group 8. The upper limit on the ppm of metal A in the first ethylene
interpolymer may
be about 12.0 ppm, in other cases about 10.0 ppm and in still other cases
about 8.0
ppm. The lower limit on the ppm of metal A in the first ethylene interpolymer
may be
about 0.01 ppm, in other cases about 0.1 ppm and in still other cases about
0.2 ppm.
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The upper limit on the weight percent (wt%) of the first ethylene interpolymer
in the
ethylene interpolymer product may be about 60 wt%, in other cases about 55 wt%
and
in still other cases about 50 wt%. The lower limit on the wt % of the first
ethylene
interpolymer in the ethylene interpolymer product may be 0 wt%; in other cases
about
5 wt% and in still other cases about 10 wt%.
Third Ethylene Interpolymer
In this disclosure, the term 'third ethylene interpolymer' refers to an
ethylene
interpolymer synthesized in a third reactor. This disclosure described several
embodiments of intermediately branched ethylene interpolymer products; and the
third
ethylene interpolymer may, or may not, be present. If present, the third
ethylene
interpolymer may be an intermediately branched ethylene interpolymer and
characterized as described above (e.g. via Eq.(1a), Eq.(1b) and Eq.(2), etc.).
If
present, the third ethylene interpolymer may also be produced using a
heterogeneous
catalyst formulation, e.g. a comparative batch Ziegler-Natta catalyst
formulation that
does not produce intermediate branching. If present, the third ethylene
interpolymer
may also be produced using a homogeneous catalyst formulation that does not
produce intermediate branching and may, or may not, produced long chain
branching.
The upper limit on the density (e) of the third ethylene interpolymer in some
cases
may be about 0.975 g/cm3, in other cases about 0.965 g/cm3 and in still other
cases
about 0.955 g/cm3; while the lower a3 limit may be about 0.855 g/cm3, in other
cases
about 0.865 g/cm3, and in still other cases about 0.875 g/cm3.
The amount of hydrogen added to the third reactor (R3), H2R3 (ppm), may vary
over a
wide range to produce a third ethylene interpolymer having a wide range of
melt
indexes (l23). The upper limit on 123 may be about 10000 dg/min, in other
cases about
5000 dg/min, in still cases about 2000 dg/min, and in other cases about 1000
dg/min;
while the lower limit on 123 may be about 0.1 dg/min, in other cases about 0.2
dg/min,
in still other cases about 0.3 dg/min, and in other cases 0.5 dg/min.
The upper limit on the CDBI50 of the third ethylene interpolymer may be about
98%, in
other cases about 95% and in still other cases about 90%; while the lower
limit on
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CDBI50 of the third ethylene interpolymer may be about 20%, in other cases
about
30% and in still other cases about 40%.
The upper limit on the Mw/Mn of the third ethylene interpolymer may be about
6.0, in
other cases about 5.0 and in still other cases about 4Ø The lower limit on
the Mw/Mn
of the third ethylene interpolymer may be about 1.7, in other cases about 1.8
and in
still other cases about 1.9.
The catalyst residues in the third ethylene interpolymer reflect the chemical
.. composition of catalyst formulation used. In this disclosure, the term
'metal C' refers
to the catalytic metal employed in the catalyst formulation that was used to
synthesize
the third ethylene interpolymer. Non-limiting examples of metal C include
metals
selected from Group 4 through Group 8 of the Periodic Table, or mixtures of
metals
selected from Group 4 through Group 8. Metal C was may be the same or
different
relative to metal A and metal B. The upper limit on the ppm of metal C in the
third
ethylene interpolymer may be about 12 ppm, in other cases about 10 ppm and in
still
other cases about 8 ppm; and the lower limit on the ppm of metal C in the
third
ethylene interpolymer may be about 0.01 ppm, in other cases about 0.1 ppm and
in
still other cases about 0.2 ppm.
The upper limit on the weight percent (wt%) of the optional third ethylene
interpolymer
in the ethylene interpolymer product may be about 30 wt%, in other cases about
25
wt% and in still other cases about 20 wt%. The lower limit on the wt% of the
optional
third ethylene interpolymer in the ethylene interpolymer product may be 0 wt%;
in
other cases about 5 wt% and in still other cases about 10 wt%.
Manufactured Articles
Ethylene interpolymer products having intermediate branching may be converted
into
a wide variety of flexible manufactured articles. Non-limiting examples
include
monolayer or multilayer films. Non-limiting examples of processes to prepare
such
films include blown film processes, double bubble processes, triple bubble
processes,
cast film processes, tenter frame processes and machine direction orientation
(MDO)
processes.
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In the blown film extrusion process an extruder heats, melts, mixes and
conveys a
thermoplastic, or a thermoplastic blend. Once molten, the thermoplastic is
forced
through an annular die to produce a thermoplastic tube. In the case of co-
extrusion,
multiple extruders are employed to produce a multilayer thermoplastic tube.
The
temperature of the extrusion process is primarily determined by the
thermoplastic or
thermoplastic blend being processed, for example the melting temperature or
glass
transition temperature of the thermoplastic and the desired viscosity of the
melt. In
the case of polyolefins, typical extrusion temperatures are from 330 F to 550
F (166 C
to 288 C). Upon exit from the annular die, the thermoplastic tube is inflated
with air,
cooled, solidified and pulled through a pair of nip rollers. Due to air
inflation, the tube
increases in diameter forming a bubble of desired size. Due to the pulling
action of
the nip rollers the bubble is stretched in the machine direction. Thus, the
bubble is
stretched in two directions: the transverse direction (TD) where the inflating
air
increases the diameter of the bubble; and the machine direction (MD) where the
nip
rollers stretch the bubble. As a result, the physical properties of blown
films are
typically anisotropic, i.e. the physical properties differ in the MD and TD
directions; for
example, film tear strength and tensile properties typically differ in the MD
and TD. In
some prior art documents, the terms "cross direction" or "CD" is used; these
terms are
equivalent to the terms "transverse direction" or "TD" used in this
disclosure. In the
blown film process, air is also blown on the external bubble circumference to
cool the
thermoplastic as it exits the annular die. The final width of the film is
determined by
controlling the inflating air or the internal bubble pressure; in other words,
increasing
or decreasing bubble diameter. Film thickness is controlled primarily by
increasing or
decreasing the speed of the nip rollers to control the draw-down rate. After
exiting
the nip rollers, the bubble or tube is collapsed and may be slit in the
machine direction
thus creating sheeting. Each sheet may be wound into a roll of film. Each roll
may be
further slit to create film of the desired width. Each roll of film is further
processed into
a variety of consumer products as described below.
__ 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.
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In the double bubble process a first blown film bubble is formed and cooled,
then the
first bubble is heated and re-inflated forming a second blown film bubble,
which is
subsequently cooled. The ethylene interpolymer products, disclosed herein, are
also
suitable for the triple bubble blown process. Additional film converting
processes,
suitable for the disclosed ethylene interpolymer products, include processes
that
involve a Machine Direction Orientation (MDO) step; for example, blowing a
film or
casting a film, quenching the film and then subjecting the film tube or film
sheet to a
MDO process at any stretch ratio. Additionally, the ethylene interpolymer
product
films disclosed herein are suitable for use in tenter frame processes as well
as other
processes that introduce biaxial orientation.
Depending on the end-use application, the disclosed ethylene interpolymer
products
having intermediate branching may be converted into films that span a wide
range of
thicknesses. Non-limiting examples include, food packaging films where
thicknesses
may range from about 0.5 mil (13 pm) to about 4 mil (102 pm), and; in heavy
duty
sack applications film thickness may range from about 2 mil (51pm) to about 10
mil
(254 pm).
Intermediately branched ethylene interpolymer products may be used in
monolayer
films; where the monolayer comprises one or more of the disclosed ethylene
interpolymer products having intermediate branching and optionally one or more
ethylene polymers and/or one or more polyolefins. The lower limit on the
weight
percent of intermediately branched ethylene interpolymer 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 intermediately branched
ethylene
interpolymer product in the monolayer film may be 100 wt%, in other cases
about 90
wt% and in still other cases about 70 wt%.
Intermediately branched ethylene interpolymer products may also be used in one
or
more layers of a multilayer film; non-limiting examples of multilayer films
include two,
three, five, seven, nine, eleven or more layers. The disclosed ethylene
interpolymer
products are also suitable for use in processes that employ micro-layering
dies and/or
feedblocks, such processes can produce films having many layers, non-limiting
examples include from 10 to 10,000 layers.
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The thickness of a specific layer (containing one or more intermediately
branched
ethylene interpolymer product(s)) within the 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
one or
more intermediately branched ethylene interpolymer product(s)) within the
multilayer
film may be about 95%, in other cases about 80% and in still other cases about
65%
of the total multilayer film thickness. Each individual layer of a multilayer
film may
contain more than one intermediately branched ethylene interpolymer product;
may
contain one or more ethylene polymer and/or one or more polyolefin.
Additional embodiments include laminations and coatings, where mono or
multilayer
films containing an ethylene interpolymer product having intermediate
branching 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
of
ordinary experience in the art. Frequently, adhesive lamination or extrusion
lamination are used to bond dissimilar materials, non-limiting examples
include the
bonding of a paper web to a thermoplastic web, or the bonding of an aluminum
foil
containing web to a thermoplastic web, or the bonding of two thermoplastic
webs that
are chemically incompatible, e.g. the bonding of an intermediately branched
ethylene
interpolymer product containing web to a polyester or polyamide web. Prior to
lamination, the web containing intermediately branched ethylene interpolymer
product(s) may be monolayer or multilayer. Prior to lamination the individual
webs
may be surface treated to improve the bonding, a non-limiting example of a
surface
treatment is corona treating. A primary web or film may be laminated on its
upper
surface, its lower surface, or both its upper and lower surfaces with a
secondary web.
A secondary web and a tertiary web could be laminated to the primary web;
wherein
the secondary and tertiary webs differ in chemical composition. As non-
limiting
examples, secondary or tertiary webs may include; polyamide, 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
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(SiOx) or aluminum oxide (A10) layer. Multilayer webs (or films) may contain
three,
five, seven, nine, eleven or more layers.
Ethylene interpolymer products having intermediate branching can be used in a
wide
.. range of manufactured articles comprising one or more films (monolayer or
multilayer). Non-limiting examples of such manufactured articles include: food
packaging films (fresh and frozen foods, liquids and granular foods), stand-up
pouches, retortable packaging and bag-in-box packaging; barrier films (oxygen,
moisture, aroma, oil, etc.) and modified atmosphere packaging; light and heavy
duty
shrink films and wraps, collation shrink film, pallet shrink film, shrink
bags, shrink
bundling and shrink shrouds; light and heavy duty stretch films, hand stretch
wrap,
machine stretch wrap and stretch hood films; high clarity films; heavy-duty
sacks;
household wrap, overwrap films and sandwich bags; industrial and institutional
films,
trash bags, can liners, magazine overwrap, newspaper bags, mail bags, sacks
and
.. envelopes, bubble wrap, carpet film, furniture bags, garment bags, coin
bags, auto
panel films; medical applications such as gowns, draping and surgical garb;
construction films and sheeting, asphalt films, insulation bags, masking film,
landscaping film and bags; geomembrane liners for municipal waste disposal and
mining applications; batch inclusion bags; agricultural films, mulch film and
green
.. house films; in-store packaging, self-service bags, boutique bags, grocery
bags, carry-
out sacks and t-shirt bags; oriented films, machine direction and biaxially
oriented
films and functional film layers in oriented polypropylene (OPP) films, e.g.,
sealant
and/or toughness layers. Additional manufactured articles comprising one or
more
films containing at least one ethylene interpolymer product having
intermediate
branching include laminates and/or multilayer films; sealants and tie layers
in
multilayer films and composites; laminations with paper; aluminum foil
laminates or
laminates containing vacuum deposited aluminum; polyamide laminates; polyester
laminates; extrusion coated laminates, and; hot-melt adhesive formulations.
The
manufactured articles summarized in this paragraph contain at least one film
(monolayer or multilayer) comprising at least one embodiment of the disclosed
intermediately branched ethylene interpolymer products.
