U.S. patent application number 14/950943 was filed with the patent office on 2016-03-17 for novel high clarity low haze compositions.
The applicant listed for this patent is Chevron Phillips Chemical Company LP. Invention is credited to Brooke A. Gill, Elizabeth M. Lanier, J. Todd Lanier, Guylaine St. Jean, Qing Yang.
Application Number | 20160075803 14/950943 |
Document ID | / |
Family ID | 53506674 |
Filed Date | 2016-03-17 |
United States Patent
Application |
20160075803 |
Kind Code |
A1 |
St. Jean; Guylaine ; et
al. |
March 17, 2016 |
Novel High Clarity Low Haze Compositions
Abstract
A first embodiment which is a bimodal polymer having a weight
fraction of a lower molecular weight (LMW) component ranging from
about 0.25 to about 0.45, a weight fraction of a higher molecular
weight (HMW) component ranging from about 0.55 to about 0.75 and a
density of from about 0.931 g/cc to about 0.955 g/cc which when
tested in accordance with ASTM D1003 using a 1 mil test specimen
displays a haze characterized by equation: %
Haze=2145-2216*Fraction.sub.LMW-181*a molecular weight distribution
of the LMW component (MWD.sub.LMW)-932*a molecular weight
distribution of the HMW component
(MWD.sub.HMW)+27*(Fraction.sub.LMW*MWD.sub.LMW)+1019*(Fraction.sub.LMW*MW-
D.sub.HMW)+73*(MWD.sub.LMW*MWD.sub.HMW) wherein fraction refers to
the weight fraction of the component in the polymer as a whole.
Inventors: |
St. Jean; Guylaine;
(Bartlesville, OK) ; Lanier; Elizabeth M.;
(Bartlesville, OK) ; Lanier; J. Todd;
(Bartlesville, OK) ; Yang; Qing; (Bartlesville,
OK) ; Gill; Brooke A.; (Glen Carbon, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chevron Phillips Chemical Company LP |
The Woodlands |
TX |
US |
|
|
Family ID: |
53506674 |
Appl. No.: |
14/950943 |
Filed: |
November 24, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14733457 |
Jun 8, 2015 |
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14950943 |
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14284704 |
May 22, 2014 |
9079993 |
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14733457 |
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Current U.S.
Class: |
502/153 ;
502/152; 502/155; 556/53 |
Current CPC
Class: |
C08F 4/65904 20130101;
C08J 5/18 20130101; C08L 2314/06 20130101; C08F 210/16 20130101;
C08L 2203/16 20130101; C08F 210/16 20130101; B01J 19/2415 20130101;
B01J 2219/24 20130101; C08F 4/65916 20130101; C08F 4/65927
20130101; C08F 4/65925 20130101; C08L 2205/025 20130101; B01J
19/2455 20130101; C08J 2323/06 20130101; B01J 19/24 20130101; C08F
10/02 20130101; Y10T 428/1397 20150115; C08F 4/65912 20130101; Y10T
428/139 20150115; C08L 23/0815 20130101; C08F 210/16 20130101; C08L
23/0815 20130101; C08F 110/02 20130101; C08F 2500/07 20130101; C08F
210/14 20130101; C08F 2500/12 20130101; C08F 2500/04 20130101; C08L
23/0815 20130101; C08F 2500/26 20130101 |
International
Class: |
C08F 210/16 20060101
C08F210/16 |
Claims
1. A metallocene catalyst compound having a formula:
(X.sup.1R.sup.1)(X.sup.2R.sup.2.sub.2)(X.sup.3)(X.sup.4)M.sup.1,
wherein: (X.sup.1) is cyclopentadienyl, indenyl, or fluorenyl;
(X.sup.2) is fluorenyl; (X.sup.3) and (X.sup.4) are independently
an aliphatic group, an aromatic group, a cyclic group, a
combination of aliphatic and cyclic groups, a substituted
derivative of an aliphatic group, a substituted derivative of an
aromatic group, a substituted derivative of a cyclic group, a
substituted derivative of a combination of aliphatic and cyclic
groups, an unsaturated aliphatic group having from 1 to about 20
carbon atoms, or a halide; R.sup.1 is H or an unsaturated aliphatic
group having from 3 to about 10 carbon atoms; R.sup.2 is H, an
alkyl group having from 1 to about 12 carbon atoms, or an aryl
group; and M.sup.1 is Zr or Hf; wherein (X.sup.1) and (X.sup.2) are
connected by a disubstituted bridging group comprising a first
substituent which is an aromatic group or an unsaturated aliphatic
group having from 1 to about 20 carbon atoms, and a second
substituent which is an aromatic group or an unsaturated aliphatic
group having from 1 to about 20 carbon atoms.
2. The metallocene catalyst compound of claim 1, wherein the first
substituent is a phenyl group.
3. The metallocene catalyst compound of claim 1, wherein the second
substituent is a phenyl group, an alkyl group, a butenyl group, a
pentenyl group, or a hexenyl group.
4. The metallocene catalyst compound of claim 1, wherein the second
substituent is an unsaturated aliphatic group having from 3 to
about 10 carbon atoms.
5. The metallocene catalyst compound of claim 1, wherein the
disubstituted bridging group further comprises one atom bonded to
both (X.sup.1) and (X.sup.2).
6. The metallocene catalyst compound of claim 5, wherein the one
atom is carbon or silicon.
7. A polymerization catalyst composition comprising: a first
metallocene compound having a formula:
(X.sup.1R.sup.1)(X.sup.2R.sup.2.sub.2)(X.sup.3)(X.sup.4)M.sup.1,
wherein: (X.sup.1) is cyclopentadienyl, indenyl, or fluorenyl;
(X.sup.2) is fluorenyl; (X.sup.3) and (X.sup.4) are independently
an aliphatic group, an aromatic group, a cyclic group, a
combination of aliphatic and cyclic groups, a substituted
derivative of an aliphatic group, a substituted derivative of an
aromatic group, a substituted derivative of a cyclic group, a
substituted derivative of a combination of aliphatic and cyclic
groups, an unsaturated aliphatic group having from 1 to about 20
carbon atoms, or a halide; R.sup.1 is H or an unsaturated aliphatic
group having from 3 to about 10 carbon atoms; R.sup.2 is H, an
alkyl group having from 1 to about 12 carbon atoms, or an aryl
group; and M.sup.1 is Zr or Hf; wherein (X.sup.1) and (X.sup.2) are
connected by a disubstituted bridging group comprising a first
substituent which is an aromatic group or an unsaturated aliphatic
group having from 1 to about 20 carbon atoms, and a second
substituent which is an aromatic group or an unsaturated aliphatic
group having from 1 to about 20 carbon atoms; and a second
metallocene compound.