Intermediately branched ethylene interpolymer product have performance
attributes
that are advantageous in many flexible applications. The performance
attribute(s)
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required depends on how the film will be used, i.e., the specific film
application the film
is employed in. Ethylene interpolymer products having intermediate branching
have a
desirable balance of properties. Elaborating, relative to competitive
polyethylenes of
similar density and melt index, intermediately branched ethylene interpolymers
have
one or more of: improved dart impact; improved machine direction tensile
strength;
improved transverse direction tensile strength; improved a 45 gloss; and/or
improved
haze; relative to a comparative film. To be more clear: in the comparative
film the
second ethylene interpolymer having intermediate branching has been replaced
with a
comparative second ethylene interpolymer that does not contain intermediate
branching. The improvements in film properties disclosed are not to be
construed as
limiting.
The films and/or flexible articles described above may optionally include,
depending
on its intended use, additives and adjuvants. Non-limiting examples of
additives and
adjuvants include, anti-blocking agents, antioxidants, heat stabilizers, slip
agents,
processing aids, anti-static additives, colorants, dyes, filler materials,
light stabilizers,
light absorbers, lubricants, pigments, plasticizers, nucleating agents and
combinations
thereof. Non-limiting examples of suitable primary antioxidants include
lrganox 1010
[CAS Reg. No. 6683-19-8] and lrganox 1076 [CAS Reg. No. 2082-79-3]; both
available from BASF Corporation, Florham Park, NJ, U.S.A. Non-limiting
examples of
suitable secondary antioxidants include lrgafos 168 [CAS Reg. No. 31570-04-4],
available from BASF Corporation, Florham Park, NJ, U.S.A.; Weston 705 [CAS
Reg.
No. 939402-02-5], available from Addivant, Danbury CT, U.S.A. and; Doverphos
lgp-
11 [CAS Reg. No. 1227937-46-3] available form Dover Chemical Corporation,
Dover
OH, U.S.A.
Intermediately branched ethylene interpolymer products may also be converted
into a
wide variety of rigid manufactured articles, non-limiting examples include:
deli
containers, margarine tubs, drink cups and produce trays, bottle cap liners
and bottle
caps (for carbonated or non-carbonated fluids), closures (including closures
with living
hinge functionality), household and industrial containers, cups, bottles,
pails, crates,
tanks, drums, bumpers, lids, industrial bulk containers, industrial vessels,
material
handling containers, toys, bins, playground equipment, recreational equipment,
boats,
marine equipment, safety equipment (helmets), wire and cable applications such
as
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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/medical packaging,
truck bed
liners, pallets and automotive dunnage.
The rigid manufactured articles summarized above contain one or more
intermediately
branched ethylene interpolymer product or a blend of at least one
intermediately
branched ethylene interpolymer product with at least one other thermoplastic.
Further, the rigid manufactured articles summarized above may be multilayer,
comprising at least one layer comprising one or more ethylene interpolymer
product
having intermediate branching or a blend of at least one ethylene interpolymer
product
having intermediate branching 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 rigid articles described above 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.
EXAMPLES
Polymerization
The following examples are presented for the purpose of illustrating
embodiments of
this disclosure; it being understood, that the examples presented do not limit
the
claims presented.
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In-line Intermediate Branching Catalyst Formulation
Embodiments of ethylene interpolymer products having intermediate branching
were
prepared in a pilot plant using an intermediate branching catalyst
formulation.
Methylpentane was used as the process solvent (a commercial blend of
methylpentane isomers). The volume of the first CSTR reactor (R1) was 3.2
gallons
(12 L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L) and
the
volume of the tubular reactor (R3) was 0.58 gallons (2.2 L) or 4.8 gallons (18
L). The
R1 pressure ranged from about 14 MPa to about 18 MPa; R2 was operated at a
lower
pressure to facilitate continuous flow from R1 to R2. In some embodiments R1,
R2
and R3 were operated in series mode; wherein the first exit stream from R1
flows
directly into R2. In other embodiments R1 and R2 were operated in parallel
mode;
wherein the first exit from R1 and the second exit stream from R2 are combined
downstream of R2. R2 was agitated such that the reactor contents were well
mixed;
R1 was agitated if this reactor was utilized. Polymerization was conducted by
continuously feeding fresh process solvent, ethylene, 1-octene and hydrogen to
the
reactor or reactors.
The solution process conditions employed to manufacture Examples 1 and 4 were
summarized in Tables la and lb. In Examples 1 an embodiment of the in-line
intermediate branching catalyst formulation was injected into the second CSTR
reactor (R2); in a similar manner, Example 2 was synthesized using the same in-
line
intermediate branching catalyst system. In Example 1, 80% of the ethylene was
injected into R2 (i.e. the ethylene split (ESR2) was 80% and the remaining
ethylene
was injected in the tubular third reactor (R3) (ESR3 20%). In Example 2, ESR2
was
100%. Example 4 was produced by injecting a batch intermediate branching
catalyst
formulation into R2 and ESR2 was 100%. In Examples 1, 2 and 4 all the
comonomer
(1-octene) was injected into R2, i.e. the comonomer split, CSR2, was 100%. The
physical and molecular characteristics of Examples 1, 2 and 4 were summarized
in
Table 2.
In the case of Examples 1 and 2, embodiments of the in-line intermediate
branching
catalyst formulation were prepared from the following components: component
(v),
butyl ethyl magnesium; component (vi), tertiary butyl chloride; component
(vii),
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titanium tetrachloride; component (viii), diethyl aluminum ethoxide, and;
component
(ix), triethyl aluminum. In step one, a solution of triethylaluminum and
dibutylmagnesium ((triethylaluminum)/(dibutylmagnesium) molar ratio of 20) was
combined with a solution of tertiary butyl chloride and allowed to react for
about 30
seconds (HUT-1); in step two, a solution of titanium tetrachloride was added
to the
mixture formed in step one and allowed to react for about 14 seconds (HUT-2),
and; in
step three, the mixture formed in step two was allowed to reactor for an
additional 3
seconds (HUT-3) prior to injection into R2. The average solution temperature
during
HUT-1, THuT-1 was 65.3 C; and the average solution temperature during HUT-2,
THUT-2
was 71.1 C. The in-line intermediate branching catalyst formulation was formed
in R2
by injecting a solution of diethyl aluminum ethoxide into R2. The quantity of
component (vii), i.e. `1R2 (vii) (ppm)' added to reactor 2 (R2) was shown in
Table 1a; to
be more clear, in Example 1 the solution in R2 contained 6.4 ppm of T1C14. The
mole
ratios of the in-line intermediate branching catalyst components were also
shown in
Table la, specifically: (vi)/(v) or (tertiary butyl chloride)/(butyl ethyl
magnesium);
(viii)/(vii) or (diethyl aluminum ethoxide)/(titanium tetrachloride), and;
(ix)/(vii) or
(triethyl aluminum)/(titanium tetrachloride). In Example 1, the following mole
ratios
were used to synthesize the in-line intermediate branching catalyst
formulation: R2
(vi)/(v) = 1.78; R2 (viii)/(vii) = 1.35, and; R2 (ix)/(vii) = 0.35. Referring
to Figure 19, in
Examples 1 and 2, 100% of the diethyl aluminum ethoxide in stream 10d,
component
(viii), was added to reactor 12a via stream 10h.
Average residence time of the solvent in a reactor is primarily influenced by
the
amount of solvent flowing through each reactor and the total amount of solvent
flowing
through the solution process, in the case of Examples 1 and 2 the typical
average
reactor residence times for R2 and R2 was about 73 and 50 seconds,
respectively (R3
volume 18L (4.8 gallons)).
Polymerization in the continuous solution polymerization process was
terminated by
adding a catalyst deactivator to the third exit stream exiting the tubular
reactor (R3).
The catalyst deactivator used was octanoic acid (caprylic acid), commercially
available from P&G Chemicals, Cincinnati, OH, U.S.A. The catalyst deactivator
was
added such that the moles of fatty acid added were 50% of the total molar
amount of
titanium and aluminum added to the polymerization process; i.e. moles of
octanoic
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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 ethylene
interpolymer
product from the process solvent, i.e. two vapor/liquid separators were used
and the
second bottom stream (from the second V/L separator) was passed through a gear
pump/pelletizer combination. DHT-4V (hydrotalcite), supplied by Kyowa Chemical
Industry Co. LTD, Tokyo, Japan was used as a passivator, or acid scavenger. A
slurry of DHT-4V in process solvent was added prior to the first V/L
separator. The
molar amount of DHT-4V added was 10-fold higher than the molar amount of
tertiary
butyl chloride and titanium tetrachloride added to the solution process.
Prior to pelletization the ethylene interpolymer product was stabilized by
adding about
500 ppm of lrganox 1076 (a primary antioxidant) and about 500 ppm of Irgafos
168 (a
secondary antioxidant), based on weight of the ethylene interpolymer product.
Antioxidants were dissolved in process solvent and added between the first and
second V/L separators. The targeted ethylene interpolymer product was 1.0 melt
index (12) (ASTM D1239, 2.16kg load, 190 C) and 0.920 g/cm3 (ASTM D792). As
shown in Table lb, Examples 1 was produced at production rates of 98.3 kg/hr.
Batch Intermediate Branching Catalyst Formulation
Using a batch intermediate branching catalyst formulation an intermediately
branched
ethylene interpolymer product was prepared in the pilot plant (described
above);
specifically, Example 4 in Tables la and lb.
The batch intermediate branching procatalyst was injected into R2 using a
batch
delivery system. The batch delivery system consisted of an agitated catalyst
storage
tank, recirculation loop, a metering pump and solvent diluent loop. The batch
intermediate branching procatalyst was prepared in the Catalyst Synthesis Unit
(CSU), described below, and transferred to the agitated catalyst storage tank
using
nitrogen. Once transferred, the agitator in the catalyst storage tank and the
recirculation pump were started to keep the batch intermediate branching
procatalyst
suspended to maintain a constant composition in the slurry. The temperature in
the
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storage tank was maintained at ambient temperature and the tank pressure was
300
kPag. The batch intermediate branching procatalyst was transferred from the
storage
tank to the reactor using the metering pump and a high flow solvent diluent.
To be
more clear, the discharge from the metering pump was combined with a high flow
solvent diluent having a flow rate of 15 kg/hr; the diluent was used to
facilitate
procatalyst injection into R2. A flow meter recorded the flow rate of the
combined
batch intermediate branching procatalyst and the high flow diluent. The amount
of
batch intermediate branching procatalyst injected into R2 was
controlled/adjusted by
changing the metering pump's variable frequency drive or pump stoker. The co-
catalyst, diethyl aluminum ethoxide (component (viii)), was injected into the
reactor
(R2) through a separate line forming the active batch intermediate branching
catalyst
formulation. Typically, procatalyst flow rate was adjusted such that more than
80% of
the ethylene was converted to polyethylene in R2. The quantity of the batch
intermediate branching catalyst formulation added to R2 was expressed as the
parts-
per-million (ppm) of component (vii) in the reactor solution, i.e. R2 batch
(vii) was 0.97
ppm for Example 4, as shown in Table la; the R2 batch (viii)/(vii) was 4.0,
stream 60e
flow rate was 30,370 g/hr and the R2 batch catalyst inlet temperature was 31.9
C.
The physical properties of Example 4 were summarized in Table 2.
Batch Intermediate Branching Procatalyst Formulation
The batch intermediate branching procatalyst was prepared in the Catalyst
Synthesis
Unit (CSU). The CSU included a continuously stirred tank reactor coded CSU-1,
having a volume of 2.1 L, designed for pressures up to 20.6 MPa and
temperatures up
to 350 C. As described below, the batch intermediate branching procatalyst was
prepared in a batch-wise fashion in CSU-1 from the following components:
component
(v), butyl ethyl magnesium; component (vi), tertiary butyl chloride; component
(vii),
titanium tetrachloride; component (viii), diethyl aluminum ethoxide, and;
component
(x), isobutyl aluminum dichloride. First, magnesium dichloride was formed in
CSU-1.
Although the MgCl2 reaction did not require pressure, CSU-1 was operated at
100 psi
N2 pressure to ensure inert conditions, temperature was controlled at 50 C
using a
recirculating heating bath connected to the jacket on CSU-1 and agitator speed
was
600 rpm. Using diaphragm pumps, components (v) and (vi) were continuously
added
to CSU-1 from their respective 5.5 L reagent vessels such that the [component
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(vi)]/[component (v)] mole ratio was about 2.2. After about 100 minutes 1.5 L
of MgCl2
slurry had been collected in CSU-1 and the flows of components (v) and (vii)
were
stopped. Using a diaphragm pump component (x), stored in a 0.15 L reagent
vessel,
was pumped to CSU-1 and the reactor was stirred at 50 C for an additional 15
minutes; the [(component (x)]/[(component (v)] mole ratio was about 0.23.
Using a
diaphragm pump component (vii), stored in a 0.15 L reagent vessel, was pumped
to
CSU-1 and the reactor was stirred at 50 C for an additional 10 minutes; the
[(component (v)]/[(component (yip] mole ratio was about 7.5. The batch
intermediate
branching procatalyst formulation was formed by adding component (viii). Using
a
diaphragm pump, component (viii) was pumped from its 0.15 L reagent vessel to
CSU-1 and the reactor was heated to 85 C and stirred for 90 minutes; the
[(component (viii)]/[(component (yip] mole ratio was from about 1.0 to about
1.65. The
batch intermediate branching procatalyst was pumped from CSU-1 to the catalyst
storage tank and injected in R2 was required.
Mixed Catalyst Examples
The following examples were presented to illustrate embodiments of ethylene
interpolymer products produced using two catalyst formulations; these
interpolymers
contained a component A and a component B; wherein component B contained
intermediate branching and component A did not contain intermediate branching
and
may, or may not, contain long chain branching. It is understood that the
following
examples do not limit the claims presented.
The solution pilot plant described above was used to manufacture Example 5.
Tables
10a and 10b disclosed the process conditions employed to manufacture Example
5;
where an unbridged single site catalyst formulation was employed in reactor 1
(R1)
and an in-line intermediate branching catalyst formulation (fully described
above) was
.. employed in reactor 2 (R2). The unbridged single site catalyst formulation
included
the following components: component (i), cyclopentadienyl tri(tertiary
butyl)phosphinimine titanium dichloride, (Cp[(t-Bu)3PN]TiC12) (abbreviated PIC-
1 in
Table 10a); component (ii), methylaluminoxane (MA0-07); component (iii),
trityl
tetrakis(pentafluoro-phenyl)borate, and; component (iv), 2,6-di-tert-buty1-4-
ethylphenol. The unbridged single site catalyst component solvents used were
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methylpentane for components (ii) and (iv) and xylene for components (i) and
(iii).
The quantity of PIC-1 added "R1 (i) (ppm)" was 0.12 ppm; i.e. the solution in
R1
contained 0.12 ppm of PIC-1. The mole ratios of the catalyst components in R1
were:
(ii)/(i) or [(MAO-07)/(PIC-1)] was 100; (iv)/(ii) or [(2,6-di-tert-butyl-4-
ethylphenol)/(MA0-
07)] was 0.0, and; (iii)/(i) or [(trityl tetrakis(pentafluoro-
phenyl)borate)/(PIC-1)] was 1.1.
Additional solution process parameters are disclosed in Table 10b; for
example, given
the ethylene splits of 40/60 (ESR1/ESR2), Example 5 contained about 40 wt% of
component A and about 60 wt% of component B. PIC-1 produced an ethylene/1-
octene interpolymer, component A, that did not contain long chain branching or
intermediate branching. The in-line intermediate branching catalyst
formulation
produced an ethylene/1-octene interpolymer, component B, that contained
intermediate branching and did not contain long chain branching. In Example 5,
the
average solution temperature during HUT-1, ruT-1 was 64.0 C; and the average
solution temperature during HUT-2, THUT-2 was 70.5 C. The in-line intermediate
branching catalyst formulation was formed in R2 by injecting a solution of
diethyl
aluminum ethoxide into R2.
The solution pilot plant described above was also used to manufacture Examples
10
and 11. Examples 10 and 11 were manufactured employing a bridged metallocene
catalyst formulation in reactor 1 (R1) and the in-line intermediate branching
catalyst
formulation (described above) in reactor 2 (R2) as shown in Tables 10a and
10b. The
following components were used to prepare the bridged metallocene catalyst
formulation: component (i), diphenylmethylene(cyclopentadienyl)(2,7-di-t-
butylfuorenyl) hafnium dimethyl, [(2,7-tBu2Flu)Ph2C(Cp)HfMe2] (abbreviated CpF-
2 in
Table 10a); component (ii) methylaluminoxane (MMA0-07); component (iii) trityl
tetrakis(pentafluoro-phenyl)borate, and; component (iv) 2,6-di-tert-butyl-4-
ethylphenol.
The bridged metallocene catalyst component solvents used were methylpentane
for
components (ii) and (iv) and xylene for components (i) and (iii). The quantity
of CpF-2
added "R1 (i) (ppm)" was 0.38 ppm; i.e. the solution in R1 contained 0.38 ppm
of CpF-
2. In the case of Example 10, the mole ratios of the catalyst components in R1
were:
(ii)/(i) or [(MAO-07)/(CpF-2)] was 64.2; (iv)/(ii) or [(2,6-di-tert-butyl-4-
ethylphenol)/(MA0-07)] was 0.16, and; (iii)/(i) or [(trityl
tetrakis(pentafluoro-
phenyl)borate)/(CpF-2)] was 1.20. Additional solution process parameters were
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disclosed in Table 10b. Example 10 was manufactured with R1 and R2 operating
in
series mode and given an ethylene split of 50/50 (ESR1/ESR2); i.e. Example 10
contained about 50 wt% of a component A and about 50 wt% of a component B.
Example 11 was manufactured with R1 and R2 operating in parallel mode and
given
an ethylene split of 40/60 (ESRVESR2) Example 11 contained about 40 wt% of a
component A and about 60 wt% of a component B. CpF-2 produced an ethylene/1-
octene interpolymer, component A, that contained long chain branching but did
not
contain intermediate branching. The in-line intermediate branching catalyst
formulation produced an ethylene/1-octene interpolymer, component B, that
contained
intermediate branching and did not contain long chain branching.
In Example 10, the average solution temperature during HUT-1, THuT-1 was 65.3
C;
and the average solution temperature during HUT-2, THUT-2 was 62.8 C. In
Example
11, the average solution temperature during HUT-1, THuT-1 was 64.8 C; and the
average solution temperature during HUT-2, THUT-2 was 66.1 C. In both Examples
10
and 11, the in-line intermediate branching catalyst formulation was formed in
R2 by
injecting a solution of diethyl aluminum ethoxide into R2.
Blown Films
The following examples are presented for the purpose of illustrating
embodiments of
manufactured articles, specifically blown films; it being understood that
articles of
manufacture are not limited to blown films.
Monolayer blown films were produced on a monolayer blown film line (Macro
Engineering, Mississauga, Ontario, Canada). This line was equipped with: a 3-
inch
diameter (7.62-cm) barrel; a Maddox mixing screw; a low pressure, four-port
spiral
mandrel die with a 35 mil (0.089 cm) die gap; and a dual ring. Blown films
were
produced at thicknesses of 1.0, 2.0 and 4.0 mil (25.4, 50.8 and 101.6 p.m)
employing
the experimental conditions disclosed in Table 22. Examples 2 and 3 were
produced
in the solution pilot plant (described above) using an in-line intermediate
branching
catalyst formulation and similar process conditions as those used to
manufacture
Example 1 (0.9191 g/cm3, 0.90 dg/min) as disclosed in Tables la and lb;
Example 2
was an ethylene/1-octene interpolymer having a density of 0.9208 g/cm3 and a
melt
index of 1.02; Example 3 was an ethylene/1-octene interpolymer having a
density of
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0.9200 g/cm3 and a melt indexes of 0.96 dg/min. Given the fact that Examples 2
and
3 were manufactured using a similar in-line intermediate branching catalyst
formulation, the same pilot plant and similar process conditions; Examples 2
and 3
contained a level of intermediate branching similar to Example 1. Comparative
2 was
an ethylene/1-octene interpolymer produced with a comparative batch Ziegler-
Natta
catalyst formulation that did not produce intermediate branching; the physical
properties of Comparative 2 were summarized in Table 2, e.g. 0.9208 g/cm3 and
0.97
dg/min.
Table 23 disclosed the blown film properties of: (i) Example 2; about 1 mil
film; (ii)
Example 3, about 2 mil and about 4 mil films; and (iii) Comparative Example 2,
about
2 mil and about 4 mil films. At least one advantage of films manufactured from
ethylene interpolymer products having intermediate branching was an improved
(higher) dart impact; relative to comparative films manufactured from
comparative
ethylene interpolymer products that do not contain intermediate branching.
More
specifically, as disclosed in Table 23, the 2 mil film prepared from Example 3
had a
dart impact of 365 g/mil which was 109% improved relative to the dart impact
of the
film prepared from Comparative 2, i.e. 175 g/mil. Similarly, the 4 mil film
prepared
from Example 3 had a dart impact of 256 g/mil which was 71% improved relative
to
the dart impact of the film prepared from Comparative 2, i.e. 150 g/mil.
Table 24 compares the monolayer blown film properties of Example 6 with
Comparative 9. Example 6 has been discussed previously. Example 6 was an
ethylene/1-octene interpolymer product containing the following two
components: A)
about 40 wt% of a first ethylene interpolymer produced using an unbridged
single site
catalyst formulation in a first reactor; and B) about 60 wt% of a second
ethylene
interpolymer produced using an in-line intermediate branching catalyst
formulation in a
second reactor; where the two reactors were operated in series. As shown in
Table
24, Example 6 and Comparative 9 had the same density and melt index. However,
Comparative 9 did not contain intermediate branching. Comparative 9 was an
ethylene/1-octene interpolymer product containing two components: A) about 40
wt%
of a first ethylene interpolymer produced using an unbridged single site
catalyst
formulation in a first reactor; and B) about 60 wt% of a second ethylene
interpolymer
produced using an unbridged single site catalyst formulation in a second
reactor
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(same catalyst in both reactors); where the two reactors were operated in
series.
Several advantages of films manufactured from ethylene interpolymer products
having
intermediate branching are evident in Table 24; relative to the Comparative 9
film. For
example, monolayer films (1.0 mil) prepared from Example 6 had improved
(higher)
dart impact relative to Comparative 9 monolayer films (1.0 mil); i.e. 824 g,
relative to
475 g, respectively, a 74% higher dart impact. The Example 6 film had improved
(higher) machine direction (MD) tensile strength relative to the Comparative 9
film; i.e.
56 MPa, relative to 49 MPa, respectively, a 14% higher MD tensile strength.
The
Example 6 film had improved (higher) transverse direction (TD) tensile
strength
relative to the Comparative 9 film; i.e. 47 MPa, relative to 40 MPa,
respectively, an
18% higher TD tensile strength. Example 6 films also had improved optical
properties
relative to Comparative 9 films. Specifically, the Example 6 film had improved
(higher)
45 gloss relative to the Comparative 9 film, i.e. 73, relative to 35,
respectively, which
was a 108% improvement in film 45 gloss; and the film haze was improved
(lower);
i.e. 11%, relative to 22%, respectively, a -73% improvement in film haze.
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Testing Methods
Prior to testing, each specimen was conditioned for at least 24 hours at 23 2
C and
50 10% relative humidity and subsequent testing was conducted at 23 2 C and
50
10% relative humidity. Herein, the term "ASTM conditions" refers to a
laboratory that
is maintained at 23 2 C and 50 10% relative humidity; and specimens to be
tested
were conditioned for at least 24 hours in this laboratory prior to testing.
ASTM refers
to the American Society for Testing and Materials.
Density
Ethylene interpolymer density was determined using ASTM D792-13 (November 1,
2013).