8. The polymerization catalyst composition of claim 7, wherein the
first substituent is a phenyl group.
9. The polymerization catalyst composition of claim 7, wherein the
second substituent is a phenyl group, an alkyl group, a butenyl
group, a pentenyl group, or a hexenyl group.
10. The polymerization catalyst composition of claim 7, wherein the
second substituent is an unsaturated aliphatic group having from 3
to about 10 carbon atoms.
11. The polymerization catalyst composition of claim 7, wherein the
disubstituted bridging group of the first metallocene compound
further comprises one atom bonded to both (X.sup.1) and
(X.sup.2).
12. The polymerization catalyst composition of claim 11, wherein
the one atom is carbon or silicon.
13. The polymerization catalyst composition of claim 7, the second
metallocene compound having a formula:
(X.sup.5)(X.sup.6)(X.sup.7)(X.sup.8)M.sup.2, wherein: (X.sup.5) and
(X.sup.6) are independently cyclopentadienyl, indenyl, substituted
cyclopentadienyl, or substituted indenyl; (X.sup.7) and (X.sup.8)
are independently an aliphatic group, an aromatic group, a cyclic
group, a combination of aliphatic and cyclic groups, a substituted
derivative of an aliphatic group, a substituted derivative of an
aromatic group, a substituted derivative of a cyclic group, a
substituted derivative of a combination of aliphatic and cyclic
groups, an unsaturated aliphatic group having from 1 to about 20
carbon atoms, or a halide; and M.sup.2 is Zr or Hf.
14. The polymerization catalyst composition of claim 13, wherein
each substituent on (X.sup.5) and (X.sup.6) is independently
selected from a linear or branched alkyl group, or a linear or
branched alkenyl group.
15. The polymerization catalyst composition of claim 14, wherein
the alkyl group or the alkenyl group is unsubstituted or
substituted.
16. The polymerization catalyst composition of claim 13, wherein
any substituent on (X.sup.5) and (X.sup.6) has from 1 to about 20
carbon atoms.
17. The polymerization catalyst composition of claim 7, wherein the
ratio of the first metallocene compound to the second metallocene
compound is from about 1:10 to about 10:1.
18. The polymerization catalyst composition of claim 7, further
comprising an activator.
19. The polymerization catalyst composition of claim 18, wherein
the activator is a solid oxide activator-support, a chemically
treated solid oxide, a clay mineral, a pillared clay, an exfoliated
clay, an exfoliated clay gelled into another oxide matrix, a
layered silicate mineral, a non-layered silicate mineral, a layered
aluminosilicate mineral, a non-layered aluminosilicate mineral, an
aluminoxane, a supported aluminoxane, an ionizing ionic compound,
an organoboron compound, or any combination thereof.
20. The polymerization catalyst composition of claim 7, further
comprising an organoaluminum compound.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of and claims priority to
U.S. patent application Ser. No. 14/733,457, filed on Jun. 8, 2015,
and entitled "Novel High Clarity Low Haze Compositions," which is a
continuation of and claims priority to U.S. patent application Ser.
No. 14/284,704, filed on May 22, 2014, now U.S. Pat. No. 9,079,993,
and entitled "Novel High Clarity Low Haze Compositions," each of
which is incorporated by reference herein in its entirety.
FIELD
[0002] The present disclosure relates to novel polymer compositions
and film made from same, more specifically to polyethylene
compositions for the manufacture of high clarity, low haze
films.
BACKGROUND
[0003] Polyolefins are plastic materials useful for making a wide
variety of valued products due to their combination of stiffness,
ductility, barrier properties, temperature resistance, optical
properties, availability, and low cost. In particular, polyethylene
(PE) is one of the largest volume polymers consumed in the world.
It is a versatile polymer that offers high performance relative to
other polymers and alternative materials such as glass, metal or
paper. One of the most valued products is plastic films. Plastic
films such as PE films are mostly used in packaging applications
but they also find utility in the agricultural, medical and
engineering fields.
[0004] PE films are manufactured in a variety of polymer grades
that are usually differentiated by the polymer density such that PE
films can be designated for example, low density polyethylene
(LDPE), medium density polyethylene (MDPE) and, high density
polyethylene (HDPE) wherein each density range has a unique
combination of properties making it suitable for a particular
application. Generally speaking, films prepared from MDPE and HDPE
display poor optical properties in terms of a high degree of haze
and low clarity. An ongoing need exists for MDPE and HDPE polymer
compositions having improved optical properties.
SUMMARY
[0005] Disclosed herein is a bimodal polymer having a weight
fraction of a lower molecular weight (LMW) component ranging from
about 0.25 to about 0.45, a weight fraction of a higher molecular
weight (HMW) component ranging from about 0.55 to about 0.75 and a
density of from about 0.931 g/cc to about 0.955 g/cc which when
tested in accordance with ASTM D1003 using a 1 mil test specimen
displays a haze characterized by equation: %
Haze=2145-2216*Fraction.sub.LMW-181*a molecular weight distribution
of the LMW component (MWD.sub.LMW)-932*a molecular weight
distribution of the HMW component
(MWD.sub.HMW)+27*(Fraction.sub.LMW*MWD.sub.LMW)+1019*(Fraction.sub.LMW*MW-
D.sub.HMW)+73*(MWD.sub.LMW*MWD.sub.HMW) wherein fraction refers to
the weight fraction of the component in the polymer as a whole.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] For a more complete understanding of the present disclosure
and the advantages thereof, reference is now made to the following
brief description, taken in connection with the accompanying
drawings and detailed description, wherein like reference numerals
represent like parts.
[0007] FIG. 1 is a size exclusion chromatograph overlay of samples
from example 1.
[0008] FIGS. 2 and 3 are deconvoluted size exclusion chromatographs
of samples from example 1.
[0009] FIG. 4 is a plot of the measured haze as a function of the
lower molecular weight fraction present for each sample from
example 1.
[0010] FIG. 5 is a plot of the predicted haze as a function of the
measured haze for the samples from example 1.