Melt Index
Ethylene interpolymer melt index was determined using ASTM D1238 (August 1,
2013). Melt indexes, 12, 16, 110 and 121 were measured at 190 C., using
weights of 2.16
kg, 6.48 kg, 10 kg and a 21.6 kg respectively. The terms High Load Melt Index
(HLMI)
and 121 are equivalent. The term Melt Flow Ratio (MFR) is defined as 121/12.
Herein,
the term "stress exponent" or its acronym "S.Ex.", is defined by the following
relationship:
S.Ex.= log (16/12)/log(6480/2160)
wherein 16 and 12 are the melt flow rates measured at 190 C using 6.48 kg and
2.16 kg
loads, respectively.
Conventional Size Exclusion Chromatography (SEC)
Ethylene interpolymer (polymer) solutions (1 to 3 mg/mL) were prepared by
heating
the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4
hours at
150 C in an oven. An antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was
added
to the mixture in order to stabilize the polymer against oxidative
degradation. The
BHT concentration was 250 ppm. Polymer solutions were chromatographed at 140 C
on a PL 220 high-temperature chromatography unit equipped with four Shodex
columns (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
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ppm to protect GPO columns from oxidative degradation. The sample injection
volume was 200 pL. The GPC columns were calibrated with narrow distribution
polystyrene standards. The polystyrene molecular weights were converted to
polyethylene molecular weights using the Mark-Houwink equation, as described
in the
ASTM standard test method D6474-12 (December 2012). The GPO raw data were
processed with the Cirrus GPO software, to produce molar mass averages (Mn,
Mw,
Mz) and molar mass distribution (e.g. Polydispersity, Mw/Mn). In the
polyethylene art, a
commonly used term that is equivalent to SEC is GPO, i.e. Gel Permeation
Chromatography.
Triple Detection Size Exclusion Chromatography (3D-SEC)
Ethylene interpolymer (polymer) sample solutions (1 to 3 mg polymer/mL) were
prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating
on a
wheel for 4 hours at 150 C in an oven. An antioxidant (2,6-di-tert-butyl-4-
methylphenol
(BHT)) was added to the mixture to stabilize the polymer against oxidative
degradation. The BHT concentration was 250 ppm. Sample solutions were
chromatographed at 140 C on a PL 220 high temperature chromatography unit
equipped with a differential refractive index (DRI) detector, a dual-angle
light
scattering detector (15 and 90 degree) and a differential viscometer. The SEC
columns used were either four Shodex columns (HT803, HT804, HT805 and HT806),
or four PL Mixed ALS or BLS columns. TCB was the mobile phase with a flow rate
of
1.0 mL/minute, BHT was added to the mobile phase at a concentration of 250 ppm
to
protect SEC columns from oxidative degradation. The sample injection volume
was
200 pL. The SEC raw data were processed with the Cirrus GPO software, to
produce
absolute molar masses and intrinsic viscosity ([9]) and viscosity average
molar mass
(Mv). The term "absolute" molar mass was used to distinguish 3D-SEC determined
absolute molar masses from the molar masses determined by conventional SEC.
The
viscosity average molar mass (Mu) and intrinsic viscosity (N) determined by 3D-
SEC
were used in calculations to determine the Long Chain Branching Factor (LCBF).
Triple Detection Cross Fractionation Chromatography (3D-CFC)
A polymer sample (150 to 300 mg) was introduced into the sample dissolution
vessel
of the Polymer Char Crystaf-TREF unit. The sample dissolution vessel was then
filled
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with 35 ml 1,2,4-trichlorobenzene (TCB) containing 250 ppm antioxidant 2,6-di-
tert-
butyl-4-methylphenol (BHT), heated to the desired dissolution temperature
(e.g.
140 C) and stirred for 2 to 3 hours. The polymer solution (1.5 ml) was then
loaded
into the TREF column filled with stainless steel beads. After being allowed to
equilibrate at a given stabilization temperature (e.g. 110 C) for 20 to 45
minutes, the
polymer solution was allowed to crystallize with a temperature drop from the
stabilization temperature to 30 C (0.2 C/minute). After equilibrating at 30 C
for 90
minutes, the crystallized sample was eluted with TCB from 30 to 140 C, while
dividing
the effluent into a number of fractions (e.g. 5 to 20 fractions). For each
fraction, the
TREF column was heated (the heating rate in the step-elution was 1.0 C/minute)
to
the specific dissolution temperature and maintained at that temperature for at
least 50
minute before the solution of the fraction was eluted and introduced directly
to a SEC
system through a heated transfer line. All above steps, including the sample
dissolution, sample solution loading into TREF column, crystallization and
elution,
were programmed and controlled with the Polymer Char TREF software with the
step-
elution capability. The various polymer fractions were chromatographed at 140
C on a
PL 220 high-temperature chromatography unit equipped with either four Shodex
columns (HT803, HT804, HT805 and HT806), or four PL Mixed ALS or BLS columns,
and with a differential refractive index (DR I) as the concentration detector.
A dual-
angle light scattering detector (15 and 90 degree) and a differential
viscometer were
used to measure the molar mass and intrinsic viscosity, respectively. TCB was
the
mobile phase with a flow rate of 1.0 mL/minute, BHT was added to the mobile
phase
at a concentration of 250 ppm to protect SEC columns from oxidative
degradation.
The data were acquired using Cirrus GPO software and processed with Cirrus GPO
.. software and Excel spreadsheet to produce absolute molar masses and
intrinsic
viscosity [11]. The term "absolute" molar mass was used to distinguish 3D-SEC
determined absolute molar masses from the molar masses determined by
conventional SEC. The viscosity average molar mass (Mu) and intrinsic
viscosity [9]
of each 3D-CFC TREF fraction determined by 3D-CFC were used in calculations to
determine the Non-Comonomer Index (NCI) and the Non-Comonomer Index
Distribution (NCIDi).
Referring to Eq.(4) where NCI f was defined; (Mvf) (g/mole) and [q]f (dL/g)
were the
viscosity average molar mass and the intrinsic viscosity, respectively, of the
ffh TREF
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fraction as determined with 3D-CFC; Tf was the weight average TREF elution
temperature of the fth TREF fraction (details regarding Tf are described
below); and A,
B and C were constants specific to the a¨olefin comonomer in the
ethylene/a¨olefin
interpolymer under test. In the case of 1-octene: A was 2.1626; B was -0.6737
and C
was 63.6727. Constants A, B and C for other a-olefins were determined
experimentally (non-limiting examples include 1-hexene). Elaborating, a series
of
linear ethylene/a¨olefin interpolymers with different comonomer contents were
analyzed with triple detection size exclusion chromatography (3D-SEC) in TCB
at
140 C, in which the viscosity average molar masses (My) and the intrinsic
viscosities
.. (m) of the linear ethylene/a¨olefin interpolymers were determined and were
used to
calculate the Mark-Houwink constants K based on the Mark-Houwink equation ([q]
= K
x (Mv)a). Well-known to those of ordinary experience, the Mark-Houwink
constant a is
0.725 for ethylene/a¨olefin interpolymers. Using simple regression, a plot of
Mark-
Houwink constants K versus comonomer contents [CH3/1000C] of the linear
ethylene/a¨olefin interpolymers generated the following relationship:
K = (slope) [CH3/1000C] + intercept Eq.(16)
In this disclosure, the constant A in Eq.(4) was defined by the (slope) in
Eq.(16);
specifically, A = -1000000 x (slope). The constants B and C in Eq.(4) were
calculated
from the linear correlation between comonomer contents and the weight average
elution temperatures of ethylene/a¨olefin interpolymers based on re-
constructed
analytical TREF profiles of the ethylene/a-olefin interpolymers (see details
below); the
constant B was the slope and the constant C was the intercept. For example, in
this
disclosure for a¨octene comonomer, constants A, B and C were 2.1626, -0.6737
and
63.6727 respectively.
Tf, in Eq.(4), the weight average TREF elution temperature of the fth 3D-CFC
TREF
fraction, was calculated based on the re-constructed analytical TREF profile
of the
ethylene/a¨olefin interpolymer. The re-constructed analytical TREF profile was
obtained by simply replacing the original elution temperatures in analytical
TREF
analysis performed on a Polymer Char Crystaf-TREF instrument, hereafter CTREF,
with the equivalents of 3D-CFC elution temperature. The conversion of the
original
elution temperatures to the equivalents of 3D-CFC elution temperature enables
one to
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compensate for differences in flow during the elution stage, i.e. dynamic
(with a flow)
while heating in CTREF, in contrast with static elution (without a flow) while
heating in
3D-CFC; as well as for any other difference between these instruments (if
any). To do
this conversion, a series of ethylene/a¨olefin interpolymers having different
comonomer contents and randomly distributed comonomer units were analyzed with
both CTREF (Polymer Char Crystaf-TREF unit) and 3D-CFC. In this calibration
procedure, the range of elution temperature in 3D-CFC analysis for each TREF
fraction was very narrow (e.g., 1 to 2 degrees whenever possible and not
greater than
5 degrees) and the average of the low and high temperatures of the TREF
fraction
was used to define the elution temperature of the 3D-CFC TREF fraction, e.g.
42.5 C
was the elution temperature for the 40 C to 45 C fraction. The weight average
elution
temperature of the entire ethylene/a¨olefin interpolymer was calculated from
the
weight fraction and the elution temperature of each 3D-CFC TREF fraction. From
the
correlations between comonomer contents and the weight average elution
temperatures of ethylene/a¨olefin interpolymers in 3D-CFC and CTREF, the
relation
between the weight average elution temperatures between 3D-CFC and CTREF could
be established and this relation was used to convert the original elution
temperatures
in CTREF analysis to 3D-CFC elution temperatures. In this disclosure, the
relation
between the weight average elution temperatures of 3D-CFC (TcFc) and the
weight
average elution temperatures of CTREF (TcTREF) was described by the following
relationship.
TCFC = 0.9776 TCTREF ¨ 0.7156
This relationship was used to convert the original CTREF elution temperatures
to the
equivalents of 3D-CFC elution temperature in re-construction of the analytical
TREF
profiles, for calculating the Tf, the weight average TREF elution temperature
of the fth
3D-CFC TREF fraction and for calculating the constants B and C in Eq.(4).
Dynamic Mechanical Analysis (DMA)
Oscillatory shear measurements under small strain amplitudes were carried out
to
obtain linear viscoelastic functions at 190 C under nitrogen atmosphere, at a
strain
amplitude of 10% and over a frequency range of 0.02-126 rad/s at 5 points per
decade. Frequency sweep experiments were performed with a TA Instruments DHR3
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stress-controlled rheometer using cone-plate geometry with a cone angle of 5 ,
a
truncation of 137 pm and a diameter of 25 mm. In this experiment a sinusoidal
strain
wave was applied and the stress response was analyzed in terms of linear
viscoelastic functions. The zero shear rate viscosity (p) based on the DMA
frequency
sweep results was determined using the Ellis model (see R.B. Bird et al.
"Dynamics of
Polymer Liquids. Volume 1: Fluid Mechanics" Wiley-lnterscience Publications
(1987)
p.228).
Composition Distribution Branching Index (CDBI)
The "Composition Distribution Branching Index", hereinafter CDBI, of the
disclosed
Examples and Comparative Examples were measured using a CRYSTAF/TREF 200+
unit equipped with an IR detector, hereinafter CTREF. The acronym "TREF"
refers to
Temperature Rising Elution Fractionation. The CTREF was supplied by
PolymerChAR S.A. (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-
46980
Valencia, Spain). The CTREF was operated in the TREF mode, which generates the
chemical composition of the polymer sample as a function of elution
temperature, the
Co/Ho ratio (Copolymer/Homopolymer ratio) and the CDBI (the Composition
Distribution Breadth Index), i.e. CDBI50. A polymer sample (80 to 100 mg) was
placed
into the reactor vessel of the CTREF. The reactor vessel was filled with 35 ml
of
1,2,4-trichlorobenzene (TCB) and the polymer was dissolved by heating the
solution
to 150 C for 2 hours. An aliquot (1.5 mL) of the solution was then loaded into
the
CTREF column which was packed with stainless steel beads. The column, loaded
with sample, was allowed to stabilize at 110 C for 45 minutes. The polymer was
then
crystallized from solution, within the column, by dropping the temperature to
30 C at a
cooling rate of 0.09 C/minute. The column was then equilibrated for 30 minutes
at
C. The crystallized polymer was then eluted from the column with TCB flowing
through the column at 0.75 mL/minute, while the column was slowly heated from
30 C
to 120 C at a heating rate of 0.25 C/minute. The raw CTREF data were processed
30 using Polymer ChAR software, an Excel spreadsheet and CTREF software
developed
in-house. CDBI50 was defined as the percent of polymer whose composition was
within 50% of the median comonomer composition; CDBI50 was calculated from the
composition distribution cure and the normalized cumulative integral of the
composition distribution curve, as described in United States Patent
5,376,439.
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Those skilled in the art will understand that a calibration curve was required
to convert
a CTREF elution temperature to comonomer content, i.e. the amount of comonomer
in
the ethylene/a-olefin polymer fraction that eluted at a specific temperature.
The
generation of such calibration curves were described in the prior art, e.g.
Wild, et al.,
J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455: hereby fully
incorporated by reference. At the end of each sample run, the CTREF column was
cleaned for 30 minutes; specifically, with the CTREF column temperature at 160
C,
TCB flowed (0.5 mL/minute) through the column for 30 minutes.
Neutron Activation (Elemental Analysis)
Neutron Activation Analysis, hereinafter N.A.A., was used to determine
catalyst
residues in ethylene interpolymer products as follows. A radiation vial
(composed of
ultrapure polyethylene, 7 mL internal volume) was filled with an ethylene
interpolymer
.. product sample and the sample weight was recorded. Using a pneumatic
transfer
system the sample was placed inside a SLOWPOKE TM nuclear reactor (Atomic
Energy of Canada Limited, Ottawa, Ontario, Canada) and irradiated for 30 to
600
seconds for short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3 to 5
hours for long
half-life elements (e.g. Zr, Hf, Cr, Fe and Ni). The average thermal neutron
flux within
the reactor was 5x1011/cm2/s. After irradiation, samples were withdrawn from
the
reactor and aged, allowing the radioactivity to decay; short half-life
elements were
aged for 300 seconds or long half-life elements were aged for several days.
After
aging, the gamma-ray spectrum of the sample was recorded using a germanium
semiconductor gamma-ray detector (Ortec model GEM55185, Advanced
Measurement Technology Inc., Oak Ridge, TN, USA) and a multichannel analyzer
(Ortec model DSPEC Pro). The amount of each element in the sample was
calculated from the gamma-ray spectrum and recorded in parts per million
relative to
the total weight of the ethylene interpolymer product sample. The N.A.A.
system was
calibrated with Specpure standards (1000 ppm solutions of the desired element
(greater than 99% pure)). One mL of solutions (elements of interest) were
pipetted
onto a 15 mm x 800 mm rectangular paper filter and air dried. The filter paper
was
then placed in a 1.4 mL polyethylene irradiation vial and analyzed by the
N.A.A.
system. Standards are used to determine the sensitivity of the N.A.A.
procedure (in
counts/pg).
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Unsaturation
The quantity of unsaturated (Unsat.) groups, i.e. double bonds, in an ethylene
interpolymer product was determined according to ASTM D3124-98 (vinylidene
unsaturation, published March 2011) and ASTM D6248-98 (vinyl and trans
unsaturation, published July 2012). An ethylene interpolymer product sample
was: a)
first subjected to a carbon disulfide extraction to remove additives that may
interfere
with the analysis; b) the sample (pellet, film or granular form) was pressed
into a
plaque of uniform thickness (0.5 mm), and; c) the plaque was analyzed by FTIR.
Comonomer Content: Fourier Transform Infrared (FTIR) Spectroscopy
The quantity (mol% (or wt%)) of comonomer in an ethylene interpolymer product
was
determined by FTIR and reported as the Short Chain Branching (SCB) content
having
dimensions of CH3#/1000C (number of methyl branches per 1000 carbon atoms).
This test was completed according to ASTM D6645-01 (2001), employing a
compression molded polymer plaque and a Thermo-Nicolet 750 Magna-IR
Spectrophotometer. The polymer plaque was prepared using a compression molding
device (Wabash-Genesis Series press) according to ASTM D4703-16 (April 2016).
Creep Test
Creep measurements were performed by an Anton Paar MCR 501 rheometer at
190 C using 25 mm parallel plate geometry under nitrogen atmosphere. In this
experiment, a compression molded circular plaque with a thickness of 1.8 mm
was
placed between the pre-heated upper and lower measurement fixtures and allowed
to
come to thermal equilibrium. The upper plate was then lowered to 50 pm above
the
testing gap size of 1.5 mm. At this point, the excess material was trimmed off
and the
upper fixture was lowered to the measurement gap size. A waiting time of 10
min
after sample loading and trimming was applied to avoid residual stresses
causing the
strain to drift. In the creep experiment, the shear stress was increased
instantly from 0
to 20 Pa and the strain was recorded versus time. The sample continued to
deform
under the constant shear stress and eventually reached a steady rate of
straining.
Creep data was reported in terms of creep compliance (1(0) which has the units
of
reciprocal modulus. The inverse of J(t) slope in the steady creeping regime
was used
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to calculate the zero shear rate viscosity based on the linear regression of
the data
points in the last 10% time window of the creep experiment.
In order to determine if the sample was degraded during the creep test,
frequency
sweep experiments under small strain amplitude (10%) were performed before and
after creep stage over a frequency range of 0.1-100 rad/s. The difference
between
the magnitude of complex viscosity at 0.1 rad/s before and after the creep
stage was
used as an indicator of thermal degradation. The difference should be less
than 5% to
consider the creep determined zero shear rate viscosity acceptable.
Creep experiments confirmed that Linear Reference Line (see Figure 18) for
linear
ethylene interpolymers was also valid if the creep determined 'go was used
rather than
the DMA determined rio. In this disclosure, the LCBF (Long Chain Branching
Factor)
was determined using the DMA determined io. To be absolutely clear, the zero
shear
viscosity (ZSV [poise]) data reported in Tables 19a, 19b, 20 and 21 were
measured
using DMA.
Hexane Extractables (Plaque)
Hexane extractables using compression molded plaques were determined according
to ASTM D5227.
Film Dart Impact
Film dart impact strength was determined using ASTM D1709-09 Method A (May 1,
2009). In this disclosure the dart impact test employed a 1.5 inch (38 mm)
diameter
hemispherical headed dart.
Film Tensile
The following film tensile properties were determined using ASTM D882-12
(August 1,
2012): tensile break strength (MPa), elongation at break (%), tensile yield
strength
(MPa), tensile elongation at yield (%) and tensile energy to break (J).
Tensile
properties were measured in the both the machine direction (MD) and the
transverse
direction (TD) of the blown films.
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Film Secant Modulus
The secant modulus is a measure of film stiffness. The secant modulus is the
slope of
a line drawn between two points on the stress-strain curve, i.e. the secant
line. The
first point on the stress-strain curve is the origin, i.e. the point that
corresponds to the
origin (the point of zero percent strain and zero stress), and; the second
point on the
stress-strain curve is the point that corresponds to a strain of 1%; given
these two
points the 1% secant modulus 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 lnstron software. Samples were loaded in the lnstron 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 lnstron
software.
Film Elmendorf Tear
Film tear performance was determined by ASTM D1922-09 (May 1, 2009); an
equivalent term for tear is "Elmendorf tear". Film tear was measured in both
the
machine direction (MD) and the transverse direction (TD) of the blown films.
Film Opticals
Film optical properties were measured as follows: Haze, ASTM D1003-13
(November
15, 2013), and; Gloss ASTM D2457-13 (April 1,2013).
Film Hot Tack
In this disclosure, the "Hot Tack Test" was performed as follows, using ASTM
conditions. Hot tack data was generated using a J&B Hot Tack Tester which is
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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/mm2; 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 disclosed 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); "Hot
tack
Strength (N)" was the maximum hot tack force observed (average of 5-film
samples)
over the testing temperature range.
Film Heat Seal Strength
In this disclosure, the "Heat Seal Strength 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-
m)
thick film). The following parameters were used in the Heat Seal Strength
Test: film
specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film sealing
pressure,
40 psi (0.28 N/mm2); temperature range, 212 F to 302 F (100 C to 150 C) and
temperature increment, 9 F (5 C). After aging for at least 24 hours at ASTM
conditions, seal strength was determined using the following tensile
parameters: pull
(crosshead) speed, 12 inch/min (2.54 cm/min); direction of pull, 90 to seal,
and; 5
samples of film were tested at each temperature increment. The Seal Initiation
Temperature, hereinafter 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).
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Film Hexane Extractables
Hexane extractables was determined according to the Code of Federal
Registration
21 CFR 177.1520 Para (c) 3.1 and 3.2; wherein the quantity of hexane
extractable
material in a film is determined gravimetrically. Elaborating, 2.5 grams of
3.5 mil (89
pirn) monolayer film was placed in a stainless steel basket, the film and
basket were
weighed (wi), while in the basket the film was: extracted with n-hexane at
49.5 C for
two hours; dried at 80 C in a vabuum 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 (wi-wf)/wi.
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Table la
Continuous solution polymerization process parameters employing an
intermediate branching catalyst formulation: Examples 1 and 4.
Sample Code Example 1 Example 4
Intermediate Branching Catalyst In-line Batch
R2 (vii) (ppm) 6.4
R2 (vi)/(v) (mol ratio) 1.78
R2 (viii)/(vii) (mol ratio) 1.35
R2 (ix)/(vii) (mol ratio) 0.35
component (vii), stream 10c (g/h) 439.8
component (viii), stream 10h (g/h) 140.6
component (vi), stream 10b (g/h) 430.0
components ((v)+(ix))1, stream 10a
(g/h) 463.4
solvent stream 10a' (g/h) 3000
solvent stream 10b' (g/h) 3000
solvent stream 10c' (g/h) 4900
solvent stream 10f' (g/h) 37600
R2 batch (vii) ppm 0.97
R2 batch (viii)/(vii) (mol ratio) 4.0
R2 stream 60e (g/h)
30370
R2 batch catalyst, Ti flow (g/h)
Stream 60e' (g/h) 30000
1 Molar ratio of [component (ix)]/[component (v)] was 20/1
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Table lb
Additional solution process parameters for Examples 1 and 4
Sample Code Example 1 Example 4
R2 total solution rate (kg/hr) 522.2 427.3
Total Soluton Rate (kg/hr) 600.0 500.1
R2 ethylene concentration (wt%) 12.1 13.1
R3 ethylene concentration (wt%) 13.9 15.0
ESR2 (%) 80.0 80.0
ESR3 20.0 20.0
(1-octene/ethylene) total (wt.fr.) 0.50 0.46
CSR2 (%) 100 100
CSR3(%) 0.0 0.0
R2 Catalyst Inlet Temperature ( C) 40.0 31.9
R2 inlet temp ( C) 30.0 30.0
R2 Mean Temp ( C) 183.1 194.3
H2R2 (ppm) 1.0 1.0
R3 volume (L) 18 18
R3 inlet temp ( C) 129.9 129.9
R3 exit temp ( C) 211.9 221.0
H2R3 (ppm) 0.50 0.5
R3 ATemp ( C) 28.8 26.7
QT (%) 90.0 93.2
Production Rate (kg/hr) 98.3 88.0
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Table 2
Physical and molecular characteristics of Examples 1, 2 and 4; relative to
Comparatives 1 and 2
Example Example Example
Resin Code Comp. 1
Comp. 2
1 2 4
Comonomer 1-octene 1-
octene 1-octene 1-octene 1-octene
Density (g/cm3) 0.9191 0.9208 0.9186 0.9182
0.9208
12 (dg/min) 0.90 1.02 0.94 0.98 0.97
S.Ex. 1.32 1.32 1.31 1.31 1.30
MFR 29.0 30.9 29.1 28.2 29.5
Mn (g/mol) 29615 27100 35870 26682 33800
Mw (g/mol) 108052 101100 116340 94018
121500
Mz (g/mol) 312107 302700 329736 245077
329400
Mw/Mn 3.65 3.73 3.24 3.52 3.59
Mz/Mw 2.89 2.99 2.83 2.61 2.71
CDB150(%) 51.4 n/a 53.0 54.0 n/a
FTIR CoMo (mol%) 2.7 2.8 2.7 2.6 2.7
FTIR Branch Freq
13.5 14.2 13.7 13.2 13.7
(CH3/1000C)
Unsat. Internal/100C 0.005 n/a n/a 0.004 n/a
Unsat. Side
0.011 n/a .n/a 0.005 n/a
Chain/100C
Unsat.