[0011] FIG. 6 is a plot of the measured clarity as a function of
the lower molecular weight fraction present for each sample from
example 1.
[0012] FIG. 7 is a plot of the predicted clarity as a function of
the measured clarity for the samples from example 1.
DETAILED DESCRIPTION
[0013] Disclosed herein are polyethylene (PE) polymers, PE films,
and methods of making same. Such methods may comprise preparing a
PE polymer and forming the PE polymer into a film. In an aspect,
the PE polymer comprises a multimodal PE polymer and the film
prepared therefrom may display enhanced optical properties such as
increased clarity and reduced haze.
[0014] The PE polymers of the present disclosure can be formed
using any suitable olefin polymerization method which may be
carried out using various types of polymerization reactors. As used
herein, "polymerization reactor" includes any polymerization
reactor capable of polymerizing olefin monomers to produce
homopolymers or copolymers. Such homopolymers and copolymers are
referred to as resins or polymers.
[0015] The various types of reactors include those that may be
referred to as batch, slurry, gas-phase, solution, high pressure,
tubular, or autoclave reactors. Gas phase reactors may comprise
fluidized bed reactors or staged horizontal reactors. Slurry
reactors can comprise vertical or horizontal loops. High pressure
reactors may comprise autoclave or tubular reactors. Reactor types
can include batch or continuous processes. Continuous processes
could use intermittent or continuous product discharge. Processes
can also include partial or full direct recycle of un-reacted
monomer, un-reacted co-monomer, and/or diluent.
[0016] Polymerization reactor systems of the present disclosure can
comprise one type of reactor in a system or multiple reactors of
the same or different type. Production of polymers in multiple
reactors can include several stages in at least two separate
polymerization reactors interconnected by a transfer device making
it possible to transfer the polymers resulting from the first
polymerization reactor into the second reactor. The desired
polymerization conditions in one of the reactors can be different
from the operating conditions of the other reactors. Alternatively,
polymerization in multiple reactors can include the manual transfer
of polymer from one reactor to subsequent reactors for continued
polymerization. Multiple reactor systems can include any
combination including, but not limited to, multiple loop reactors,
multiple gas reactors, a combination of loop and gas reactors,
multiple high pressure reactors, or a combination of high pressure
with loop and/or gas reactors. The multiple reactors can be
operated in series or in parallel.
[0017] According to one aspect of the disclosure, the
polymerization reactor system can comprise at least one loop slurry
reactor comprising vertical and/or horizontal loops. Monomer,
diluent, catalyst and optionally any co-monomer can be continuously
fed to a loop reactor where polymerization occurs. Generally,
continuous processes can comprise the continuous introduction of a
monomer, a catalyst, and a diluent into a polymerization reactor
and the continuous removal from this reactor of a suspension
comprising polymer particles and the diluent. Reactor effluent can
be flashed to remove the solid polymer from the liquids that
comprise the diluent, monomer and/or co-monomer. Various
technologies can be used for this separation step including but not
limited to, flashing that can include any combination of heat
addition and pressure reduction; separation by cyclonic action in
either a cyclone or hydrocyclone; or separation by
centrifugation.
[0018] A suitable slurry polymerization process (also known as the
particle form process), is disclosed, for example, in U.S. Pat.
Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235,
6,262,191, and 6,833,415, each of which is incorporated by
reference herein in its entirety.
[0019] Suitable diluents used in slurry polymerization include, but
are not limited to, the monomer being polymerized and hydrocarbons
that are liquids under reaction conditions. Examples of suitable
diluents include, but are not limited to, hydrocarbons such as
propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane,
neopentane, and n-hexane. Some loop polymerization reactions can
occur under bulk conditions where no diluent is used. An example is
polymerization of propylene monomer as disclosed in U.S. Pat. No.
5,455,314, which is incorporated by reference herein in its
entirety.
[0020] According to yet another aspect of this disclosure, the
polymerization reactor can comprise at least one gas phase reactor.
Such systems can employ a continuous recycle stream containing one
or more monomers continuously cycled through a fluidized bed in the
presence of the catalyst under polymerization conditions. A recycle
stream can be withdrawn from the fluidized bed and recycled back
into the reactor. Simultaneously, polymer product can be withdrawn
from the reactor and new or fresh monomer can be added to replace
the polymerized monomer. Such gas phase reactors can comprise a
process for multi-step gas-phase polymerization of olefins, in
which olefins are polymerized in the gaseous phase in at least two
independent gas-phase polymerization zones while feeding a
catalyst-containing polymer formed in a first polymerization zone
to a second polymerization zone. One type of gas phase reactor is
disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and 5,436,304,
each of which is incorporated by reference herein in its
entirety.
[0021] According to still another aspect of the disclosure, a high
pressure polymerization reactor can comprise a tubular reactor or
an autoclave reactor. Tubular reactors can have several zones where
fresh monomer, initiators, or catalysts are added. Monomer can be
entrained in an inert gaseous stream and introduced at one zone of
the reactor. Initiators, catalysts, and/or catalyst components can
be entrained in a gaseous stream and introduced at another zone of
the reactor. The gas streams can be intermixed for polymerization.
Heat and pressure can be employed appropriately to obtain optimal
polymerization reaction conditions.
[0022] According to yet another aspect of the disclosure, the
polymerization reactor can comprise a solution polymerization
reactor wherein the monomer is contacted with the catalyst
composition by suitable stirring or other means. A carrier
comprising an inert organic diluent or excess monomer can be
employed. If desired, the monomer can be brought in the vapor phase
into contact with the catalytic reaction product, in the presence
or absence of liquid material. The polymerization zone is
maintained at temperatures and pressures that will result in the
formation of a solution of the polymer in a reaction medium.
Agitation can be employed to obtain better temperature control and
to maintain uniform polymerization mixtures throughout the
polymerization zone. Adequate means are utilized for dissipating
the exothermic heat of polymerization.
[0023] Polymerization reactors suitable for the present disclosure
can further comprise any combination of at least one raw material
feed system, at least one feed system for catalyst or catalyst
components, and/or at least one polymer recovery system. Suitable
reactor systems for the present disclosure can further comprise
systems for feedstock purification, catalyst storage and
preparation, extrusion, reactor cooling, polymer recovery,
fractionation, recycle, storage, loadout, laboratory analysis, and
process control.