0.050 n/a n/a 0.039 n/a
Terminal/100C
Hexane Extractables,
0.58 n/a 0.51 0.65 n/a
Plaque (%)
Ti (ppm), N.A.A. 7.52 n/a 12.84 1.7
Al (ppm), N.A.A. 94.5 n/a 186 8.8
Mg (ppm), N.A.A. 348 n/a 387 12.0
Cl (ppm), N.A.A. 93.7 n/a 166 39.0
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Table 3
3D-CFC characterization of Example 1 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5 Mx 105 Avg. rf
NCI f SCBf
Fraction Temp (g/mol) (g/mol) [n] ( C)
(CH3/1000C)
( C) (dL/g)
F1 30-60 0.1699 0.723 0.637 0.98 51.42 0.983
29.03
F2 60-65 0.0821 0.93 0.837 1.26 62.64 0.980
21.47
F3 65-70 0.1131 1.05 0.962 1.42 67.63 0.981
18.11
F4 70-74 0.1059 1.09 0.996 1.49 72.05 0.983
15.13
F5 74-78 0.1201 1.14 1.04 1.56 76.01 0.981
12.46
F6 78-82 0.1203 1.27 1.14 1.66 79.99 0.960
9.78
F7 82-87 0.1052 1.55 1.36 1.82 84.25 0.916
6.91
F8 87-92 0.0720 1.90 1.66 2.13 89.76 0.902
3.20
F9 92-110 0.1114 2.02 1.79 2.33 93.44 0.924
0.72
Table 4
3D-CFC characterization of Example 4 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5 Mx 105 Avg. [n] V (0c) Ncif SCBf
Fraction Temp (g/mol) (g/mol) (dL/g)
(CH3/1000C)
( C)
F1 30-60 0.1666 0.616 0.544 0.88 50.84 0.985
29.42
F2 60-65 0.0831 0.869 0.786 1.21 62.63 0.980
21.48
F3 65-70
0.1166 0.969 0.888 1.34 67.61 0.979 18.12
F4 70-74 0.1101 1.08 0.989 1.47 72.04 0.978
15.14
F5 74-78 0.1240 1.13 1.04 1.56 76.03 0.984
12.45
F6 78-82 0.1204 1.22 1.11 1.65 79.98 0.976
9.79
F7 82-88 0.1033 1.41 1.28 1.81 84.56 0.952
6.70
F8 88-92 0.0456 1.70 1.54 2.10 90.06 0.938
3.00
F9 92-110 0.1304 2.06 1.89 2.49 94.45 0.951
0.04
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Table 5
3D-CFC characterization of Comparative 1 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5 Mx 105
Avg. [n] Tf NCI f SCBf
Fraction Temp (g/mol) (g/mol) (dL/g) ( C) (CH3/1000C)
( C)
F1 30-65 0.1921 0.604 0.517 0.87 54.98 1.00 26.63
F2 65-70 0.0928 0.878 0.785 1.25 67.67 1.00 18.08
F3 70-74 0.1094 1.05 0.954 1.46 72.11 0.994 15.09
F4 74-78 0.1511 1.15 1.06 1.61 76.09 1.00 12.41
F5 78-82 0.1631 1.23 1.14 1.72 79.96 1.00 9.8
F6 82-88 0.1266 1.40 1.28 1.90 84.39 1.00 6.82
F7 88-92 0.0549 1.71 1.55 2.23 90.20 0.989 2.9
F8 92-110 0.1100 1.95 1.78 2.50 93.75 1.00 0.51
Table 6
3D-CFC characterization of Comparative 3 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5 Mx 105
Avg. [n] Tf NCI f SCBf
Fraction Temp (g/mol) (g/mol) (dL/g) ( C) (CH3/1000C)
( C)
F1 30-65 0.1527 0.238 0.222 0.48
57.43 0.998 24.98
F2 65-70 0.1059 0.514 0.480 0.87
67.73 0.997 18.04
F3 70-73 0.1133 0.884 0.817 1.30
71.64 0.995 15.41
F4 73-75 0.1408 1.31 1.23 1.77 74.09 1.000 13.76
F5 75-76 0.0783 1.53 1.44 2.00 75.51 0.996 12.80
F6 76-77 0.1169 1.54 1.47 2.03 76.50 0.997 12.13
F7 77-78 0.0977 1.35 1.27 1.84 77.48 0.993 11.47
F8 78-85 0.1432 1.09 1.01 1.57 79.49 0.996 10.12
F9 85-140 0.0512 2.15 2.04 2.75 92.16 0.995 1.58
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Table 7
Physical and molecular characteristics of Comparatives 3, 4 and 5
Cornparative Comparative Cornparative
Resin Code
3 4 5
Comonomer 1-octene 1-octene 1-octene
Density (g/cm3) 0.9162 0.9018 0.9028
12 (dg/min) 0.99 1.06 0.91
S.Ex. 1.27 1.41 1.44
MFR 30.8 29.5 31.1
Mn (g/mol) 33358 40133 45124
Mw (g/mol) 102603 83226 84299
M( g/mol) 238331 148667 137468
Mw/Mn 3.08 2.07 1.87
Mz/Mw 2.32 1.79 1.93
CDBI50(%) 77.5 89.5 92.5
FTIR CoMo (mol%) 2.9 4.6 4.5
FTIR Branch Freq (CH3/1000C) 14.6 23.2 22.3
Unsaturation Internal/100C 0.021 0.006 0.014
Unsaturation Side Chain/100C 0.002 0.001 0.009
Unsaturation Terminal/100C 0.006 0.008 0.009
Hexane Extractables, Plaque
0.48 0.58 n/a
(%)
Ti (ppm), N.A.A. 0.30 0.30 n/a
Al (ppm), N.A.A. 9.1 1.9 n/a
Mg (ppm), N.A.A. n/d 2.0 n/a
Cl (ppm), N.A.A. 0.47 0.9 n/a
Hf (ppm), N.A.A. n/a n/a 2.2
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Table 8
3D-CFC characterization of Comparative 4 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5
Mx 105 Avg. [n] r NCI SCEif
Fraction Temp (g/mol) (g/mol) (dL/g) ( C)
(CH3/1000C)
( C)
F1 30-50 0.1123 0.459
0.439 0.70 44.18 0.944 33.91
F2 50-55 0.1024 0.675
0.654 0.97 52.76 0.948 28.13
F3 55-58 0.0896 0.827
0.804 1.15 56.60 0.943 25.54
F4 58-60 0.0726 0.87 0.850 1.21 59.05
0.945 23.89
F5 60-62 0.108 0.978 0.956 1.32 61.04
0.942 22.55
F6 62-64 0.1386 1.080 1.05 1.44 63.03
0.947 21.21
F7 64-66 0.1435 1.110 1.09 1.49 64.99
0.948 19.89
F8 66-68 0.1111 1.100
1.08 1.47 66.93 0.94 18.58
F9 68-110 0.1218 1.120 1.07 1.50 69.99
0.944 16.52
Table 9
3D-CFC characterization of Comparative 5 and Non-Comonomer Index
3D-CFC Elution (wt.fr) M, x10-5 Mx l05 Avg. -rf (
C) NCI f SCBf
Fraction Temp (g/mol) (g/mol) [n]
(CH3/1000C)
( C) (dL/g)
F1 30-55 0.1153 0.377 0.359 0.64
48.57 0.976 30.95
F2 55-60 0.1609 0.742 0.721 1.10 57.86
0.976 24.69
F3 60-63 0.1725 0.964 0.941 1.35 61.62
0.973 22.16
F4 63-65 0.1650 1.12 1.10 1.53 64.05
0.974 20.52
F5 65-67 0.2053 1.11 1.090 1.54 65.98
0.979 19.22
F6 67-110 0.1810 0.895 0.866 1.31 68.70
0.973 17.39
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Table 10a
Mixed catalyst Continuous solution polymerization process parameters
employing an intermediate branching catalyst formulation and a homogeneous
catalyst formulation: Examples 5, 10 and 11
Example Example
Sample Code Example 5
11
Reactor Mode Series Series Parallel
R1 Catalyst (homogeneous) PIC-1 CpF-2 CpF-2
R2 Catalyst (intermediate branching) In-line In-line In-line
R1 (i) (ppm) 0.12 0.380 0.380
R1 (ii)/(i) mole ratio 100 64.2 48
R1 (iv)/(ii) mole ratio 0 0.16 0.15
R1 (iii)/(i) mole ratio 1.1 1.20 1.36
R2 (vii) (ppm) 4.2 5.16 7.24
R2 (vi)/(v) (mol ratio) 2.07 2.07 2.07
R2 (viii)/(vii) (mol ratio) 1.35 1.35 1.35
R2 (ix)/(vii) (mol ratio) 0.35 0.35 0.35
component (vii), stream 10c (g/h) 326.9 354.0 179.2
component (viii), stream 10h (g/h) 89.7 104.4 52.6
component (vi), stream 10b (g/h) 388.8 417.4 211.1
components ((v)+(ix))1, stream 10a (g/h) 391.8 389.4 201.6
solvent stream 10a' (g/h) 3200 2900 2470
solvent stream 10b' (g/h) 3300 3100 29900
solvent stream 10c' (g/h) 4700 4900 4900
solvent stream 10f' (g/h) 38600 37700 37600
1 R1 catalyst component (i) was PIC-1 or CpF-2
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Table 10b
Additional solution process parameters for Examples 5, 10 and 11
Example Example
Sample Code Example 5
10 11
R1 total solution rate (kg/h) 358.8 387.3 352.0
R2 total solution rate (kg/hr) 241.2 162.7 198.0
Total Solution Rate (kg/hr) 600 550 550
R1 ethylene concentration (wt%) 10.3 9.8 11.1
R2 ethylene concentration (wt%) 15.4 13.8 13.2
R3 ethylene concentration (wt%) 15.4 13.8 13.2
ESR1 (%) 40 50.0 60.0
EsR2 (%) 60 50.0 40.0
ES R3 0 0.0 0.0
(1-octene/ethylene) total (wt.fr.) 0.67 0.31 0.29
CSR1 (%) 100 67 100
CSR2 (%) 0 33 0.0
CSR3(%) 0 0 0
R1 Catalyst Inlet Temperature ( C) 32.5 30.6 31.4
R1 Inlet Temperature ( C) 30.0 30.0 30.0
R1 Mean Temperature ( C) 141 141.1 154.7
H2R1 (ppm) 0.2 5.35 6.82
R2 Catalyst Inlet Temperature ( C) 38.6 37.9 37.8
R2 inlet temp ( C) 30 50 50
R2 Mean Temp ( C) 206 197.7 205.7
H2R2 (ppm) 3.5 18 2.78
R3 volume (L) 18 2.2 2.2
R3 inlet temp ( C) 130.0 130 130
R3 exit temp ( C) 214.0 197.7 181.6
H2R3 (ppm) 0.0 0 0
QT (%) 93.1 90.8 89.9
Production Rate (kg/hr) 94.8 72.0 61.5
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Table 11
Physical and molecular characteristics of Examples 5-7 and Comparative 6
Resin Code Example 5 Example
6 Example 7 Comp. 6
Comonomer 1-octene 1-octene
1-octene 1-octene
Density (g/cm3) 0.9160 0.9124 0.9210 0.9189
12 (dg/min) 1.00 0.92 0.85 0.89
S.Ex. 1.26 1.25 1.23 1.36
MFR 27.2 23.4 22.1 30.4
Mn (g/mol) 28655 42765 39503 42399
Mw (g/mol) 104966 107517 111582 110940
Mz (g/m01) 251646 230247 278862 237733
Mw/Mn 3.66 2.51 2.82 2.62
Mz/Mw 2.40 2.14 2.50 2.14
CDBI50(%) 51.4 59.7 51.9 24.5
FTIR CoMo (mol%) 2.9 3.6 2.5 2.8
FTIR Branch Freq
14.5 18.1 12.7 14.1
(CH3/1000C)
Unsat. Internal/100C 0.009 0.008 0.004 0.004
Unsat. Side Chain/100C 0.005 0.003 0.003 0.002
Unsat. Terminal/100C 0.048 0.029 0.03 0.021
Hexane Extractables,
0.72 n/a n/a 0.42
Plaque (%)
Ti (ppm), N.A.A. 7.4 7.6 n/a 2.2
Al (ppm), N.A.A. 97.0 104 n/a 11.3
Mg (ppm), N.A.A. 85.8 90.1 n/a 14.6
Cl (ppm), N.A.A. 180 190 n/a 48.8
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Table 12
3D-CFC characterization of Example 5 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5 M, x10-5
Avg. Tf NCI f SCBf
Fraction Temp (g/mol) (g/mol) [n] ( C)
(CH3/100
( C) (d L/g) OC)
F1 30-60 0.1373 0.441 0.382 0.69
52.06 0.985 28.60
F2 60-65 0.0677 0.660 0.596 0.99
62.66 0.990 21.46
F3 65-69 0.0793 0.832 0.767 1.21 67.18
0.986 18.41
F4 69-71 0.0533 1.033 0.959 1.44 70.08
0.988 16.46
F5 71-73 0.0992 1.406 1.321 1.84 72.10
0.992 15.10
F6 73-74 0.0465 1.587 1.499 2.03 73.51 0.988 14.15
F7 74-75 0.0800 1.736 1.655 2.19
74.50 0.993 13.48
F8 75-76 0.0767 1.621 1.537 2.07
75.48 0.986 12.82
F9 76-78 0.1218 1.308 1.220 1.75 76.92
0.982 11.85
F10 78-88 0.1551 1.036 0.924 1.39 81.49 0.935 8.77
F11 88-140 0.0831 1.506 1.322 1.75 91.91 0.873 1.75
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Table 13
3D-CFC characterization of Example 6 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5 M, x10-5 Avg.
Tf ( C) NCI f SCBf
Fraction Temp (g/mol) (g/mol) [n]
(CH3/1000C)
( C) (dlig)
F1 30-51
0.0993 0.618 0.564 0.88 44.95 0.983 33.39
F2 51-56
0.0904 0.894 0.858 1.23 53.82 0.982 27.41
F3 56-59
0.0855 1.058 1.020 1.43 57.59 0.987 24.87
F4 59-61 0.0680 1.118 1.139 1.56 60.01 0.984 23.24
F5 61-63
0.0858 1.276 1.232 1.66 61.96 0.983 21.93
F6 63-65
0.0637 1.198 1.147 1.58 63.95 0.978 20.59
F7 65-70
0.1094 1.062 0.996 1.44 67.36 0.974 18.29
F8 70-78
0.1375 1.172 1.064 1.49 74.00 0.931 13.82
F9 78-88 0.1109 1.296 1.141 1.62 82.17 0.931 8.31
F10 88-94 0.0765 1.765 1.554 2.07 90.95 0.920 2.40
F11 94-140 0.0729 2.107 1.902 2.45 94.51 0.931 0.00
Table 14
3D-CFC characterization of Example 7 and Non-Comonomer Index
3D-CFC Elution (wt.fry Mw x10-5 Mx 105 Avg. [n] V NCI SCBf
Fraction Temp (g/mol) (g/mol)
(dL/g) ( C) (CH3/1000
( C) C)
F1 30-60 0.1188 0.730 0.674 1.05
53.82 0.994 27.41
F2 60-64 0.0977 1.078 1.041 1.49
62.23 0.994 21.75
F3 64-67 0.1226 1.290 1.255 1.72
65.54 0.991 19.52
F4 67-70 0.1085 1.265 1.222 1.71
68.40 0.989 17.59
F5 70-75 0.1024 1.055 0.985 1.48
72.33 0.985 14.94
F6 75-80 0.1031 1.016 0.928 1.45
77.66 0.988 11.35
F7 80-85 0.1138 1.135 1.030 1.56
82.40 0.967 8.16
F8 85-90 0.0555 1.269 1.122 1.66
87.22 0.945 4.91
F9 90-93 0.0505 1.538 1.369 1.94
91.88 0.936 1.77
F10 93-140 0.1272 1.813 1.641 2.23 94.24 0.944 0.18
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Table 15
3D-CFC characterization of Comparative 6 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f M, x10-5 Mx l05 Avg. [n] Tf (0c) NCI f SCBf
Fraction Temp (g/mol) (g/mol) (dL/g)
(CH3/1000
( C) C)
F1 30-55 0.1268 0.974 0.911 1.22
48.47 0.950 31.02
F2 55-58 0.0713 1.708 1.640 1.94
56.66 0.954 25.50
F3 58-60 0.0779 2.004 1.940 2.19
59.09 0.940 23.86
F4 60-62 0.1005 2.082 2.015 2.26 60.98 0.941
22.59
F5 62-68 0.0800 1.504 1.381 1.77
63.86 0.953 20.65
F6 68-80 0.1170 0.525 0.466 0.85 75.21 0.958 13.00
F7 80-90 0.1743 0.639 0.586 1.04 84.97 0.955
6.43
F8 90-94 0.1138 0.860 0.785 1.30 92.54 0.944
1.33
F9 94-110 0.1385 1.098 1.034 1.59 94.51 0.939
0.0
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Table 16
Physical and molecular characteristics of Examples 10 and 11; relative to
Comparatives 7 and 8
Example Example Comparative Comparative
Resin Code
11 7 8
Comonomer 1-octene 1-
octene 1-octene 1-octene
Density (g/cm3) 0.9170 0.9177 0.9045 0.9069
12 (dg/min) 0.70 0.92 0.93 1.12
S.Ex. 1.40 1.38 1.58 1.52
MFR 34.7 29.7 57.0 43.5
Mn (g/mol) 35536 41838 27546 36041
Mw (g/mol) 106261 93315 91509 90425
Mz (g/mol) 217647 161131 246101 220700
Mw/Mn 2.99 2.99 3.32 2.51
M2/Mw 2.05 1.73 2.69 2.44
CDBI50 (%) 49.8 57.0 89.3 92.4
FTIR CoMo (mol%) 3.3 4.0 4.7 4.2
FTIR Branch Freq
16.7 19.8 23.4 20.9
(CH3/1000C)
Unsat. Internal/100C 0.004 0.005 0.011 0.011
Unsat. Side Chain/100C 0.001 0.004 0.006 0.006
Unsat. Terminal/100C 0.025 0.025 0.008 0.007
Hexane Extractables,
0.21 0.41 n/a n/a
Plaque (%)
Ti (ppm), N.A.A. 8.45 4.24 n/d n.d.
Al (ppm), N.A.A. 187 160 - -
Mg (ppm), N.A.A. 389 327 - -
CI (ppm), N.A.A. 120 69.5 - -
Hf (ppm), N.A.A. 0.50 0.54 1.76 1.98
5
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Table 17
3D-CFC characterization of Example 10 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f x10-5 Mx l05 Avg. [n] Tf NCI f SCBf
Fraction Temp (g/mol) (g/mol) (dL/g) ( C)
(CH3/100
( C) OC)
F1 30-50 0.0812 0.983 0.932 1.23 44.64
0.961 33.60
F2 50-54 0.0957 1.582 1.532 1.81 52.27
0.955 28.46
F3 54-56 0.0666 1.884 1.835 2.10 55.09
0.955 26.56
F4 56-58 0.1395 1.991 1.944 2.22 57.05
0.963 25.24
F5 58-60 0.1096
1.988 1.934 2.21 58.93 0.954 23.97
F6 60-68 0.0582 1.467 1.346 1.70 61.96
0.943 21.93
F7 68-80 0.0777
0.364 0.314 0.64 75.67 0.955 12.69
F8 80-90 0.2018
0.564 0.499 0.89 85.34 0.915 6.18
F9 90-110 0.1696 1.044 0.892 1.23 93.01
0.814 1.01
Table 18
3D-CFC characterization of Example 11 and Non-Comonomer Index
3D-CFC Elution (wt.fr.)f Mw x10-5 Mx 105 Avg. [n] Tf ( C)
NCI f SCBf
Fraction Temp (g/mol) (g/mol) (d Lig)
(CH3/100
( C) OC)
F1 30-45 0.1250 0.705 0.680 0.94 40.78 0.943 36.20
F2 45-50 0.1581 1.156 1.128 1.41 47.83 0.944 31.45
F3 50-53 0.1496 1.368 1.341 1.61 51.60 0.937 28.91
F4 53-55 0.1028 1.431 1.397 1.67 53.99 0.931 27.30
F5 55-62 0.1044 1.357 1.321 1.62 56.60 0.929 25.54
F6 62-94 0.0586 0.271 0.203 0.49 86.11 0.962 5.66
F7 94-97 0.0938 0.565 0.504 0.97 94.51 0.955 0.0
F8 97-110 0.2078 1.209 1.114 1.71 98.00 0.957 0.0
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Table 19a
Reference resins (linear ethylene interpolvmers) having undetectable levels of
Long Chain Branching (LCB)
Reference Mv [11] SCBD ZSV
Mw/Mn A
Resins (g/mole) (d Lig) CH3#/1000C
(poise)
Resin 1 1.06E+05 1.672 2.14 1.9772 10.5 7.81E+04
Resin 2 1.11E+05 1.687 2.00 1.9772 11.2 7.94E+04
Resin 3 1.06E+05 1.603 1.94 1.9772 15.9 7.28E+04
Resin 4 1.07E+05 1.681 1.91 1.9772 11.0 8.23E+04
Resin 5 7.00E+04 1.192 2.11 1.9772 13.7 1.66E+04
Resin 6 9.59E+04 1.497 1.88 1.9772 12.6 5.73E+04
Resin 7 1.04E+05 1.592 1.85 1.9772 12.8 6.60E+04
Resin 8 5.09E+04 0.981 2.72 2.1626 0.0 6.42E+03
Resin 9 5.27E+04 0.964 2.81 2.1626 0.0 6.42E+03
Resin 10 1.06E+05 1.663 1.89 1.1398 13.3 7.69E+04
Resin 11 1.10E+05 1.669 1.81 1.1398 19.3 7.31E+04
Resin 12 1.07E+05 1.606 1.80 1.1398 27.8 6.99E+04
Resin 13 6.66E+04 1.113 1.68 2.1626 17.8 1.39E+04
Resin 14 6.62E+04 1.092 1.76 2.1626 21.4 1.45E+04
Resin 15 6.83E+04 1.085 1.70 2.1626 25.3 1.44E+04
Resin 16 7.66E+04 1.362 2.51 2.1626 4.0 3.24E+04
Resin 17 6.96E+04 1.166 2.53 2.1626 13.9 2.09E+04
Resin 18 6.66E+04 1.134 2.54 2.1626 13.8 1.86E+04
Resin 19 5.81E+04 1.079 2.44 2.1626 5.8 1.10E+04
Resin 20 7.85E+04 1.369 2.32 2.1626 3.7 3.34E+04
Resin 21 6.31E+04 1.181 2.26 2.1626 4.3 1.61E+04
Resin 22 7.08E+04 1.277 2.53 2.1626 3.6 2.58E+04
Resin 23 9.91E+04 1.539 3.09 2.1626 14.0 8.94E+04
Resin 24 1.16E+05 1.668 3.19 2.1626 13.3 1.32E+05
Resin 25 1.12E+05 1.689 2.71 2.1626 12.8 1.38E+05
Resin 26 1.14E+05 1.690 3.37 2.1626 8.0 1.48E+05
Resin 28 1.00E+05 1.547 3.33 2.1626 14.1 9.61E+04
Resin 30 1.04E+05 1.525 3.73 2.1626 13.4 1.10E+05
Resin 31 1.10E+05 1.669 3.38 2.1626 8.7 1.26E+05
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Resin 32 1.09E+05 1.539 3.42 2.1626 13.4 1.07E+05
Resin 33 8.04E+04 1.474 5.29 2.1626 1.7 7.60E+04
Resin 34 8.12E+04 1.410 7.64 2.1626 0.9 9.11E+04
Resin 35 7.56E+04 1.349 9.23 2.1626 1.0 9.62E+04
Resin 36 7.34E+04 1.339 8.95 2.1626 1.1 1.00E+05
Resin 37 1.01E+05 1.527 3.76 2.1626 13.3 1.11E+05
Table 19b
Reference resins (linear ethylene interpolymers) having undetectable levels of
Long Chain Branching (LCB)
Reference Log ZSVc Log IVc Sh Sv LCBF
Resins (log(poise)) log(dL/g) (dimensionless) (dimensionless) (dimensionless)
Resin 1 4.87E+00 2.46E-01 -5.77E-02 -1.21E-02 3.49E-04
Resin 2 4.90E+00 2.52E-01 -5.39E-02 -1.13E-02 3.05E-04
Resin 3 4.87E+00 2.41E-01 -2.46E-02 -5.16E-03 6.33E-05
Resin 4 4.93E+00 2.50E-01 -9.46E-03 -1.99E-03 9.41E-06
Resin 5 4.20E+00 1.07E-01 -6.37E-02 -1.34E-02 4.26E-04
Resin 6 4.78E+00 2.04E-01 5.83E-02 1.22E-02 3.57E-04