[0024] Conditions that are controlled for polymerization efficiency
and to provide resin properties include temperature, pressure, and
the concentrations of various reactants. Polymerization temperature
can affect catalyst productivity, polymer molecular weight and
molecular weight distribution. Suitable polymerization temperature
can be any temperature below the de-polymerization temperature
according to the Gibbs free energy equation. Typically, this
includes from about 60.degree. C. to about 280.degree. C., for
example, and from about 70.degree. C. to about 110.degree. C.,
depending upon the type of polymerization reactor.
[0025] Suitable pressures will also vary according to the reactor
and polymerization type. The pressure for liquid phase
polymerizations in a loop reactor is typically less than 1000 psig.
Pressure for gas phase polymerization is usually at about 200 to
about 500 psig. High pressure polymerization in tubular or
autoclave reactors is generally run at about 20,000 to about 75,000
psig. Polymerization reactors can also be operated in a
supercritical region occurring at generally higher temperatures and
pressures. Operation above the critical point of a
pressure/temperature diagram (supercritical phase) can offer
advantages.
[0026] The concentration of various reactants can be controlled to
produce resins with certain physical and mechanical properties. The
proposed end-use product that will be formed by the resin and the
method of forming that product determines the desired resin
properties. Mechanical properties include tensile, flexural,
impact, creep, stress relaxation, and hardness tests. Physical
properties include density, molecular weight, molecular weight
distribution, melting temperature, glass transition temperature,
temperature melt of crystallization, density, stereoregularity,
crack growth, long chain branching and rheological
measurements.
[0027] The concentrations of monomer, hydrogen, modifiers, and
electron donors can be utilized in producing these resin
properties. Co-monomer is used to control product density. Hydrogen
can be used to control product molecular weight. Modifiers can be
used to control product properties and electron donors affect
stereoregularity. In addition, the concentration of poisons is
minimized because poisons impact the reactions and product
properties. In an embodiment, hydrogen is added to the reactor
during polymerization. Alternatively, hydrogen is not added to the
reactor during polymerization.
[0028] The polymer or resin can be formed into various articles,
including, but not limited to pipes, bottles, toys, containers,
utensils, film products, drums, tanks, membranes, and liners.
Various processes can be used to form these articles, including,
but not limited to, film blowing and cast film, blow molding,
extrusion molding, rotational molding, injection molding, fiber
spinning, thermoforming, cast molding, and the like. After
polymerization, additives and modifiers can be added to the polymer
to provide better processing during manufacturing and for desired
properties in the end product. Additives include surface modifiers
such as slip agents, antiblocks, tackifiers; antioxidants such as
primary and secondary antioxidants; pigments; processing aids such
as waxes/oils and fluoroelastomers; and special additives such as
fire retardants, antistats, scavengers, absorbers, odor enhancers,
and degradation agents.
[0029] The PE polymer can include other suitable additives. Such
additives can be used singularly or in combination and can be
included in the polymer composition before, during or after
preparation of the PE polymer as described herein. Such additives
can be added via known techniques, for example during an extrusion
or compounding step such as during pelletization or subsequent
processing into an end use article. Herein the disclosure will
refer to a PE polymer although a polymer composition comprising the
PE polymer and one or more additives is also contemplated.
[0030] Any catalyst composition capable of producing a PE polymer
of the type disclosed herein can be employed in the production of
the polymer. For example, a catalyst composition for the production
of a PE polymer of the type disclosed herein can include at least
two metallocenes that are selected such that the polymers produced
therefrom have two distinctly different molecular weights. The
first metallocene can be a tightly-bridged metallocene containing a
substituent that includes a terminal olefin. The second metallocene
is generally not bridged and is more responsive to chain
termination reagents, such as hydrogen, than the first metallocene.
The metallocenes can be combined with an activator, an aluminum
alkyl compound, an olefin monomer, and an olefin comonomer to
produce the desired polyolefin. The activity and the productivity
of the catalyst can be relatively high. As used herein, the
activity refers to the grams of polymer produced per gram of solid
catalyst charged per hour, and the productivity refers to the grams
of polymer produced per gram of solid catalyst charged. Such
catalysts are disclosed for example in U.S. Pat. Nos. 7,312,283 and
7,226,886 each of which is incorporated herein by reference in its
entirety.
[0031] In an embodiment, a catalyst composition comprises a first
metallocene compound, a second metallocene compound, an activator
and optionally an organoaluminum compound. The first metallocene
compound can be characterized by the general formula:
(X.sup.1R.sup.1)(X.sup.2R.sup.2.sub.2)(X.sup.3)(X.sup.4)M.sup.1;
wherein (X.sup.1) is cyclopentadienyl, indenyl, or fluorenyl,
(X.sup.2) is fluorenyl, and (X.sup.1) and (X.sup.2) are connected
by a disubstituted bridging group comprising one atom bonded to
both (X.sup.1) and (X.sup.2), wherein the atom is carbon or
silicon. A first substituent of the disubstituted bridging group is
an aromatic or aliphatic group having from 1 to about 20 carbon
atoms. A second substituent of the disubstituted bridging group can
be an aromatic or aliphatic group having from 1 to about 20 carbon
atoms, or the second substituent of the disubstituted bridging
group is an unsaturated aliphatic group having from 3 to about 10
carbon atoms. R.sup.1 is H, or an unsaturated aliphatic group
having from 3 to about 10 carbon atoms. R.sup.2 is H, an alkyl
group having from 1 to about 12 carbon atoms, or an aryl group;
(X.sup.3) and (X.sup.4) are independently an aliphatic group, an
aromatic group, a cyclic group, a combination of aliphatic and
cyclic groups, or a substituted derivative thereof, having from 1
to about 20 carbon atoms, or a halide; and M.sup.1 is Zr or Hf. The
first substituent of the disubstituted bridging group can be a
phenyl group. The second substituent of the disubstituted bridging
group can be a phenyl group, an alkyl group, a butenyl group, a
pentenyl group, or a hexenyl group.
[0032] The second metallocene compound can be characterized by the
general formula:
(X.sup.5)(X.sup.6)(X.sup.7)(X.sup.8)M.sup.2;
wherein (X.sup.5) and (X.sup.6) are independently a
cyclopentadienyl, indenyl, substituted cyclopentadienyl or a
substituted indenyl, each substituent on (X.sup.5) and (X.sup.6) is
independently selected from a linear or branched alkyl group, or a
linear or branched alkenyl group, wherein the alkyl group or
alkenyl group is unsubstituted or substituted, any substituent on
(X.sup.5) and (X.sup.6) having from 1 to about 20 carbon atoms;
(X.sup.7) and (X.sup.8) are independently an aliphatic group, an
aromatic group, a cyclic group, a combination of aliphatic and
cyclic groups, or a substituted derivative thereof, having from 1
to about 20 carbon atoms; or a halide, and M.sup.2 is Zr or Hf.
[0033] In an embodiment of the present disclosure, the ratio of the
first metallocene compound to the second metallocene compound can
be from about 1:10 to about 10:1. According to other aspects of the
present disclosure, the ratio of the first metallocene compound to
the second metallocene compound can be from about 1:5 to about 5:1.
According to yet other aspects of the present disclosure, the ratio
of the first metallocene compound to the second metallocene
compound can be from about 1:2 to about 2:1.
[0034] In an embodiment of the present disclosure, the activator
can be a solid oxide activator-support, a chemically treated solid
oxide, a clay mineral, a pillared clay, an exfoliated clay, an
exfoliated clay gelled into another oxide matrix, a layered
silicate mineral, a non-layered silicate mineral, a layered
aluminosilicate mineral, a non-layered aluminosilicate mineral, an
aluminoxane, a supported aluminoxane, an ionizing ionic compound,
an organoboron compound, or any combination thereof. The terms
"chemically-treated solid oxide", "solid oxide activator-support",
"acidic activator-support", "activator-support", "treated solid
oxide compound", and the like are used herein to indicate a solid,
inorganic oxide of relatively high porosity, which exhibits Lewis
acidic or Bronsted acidic behavior, and which has been treated with
an electron-withdrawing component, typically an anion, and which is
calcined. The electron-withdrawing component is typically an
electron-withdrawing anion source compound. Thus, the
chemically-treated solid oxide compound comprises the calcined
contact product of at least one solid oxide compound with at least
one electron-withdrawing anion source compound. Typically, the
chemically-treated solid oxide comprises at least one ionizing,
acidic solid oxide compound. The terms "support" and
"activator-support" are not used to imply these components are
inert, and such components should not be construed as an inert
component of the catalyst composition.
[0035] The organoaluminum compound used with the present disclosure
can have the formula:
(R.sup.3).sub.3Al;
in which (R.sup.3) is an aliphatic group having from 2 to about 6
carbon atoms. In some instances, (R.sup.3) is ethyl, propyl, butyl,
hexyl, or isobutyl.
[0036] In an embodiment, the catalysts are chosen from compounds
like those represented by the chemical structures A and B with
sulfated alumina as the activator-support and with
tri-isobutylaluminum (TIBA) as the co-catalyst.
##STR00001##
[0037] The PE polymer and/or individual components of the PE
polymer can comprise a homopolymer, a copolymer, or blends thereof.
In an embodiment, the PE polymer is a polymer of ethylene with one
or more comonomers such as alpha olefins. Examples of suitable
comonomers include without limitation unsaturated hydrocarbons
having from 3 to 20 carbon atoms such as propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene,
1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof.
[0038] In an embodiment, the PE polymer is a multimodal resin.
Herein, the "modality" of a polymer resin refers to the form of its
molecular weight distribution curve, i.e. the appearance of a graph
of the polymer weight fraction, frequency, or number as a function
of its molecular weight. The polymer weight fraction refers to the
weight fraction of molecules of a given size. A polymer resin can
have two or more components that may be distinguishable from one
another, for example based upon their individual composition and/or
molecular weight distribution. A molecular weight distribution
curve may be prepared for each individual component of the polymer
resin.
[0039] The molecular weight distribution curves for the individual
components may be superimposed onto a common chart to form the
weight distribution curve for the polymer resin as a whole. Upon
such superimposition, the resultant curve for the polymer resin as
a whole may be multimodal or show n distinct peaks corresponding to
n polymer components of differing molecular weight distributions.
For example, a polymer having a molecular weight distribution curve
showing a single peak may be referred to as a unimodal polymer, a
polymer having a curve showing two distinct peaks may be referred
to as a bimodal polymer, a polymer having a curve showing three
distinct peaks may be referred to as a trimodal polymer, etc.
Polymers having molecular weight distribution curves showing more
than one peak may be collectively referred to as multimodal
polymers or resins. Furthermore, the distinct peaks may correspond
to components exhibiting distinct characteristics. For example, a
bimodal polymer resin may show two distinct peaks corresponding to
two individual components of differing molecular weights.
[0040] In an embodiment, the PE polymer is a bimodal PE resin. In
such embodiments, the PE polymer comprises a higher molecular
weight (HMW) component and a lower molecular weight (LMW)
component. In such embodiments, the weight fraction of LMW
component in the PE polymer may range from about 0.25 to about
0.45, alternatively from about 0.27 to about 0.40, or alternatively
from about 0.28 to about 0.39 while the weight fraction of the HMW
component in the PE polymer may range from about 0.55 to about
0.75, alternatively from about 0.60 to about 0.73, or alternatively
from about 0.61 to about 0.72.
[0041] The PE polymers disclosed herein may have a variety of
properties and parameters described below either singularly or in
combination. Any suitable methodology may be employed for
determination of these properties and parameters.
[0042] In an embodiment, the PE polymer as a whole may have a
weight average molecular weight (M.sub.w) ranging from about
125,000 g/mol to about 225,000 g/mol, alternatively from about
130,000 g/mol to about 210,000 g/mol, or alternatively from about
150,000 g/mol to about 200,000 g/mol. The M.sub.w is defined by
Equation 1:
M _ w = i N i M i 2 i N i M i ( 1 ) ##EQU00001##
where N.sub.i is the number of molecules of molecular weight
M.sub.i. All molecular weight averages are expressed in gram per
mole (g/mol).
[0043] The molecular weight distribution (MWD) of the PE polymer
may be characterized by determining the ratio of the M.sub.w to the
number average molecular weight (M.sub.n), which is also referred
to as the polydispersity index (PDI) or more simply as
polydispersity. The PE polymers of this disclosure as a whole may
display a MWD of from about 20 to about 40, alternatively from
about 25 to about 37, or alternatively from about 30 to about 35.