Resin 7 4.85E+00 2.31E-01 -1.73E-03 -3.65E-04 3.16E-07
Resin 8 3.69E+00 -8.43E-03 -2.17E-02 -4.55E-03 4.93E-05
Resin 9 3.68E+00 -1.58E-02 1.21E-04 2.44E-05 1.47E-09
Resin 10 4.91E+00 2.38E-01 2.19E-02 4.60E-03
5.04E-05
Resin 11 4.90E+00 2.48E-01 -2.96E-02 -6.21E-03 9.17E-05
Resin 12 4.88E+00 2.42E-01 -1.99E-02 -4.19E-03
4.17E-05
Resin 13 4.21E+00 9.14E-02 2.36E-02 4.96E-03
5.86E-05
Resin 14 4.21E+00 9.22E-02 1.89E-02 3.97E-03
3.75E-05
Resin 15 4.22E+00 1.00E-01 -9.82E-03 -2.06E-03
1.01E-05
Resin 16 4.42E+00 1.44E-01 -1.23E-02 -2.59E-03 1.60E-05
Resin 17 4.23E+00 1.01E-01 -4.64E-03 -9.75E-04 2.26E-06
Resin 18 4.18E+00 8.91E-02 1.66E-03 3.47E-04 2.87E-07
Resin 19 3.97E+00 4.73E-02 -1.09E-02 -2.29E-03 1.25E-05
Resin 20 4.47E+00 1.45E-01 2.28E-02 4.78E-03 5.44E-05
Resin 21 4.16E+00 8.23E-02 1.78E-02 3.73E-03 3.31E-05
Resin 22 4.32E+00 1.15E-01 2.45E-02 5.14E-03 6.30E-05
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Resin 23 4.78E+00 2.22E-01 -2.25E-02 -4.73E-03 5.31E-05
Resin 24 4.94E+00 2.56E-01 -3.13E-02 -6.57E-03 1.03E-04
Resin 25 5.02E+00 2.59E-01 3.91E-02 8.21E-03 1.60E-04
Resin 26 4.97E+00 2.48E-01 3.94E-02 8.27E-03 1.63E-04
Resin 28 4.79E+00 2.24E-01 -3.13E-02 -6.57E-03 1.03E-04
Resin 30 4.80E+00 2.18E-01 1.47E-02 3.08E-03 2.26E-05
Resin 31 4.90E+00 2.44E-01 -1.40E-02 -2.94E-03 2.06E-05
Resin 32 4.82E+00 2.23E-01 1.27E-02 2.66E-03 1.69E-05
Resin 33 4.51E+00 1.72E-01 -6.37E-02 -1.34E-02 4.26E-04
Resin 34 4.45E+00 1.52E-01 -2.68E-02 -5.62E-03 7.52E-05
Resin 35 4.40E+00 1.33E-01 1.55E-02 3.26E-03 2.53E-05
Resin 36 4.43E+00 1.30E-01 5.82E-02 1.22E-02 3.55E-04
Resin 37 4.80E+00 2.17E-01 1.77E-02 3.71E-03 3.28E-05
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Table 20
Long Chain Branching Factor (LCBF) of ethvIene/1-octene interpolvmers:
Examples 1, 4-7, 10 and 11
Example Example Example Example Example Example Example
Sample
1 4 5 6 7 10 11
Mv
109000 104000 101000 111000 109000 104000 102000
(g/mole)
En]
1.570 1.531 1.497 1.565 1.600 1.433
1.410
(d Lig)
Mw/Mn 3.61 3.80 3.77 2.51 3.18 2.99
2.23
A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626
2.1626
SCB
13.5 13.7 14.5 18.1 12.7 16.7
19.8
(CH3#/1000C)
ZSV
107000 106000 857000 103000 107000 247000 158000
(poise)
Log ZSVc
4.80 4.78 4.69 4.93 4.85 5.24
5.16
(log (poise))
Log IVc
0.231 0.220 0.212 0.241 0.236 0.202
0.202
(log (d Lig))
Sh
(dimension- -0.0487 -0.0202 -0.0721 0.0250 -0.0240 0.527 0.442
less)
Sv
(dimension- -0.0102 -0.0042 -0.0152 0.00526 -0.00505 0.111 0.00929
less)
LCBF
(dimension- 2.49E-04 4.28E-05 5.47E-04 6.58E-05 6.06E-05 0.0291 0.0205
less)
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Table 21
Long Chain Branching Factor (LCBF) of ethvIene/1-octene interpolvmers:
Comparatives 1 and 3-8
Sample Comp. 1 Comp 3 Comp 4 Comp 5 Comp 6 Comp 7 Comp 8
Mv
102000 94200 87900 88000 104000 91100 86500
(g/mole)
En]
1.553 1.474 1.300 1.284 1.507 1.286 1.245
(d L/g)
Mw/Mn 3.80 3.08 1.88 1.87 2.79 3.32 2.51
A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626
SCB
13.2 14.6 23.2 22.3 14.1 23.4 20.9
(CH3#/1000C)
ZSV
118000 89790 151000 180000 155000 257000 190000
(poise)
Log ZSVe
4.83 4.79 5.20 5.28 5.06 5.22 5.19
(log (poise))
Log IVc
0.224 0.205 0.174 0.167 0.215 0.172 0.151
(log(dL/g))
Sh
0.00830 0.0617 0.622 0.732 0.290 0.646 0.718
(dimensionless)
Sv
0.00174 0.0130 0.131 0.1054 0.0609 0.136 0.151
(dimensionless)
LCBF
7.23E-6 4.00E-4 0.0406 0.0563 0.00883 0.0438 0.0541
(dimensionless)
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Table 22
Blown film manufacturing conditions Examples 1 and 3 and Comparative 2
Resin Code
Example 2 Example 3 Example 3 Comp. 2 Comp. 2
Film Thickness (mil) 1 2 4 2 4
Output (lb/hr) 40.0 40.2 67.5 40.6 62.0
Die Gap (mil) 35 35 35 35 35
BUR 2.5:1 2.5:1 2.5:1 2.5:1 2.5:1
Barrel Zone 1 ( F) 420 417 418 422 418
Barrel Zone 2 ( F) 400 400 401 400 400
Barrel Zone 3 ( F) 400 400 400 400 400
Adapter Zone 4 ( F) 400 400 400 400 400
Die Body Zone 5 ( F) 420 420 420 420 420
Die Body Zone 6 ( F) 420 420 427 429 437
Die Lip Zone 7 ( F) 440 440 440 440 440
Melt Temperature
438 433 469 447 479
( F)
Current (Amp) 32.0 34.0 41.1 34.0 41.0
Voltage (V) 140 139 235 140 235
Pressure High (psi) 2835 2620 3310 3030 3700
Pressure Low (psi) 2755 2510 3250 2920 3650
Avg. Pressure (psi) 2795 2565 3280 2975 3675
Screw Speed (rpm) 87.8 87.5 157.4 88.9 157.5
Air Temperature ( F) 51 48 50 n/a 49
Frostline Height
7.0 8.25 17 9.0 16.5
(inch)
Line Speed (ft/min) 71.7 35.4 30.0 35.5 30.0
Screw Type maddox maddox maddox maddox
maddox
Specific Output
0.46 0.46 0.43 0.46 0.39
(lb/hr/rpm)
Specific Power
1.25 0.12 1.64 1.19 1.51
((lb/hr)/amp)
Specific Energy
(W/lb/hr) 112.0 117.6 143.1 117.2 155.40
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Table 23
Blown film physical properties Examples 1 and 3 and Comparative 2
Sample Code Example
2 Example 3 Example 3 Comp. 2 Comp. 2
Density (g/cm3) 0.9208 0.9200 0.9200 0.9182 0.9208
12 (dg/min) 1.02 0.96 0.96 0.98 0.97
Thickness (mil) 1.00 2.04 3.99 2.07 3.65
Dart Impact, F50 (g) 325 365 256 175 150
Tear-MD (g/mil) 318 370 491 438 429
Tear - TD (g/mil) 638 558 604 646 729
Tensile Strength
55.4 51.4 48.8 49.4 45.8
@ Break MD (MPa)
Tensile Strength
55.7 51.6 44 45 45.4
@ Break TD (MPa)
Tensile Yield Strength
10.2 10.6 10.8 11.6 11.5
- MD (MPa)
Tensile Yield Strength
10.5 10.8 11.1 11.8 12
- TD (MPa)
Tensile Elongation
MD (%) 555 603 714 699 745
@ Break MD (MPa)
Tensile Elongation
TD (%) 827 716 717 696 743
@ Break MD (MPa)
Tensile Elongation
16 14 16 15 17
@ Yield MD (%)
Tensile Elongation
24 19 17 14 12
@ Yield TD (%)
Tensile Energy (J)
MD 1.96 1.84 4.02 2.27 4.04
Tensile Energy (J) TD 2.55 2.22 3.69 2.01 3.88
1% Secant Modulus
MD (MPa) 193 185 185 203 215
1% Secant Modulus
TD (MPa) 224 213 214 241 259
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2% Sec. Modulus MD
163 160 161 174 184
(MPa)
2% Sec. Modulus TD
184 176 182 199 213
(M Pa)
Film Haze (%) 5 8 13 7 12
Film Gloss @ 450 78 69 69 73 73
Hot Tack Strength (N) n/a 5.70 5.61 4.58 5.07
Hot Tack Onset @0.5
n/a 87.0 86.9 87.0 90.3
N ( C)
Hot Tack Onset @
n/a 90.5 90.3 92.0 91.7
1.0 N ( C)
Heat Seal
Temperature @ Max.
n/a 125 110 130 110
Heat Seal Strength
( C)
Film Hexane
Extractables n/a n/a 0.76 n/a 0.70
(3.5mi1 film)
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Table 24
Blown film physical properties Example 6 relative to Comparative 9; 1.0 mil
monolayer film
Sample Code Example 6 Comparative 9
Density (g/cm3) 0.919 0.919
12 (dg/min) 0.85 0.85
Tear - MD (g/mil) 305 275
Tear - TD (g/mil) 589 470
Dart Impact, F50 (g) 824 475
Tensile Strength
@ Break MD (MPa) 56 49
Tensile Strength
@ Break TD (MPa) 47 40
Tensile Yield Strength
- MD (MPa) 9.5 9.5
Tensile Yield Strength
- TD (MPa) 9.3 9.8
Tensile Elongation MD (%)
@ Break MD (MPa) 572 520
Tensile Elongation TD (%)
@ Break MD (MPa) 715 700
1% Secant Modulus MD
(MPa) 159 165
1% Secant Modulus TD
(MPa) 167 175
Film Haze (%) 11 22
Film Gloss 45 73 35
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