In an embodiment, the LMW component of the PE polymer is
characterized by a MWD of from about 4.5 to about 10, alternatively
from about 4.7 to about 9, or alternatively from about 5 to about
8.5. In an embodiment, the HMW component of the PE polymer is
characterized by a MWD of from about 2 to about 4, alternatively
from about 2.2 to about 3.2, or alternatively from about 2.3 to
about 3.
[0044] The PE polymers of this disclosure may have a melt index
under a force of 5 kg (I5) of from about 0.10 dg/min. to about 0.90
dg/min., alternatively from about 0.5 dg/min. to about 0.85
dg/min., or alternatively from about 0.55 dg/min. to about 0.80
dg/min.
[0045] The PE polymers of this disclosure may have a melt index
under a force of 10 kg (I10) of from about 0.5 dg/min. to about 4
dg/min., alternatively from about 1 dg/min. to about 3 dg/min., or
alternatively from about 1.5 dg/min. to about 2.5 dg/min. The melt
index (MI (I5, I10) represents the rate of flow of a molten resin
through an orifice of 0.0825 inch diameter when subjected to the
indicated force at 190.degree. C. as determined in accordance with
ASTM D1238.
[0046] The PE polymers of this disclosure may have a high load melt
index (HLMI) of from about 5 dg/min to about 15 dg/min,
alternatively less than about 15 dg/min., alternatively less than
about 12 dg/min., or alternatively less than about 10 dg/min. The
HLMI represents the rate of flow of a molten resin through an
orifice of 0.0825 inch diameter when subjected to a force of 21.6
kg at 190.degree. C. as determined in accordance with ASTM
D1238.
[0047] The PE polymers of this disclosure may be further
characterized as having a density of from about 0.931 g/cc to about
0.955 g/cc, alternatively greater than about 0.930 g/cc,
alternatively greater than about 0.935 g/cc, or alternatively
greater than about 0.940 g/cc. The density refers to the mass per
unit volume of polymer and may be determined in accordance with
ASTM D1505.
[0048] In an embodiment, a PE polymer of this disclosure is
fabricated into a film. The films of this disclosure may be
produced using any suitable methodology. In an embodiment, the
polymeric compositions are formed into films through a blown film
process. In a blown film process, plastic melt is extruded through
an annular slit die, usually vertically, to form a thin walled
tube. Air is introduced via a hole in the center of the die to blow
up the tube like a balloon. Mounted on top of the die, a high-speed
air ring blows onto the hot film to cool it. The tube of film then
continues upwards, continually cooling, until it passes through nip
rolls where the tube is flattened to create what is known as a
lay-flat tube of film. This lay-flat or collapsed tube is then
taken back down the extrusion tower via more rollers. On higher
output lines, the air inside the bubble is also exchanged. This is
known as Internal Bubble Cooling (IBC).
[0049] The lay-flat film is then either kept as such or the edges
of the lay-flat are slit off to produce two flat film sheets and
wound up onto reels. Typically, the expansion ratio between die and
blown tube of film would be 1.5 to 4 times the die diameter. The
films are extruded using "HDPE film" or "high-stalk extrusion"
conditions with a neck height (freeze line height) to die diameter
ratio from about 6:1 to 10:1. The drawdown between the melt wall
thickness and the cooled film thickness occurs in both radial and
longitudinal directions and is easily controlled by changing the
volume of air inside the bubble and by altering the haul off speed.
The films formed from PE polymers of this disclosure may be of any
thickness desired by the user. Alternatively, the PE polymers of
this disclosure may be formed into films having a thickness of from
about 0.1 mils (2.54 .mu.m) to about 2 mils (50.8 .mu.m),
alternatively less than about 2 mils (50.8 .mu.m), alternatively
less than about 1.5 mils (38.1 .mu.m), or alternatively less than
about 1 mil (25.4 .mu.m).
[0050] Films formed from PE polymers of this disclosure may be
characterized by a 1% secant modulus in the transverse direction
(TD) of from about 100,000 psi (690 MPa) to about 300,000 psi (2068
MPa), alternatively greater than about 100,000 psi (690 MPa),
alternatively greater than about 120,000 psi (825 MPa), or
alternatively greater than about 150,000 psi (1030 MPa) as
determined in accordance with ASTM D882, using a test specimen
having a 1.0 mil thickness. In an embodiment, the films formed from
PE polymers of this disclosure may be characterized by a 1% secant
modulus in the machine direction (MD) of from about 90,000 psi (620
MPa) to about 160,000 psi (1103 MPa), alternatively greater than
about 95,000 psi (655 MPa), alternatively greater than about
100,000 psi (690 MPa), or alternatively greater than about 120,000
psi (825 MPa) as determined in accordance with ASTM D882, using a
test specimen having a 1.0 mil thickness.
[0051] Films formed from PE polymers of this disclosure may be
characterized by a 2% secant modulus in the TD of from about 80,000
psi (551 MPa) to about 200,000 psi (1379 MPa), alternatively
greater than about 85,000 psi (585 MPa), alternatively greater than
about 100,000 psi (690 MPa), or alternatively greater than about
140,000 psi (965 MPa) as determined in accordance with ASTM D882,
using a test specimen having a 1.0 mil thickness. In an embodiment,
the films formed from PE polymers of this disclosure may be
characterized by a 2% secant modulus in the MD of from about 75,000
psi (515 MPa) to about 125,000 psi (862 MPa), alternatively greater
than about 75,000 psi (515 MPa), alternatively greater than about
85,000 psi (585 MPa), or alternatively greater than about 100,000
psi (690 MPa) as determined in accordance with ASTM D882, using a
test specimen having a 1.0 mil thickness.
[0052] The secant modulus is a measure of the rigidity or stiffness
of a material. It is basically the applied tensile stress, based on
the force and cross-sectional area, divided by the observed strain
at that stress level. It is generally constant before the material
approaches the point at which permanent deformation will begin to
occur.
[0053] Films formed from PE polymers of this disclosure may be
characterized by a Young's modulus in the TD of from about 110,000
psi (755 MPa) to about 290,000 psi (1999 MPa), alternatively
greater than about 110,000 psi (755 MPa), alternatively greater
than about 135,000 psi (930 MPa), or alternatively greater than
about 150,000 psi (1030 MPa) as determined in accordance with ASTM
D882, using a test specimen having a 1.0 mil thickness. In an
embodiment, the films formed from PE polymers of this disclosure
may be characterized by a Young modulus in the MD of from about
100,000 psi (690 MPa) to about 180,000 psi (1241 MPa),
alternatively greater than about 100,000 psi (690 MPa),
alternatively greater than about 125,000 psi (860 MPa) or
alternatively greater than about 140,000 psi (965 MPa) as
determined in accordance with ASTM D882, using a test specimen
having a 1.0 mil thickness. Young's modulus, also referred to as
modulus of elasticity, is a measure of the stiffness of a given
material.
[0054] In an aspect, films formed from PE polymers of this
disclosure have a dart drop strength, also termed a dart impact
strength, ranging from about 100 g to about 500 g, alternatively
greater than about 100 g, alternatively greater than about 200 g,
or alternatively greater than about 300 g as measured in accordance
with ASTM D1709 Method A using a test specimen having a 1 mil
thickness. The dart drop strength refers to the weight required to
cause 50% of tested films to fail by impact from a falling dart
under specified test conditions. Specifically, one method employs
the use of a dart having a 38 mm (1.5 in) head diameter dropped
from a height of 0.66 m (26. in).
[0055] In an embodiment, films formed from PE polymers of this
disclosure have an Elmendorf tear strength in the MD ranging from
about 40 g to about 150 g, alternatively greater than about 40 g,
alternatively greater than about 50 g, or alternatively greater
than about 75 g. In an embodiment, films formed from PE polymers of
this disclosure have an Elmendorf tear strength in the TD of from
about 500 g to about 1200 g, alternatively greater than about 500
g, alternatively greater than about 600 g, or alternatively greater
than about 700 g. as measured in accordance with ASTM D1922 using a
test specimen having a 1.0 mil thickness. The Elmendorf tear
strength refers to the average force required to propagate tearing
through a specified length of plastic film or nonrigid sheeting on
an Elmendorf-type tear tester. Specifically, test specimens having
a pre-cut slit are contacted with a knife-tipped pendulum. The
average force required to propagate tearing is calculated from the
pendulum energy lost while tearing the test specimen. The tear may
be propagated either in the MD or TD.
[0056] In an embodiment, the films formed from the PE polymers of
this disclosure have a Spencer impact of from about 0.5 J to about
1.8 J, alternatively greater than about 0.5 J, alternatively
greater than about 0.75 J, or alternatively greater than about 1.0
J as measured in accordance with ASTM D3420 using a test specimen
having a 1 mil thickness. Spencer impact measures the energy
necessary to burst and penetrate the center of a specimen, mounted
between two rings with a 3.5 inch diameter. The following equation,
Equation 2, may be used to obtain an impact value in joules:
E=RC/100 (2)
where E is the energy to rupture, Joules, C is the apparatus
capacity and, R is the scale reading on a 0 to 100 scale.
[0057] In an embodiment, films formed from the PE polymers of this
disclosure are characterized by a TD yield strength ranging from
about 3500 psi (24 MPa) to about 6500 psi (45 MPa), alternatively
greater than about 3500 psi (24 MPa), alternatively greater than
about 4000 psi (27 MPa), or alternatively greater than about 4500
psi (30 MPa). In an embodiment, films formed from the PE polymers
of this disclosure are characterized by a MD yield strength ranging
from about 2500 psi (17 MPa) to about 4500 psi (31 MPa),
alternatively greater than about 2500 psi (17 MPa), alternatively
greater than about 3000 psi (20 MPa), or alternatively greater than
about 3100 psi (21 MPa).
[0058] In an embodiment, films formed from the PE polymers of this
disclosure are characterized by a TD break strength ranging from
about 8000 psi (57 MPa) to about 10000 psi (69 MPa), alternatively
greater than about 8300 psi (57 MPa), alternatively greater than
about 8500 psi (58 MPa), or alternatively greater than about 9000
psi (62 MPa). In an embodiment, films formed from the PE polymers
of this disclosure are characterized by a MD break strength ranging
from about 9,000 psi (60 MPa) to about 12,000 psi (83 MPa),
alternatively greater than about 9000 psi (60 MPa), alternatively
greater than about 10,000 psi (69 MPa), or alternatively greater
than about 11,000 psi (75 MPa). In an embodiment, films formed from
the PE polymers of this disclosure are characterized by a TD break
strain ranging from about 500% to about 700%, alternatively greater
than about 500%, alternatively greater than about 525%, or
alternatively greater than about 550%. In an embodiment, films
formed from the PE polymers of this disclosure are characterized by
a MD break strain ranging from about 350% to about 450%,
alternatively greater than 350%, alternatively greater than about
400%, or alternatively greater than about 440%.
[0059] The yield strength refers to the stress a material can
withstand without permanent deformation of the material while the
yield strain refers to amount of deformation elongation that occurs
without permanent deformation of the material. The break strength
refers to the tensile stress corresponding to the point of rupture
while the break strain refers to the tensile elongation in the
indicated direction corresponding to the point of rupture. The
yield strength, yield strain, break strength, and break strain may
be determined in accordance with ASTM D882.
[0060] In an embodiment, films formed from the PE polymers of this
disclosure are characterized by a haze of from about 5% to about
80%, alternatively less than about 80%, alternatively less than
about 40%, or less than about 20%. Haze is the cloudy appearance of
a material caused by light scattered from within the material or
from its surface. The haze of a material can be determined in
accordance with ASTM D1003. In an embodiment the haze of a film
formed from the PE polymers of this disclosure are characterized by
Equation (3):
%
Haze=2145-2216*Fraction.sub.LMW-181*(MWD.sub.LMW)-932*(MWD.sub.HMW)+27-
*(Fraction.sub.LMW*MWD.sub.LMW)+1019*(Fraction.sub.LMW*MWD.sub.HMW)+73*(MW-
D.sub.LMW*MWD.sub.HMW) [Equation 3]
[0061] In an embodiment a film formed from a PE polymer of this
disclosure may display a haze of less than about 40%, alternatively
less than about 20% and is further characterized by a weight
fraction of the LMW component ranging from about 0.25 to about
0.45, a MWD of the LMW component of from about 5.1 to about 8.3, a
MWD of the HMW component ranging from about 2.3 to about 2.6. In an
embodiment, films having a haze of greater than about 70% and
further characterized by a weight fraction of the LMW component
ranging from about 0.50 to about 0.70, a MWD of the LMW component
ranging from about 4.4 to about 5.9, and a MWD of the HMW component
ranging from about 2 to about 2.3 are excluded from this
disclosure.
[0062] In an embodiment, films formed from PE polymers of this
disclosure are characterized by a clarity of from about 40% to
about 90%, alternatively greater than about 40%, alternatively
greater than about 60%, or alternatively greater than about 80% as
determined in accordance with ASTM D1746. In an embodiment, the
clarity of a film formed from the PE polymers of this disclosure
are characterized by Equation (4):
%
Clarity=1934*Fraction.sub.LMW+139*(MWD.sub.LMW)+709*(MWD.sub.HMW)-60*(-
Fraction.sub.LMW*MWD.sub.LMW)-819*(Fraction.sub.LMW*MWD.sub.HMW)-47*(MWD.s-
ub.LMW*MWD.sub.HMW)-1632 [Equation 4]
[0063] Herein haze is defined as the percent of transmitted light
that is scattered more than 2.5.degree. from the direction of the
incident beam while clarity refers to the cloudiness of specimen
prepared from the polymeric composition.
[0064] In an embodiment, the films produced from PE polymers of the
type described herein have a gloss 60.degree. of from about 20 to
about 60, or alternatively greater than about 20, alternatively
greater than about 25, or alternatively greater than about 50 as
determined in accordance with ASTM D2457. The gloss of a material
is based on the interaction of light with the surface of a
material, more specifically the ability of the surface to reflect
light in a specular direction. Gloss is measured by measuring the
degree of gloss as a function of the angle of the incident light,
for example at 60.degree. incident angle (also known as "gloss
60.degree.").
[0065] In an embodiment, films formed from the PE polymers of this
disclosure have an oxygen transmission rate (OTR) of from about 215
cc/100 in.sup.2/day to about 140 cc/100 in.sup.2/day, alternatively
less than about 215 cc/100 in.sup.2/day, alternatively less than
about 175 cc/100 in.sup.2/day, or alternatively less than about 150
cc/100 in.sup.2 for a 1-mil film as measured in accordance with
ASTM D3985. OTR is the measurement of the amount of oxygen gas that
passes through a film over a given period. Testing may be conducted
under a range of relative humidity conditions at a range of
temperatures. Typically, one side of the film is exposed to the
oxygen permeant. As it solubilizes into the film and permeates
through the sample material, nitrogen sweeps the opposite side of
the film and transports the transmitted oxygen molecules to a
coulometric sensor. This value is reported as a transmission rate.
When this rate is multiplied by the average thickness of the
material, the results are considered a permeability rate.
[0066] In an embodiment, the films formed from the PE polymers of
this disclosure have an moisture vapor transmission rate (MVTR) of
from about 0.6 g-mil/100 in.sup.2/day to about 0.35 g-mil/100
in.sup.2/day, alternatively less than about 0.60 g-mil/100
in.sup.2/day; alternatively less than about 0.50 g-mil/100
in.sup.2/day, or alternatively less than about 0.45 g-mil/100
in.sup.2/day for a 1-mil film as measured in accordance with ASTM F
1249 at 100.degree. F. and 90% relative humidity (RH). The MVTR
measures passage of gaseous H.sub.2O through a barrier. The MVTR
may also be referred to as the water vapor transmission rate
(WVTR). Typically, the MVTR is measured in a special chamber,
divided vertically by the substrate/barrier material. A dry
atmosphere is in one chamber, and a moist atmosphere is in the
other. A 24-hour test is run to see how much moisture passes
through the substrate/barrier from the "wet" chamber to the "dry"
chamber under conditions which can specify any one of five
combinations of temperature and humidity in the "wet" chamber.
EXAMPLES
[0067] The invention having been generally described, the following
examples are given as particular embodiments of the invention and
to demonstrate the practice and advantages thereof. It is
understood that the examples are given by way of illustration and
are not intended to limit the specification of the claims in any
manner.
Example 1
[0068] Fifteen experimental resins of the type disclosed herein,
designated 1-15, were prepared. The polymerization conditions
utilized to prepare each resin sample are presented in Table 1.
TABLE-US-00001 TABLE 1 Sample# 1 2 3 4 5 6 7 8 Activator-Support
Sulfated Sulfated Sulfated Sulfated Sulfated Sulfated Sulfated
Sulfated Alumina Alumina Alumina Alumina Alumina Alumina Alumina
Alumina Feeder size (cc) 0.9 0.35 0.35 Activator-Support to reactor
(rounds/hr) 37 33 34 34 34 33 34 33 Metallocene A to reactor based
on i-C4 (ppm) 1.36 1.02 1.24 1.19 0.95 1.26 1.03 1.22 Metallocene B
to reactor based on i-C4 (ppm) 1.44 1.28 1.31 1.26 0.86 1.33 1.29
1.11 Autoclave residence time (Min) 29 31 30 31 31 30 30 30 Tiba to
Reactor based on i-C4 (ppm) 83.7 75.8 72.2 73.7 68.8 77.9 76.8 72.5
Rx Temp (.degree. F.) 201.0 201.1 192.1 196.7 197.1 191.8 192.0
197.2 Ethylene (mol %) 16.3 13.4 13.4 16.1 12.6 15.8 14.0 14.0
1-hexene (mol %) 0.8 0.5 0.4 0.7 0.6 0.8 0.7 0.7 H.sub.2 feed
rate(lb/hr) 0.0254 0.0258 0.0261 0.0259 0.0155 0.0254 0.0259 0.0154
Ethylene feed rate (lb/hr) 50.4 51.4 50.7 51.1 51.3 51.4 50.9 51.3
1-Bexene feed rate (lb/hr) 1.7 1.7 0.3 1.7 1.6 1.6 1.8 1.7 Total
i-C4 flow rate (lb/hr) 52.4 52.3 52.8 52.1 52.3 52.0 52.3 52.3
Solids concentration (wt %) 43.1 44.3 44.1 43.7 45.5 44.0 44.0 44.7
Polymer production (lb/hr) 46.0 47.7 46.8 46.8 48.8 47.1 47.2 48.0
Density (pellet) (g/cc) 0.9419 0.9409 0.9545 0.9464 0.9431 0.9495
0.9491 0.9448 HLMI (pellet) 6.43 5.25 7.57 12.99 3.35 12.09 22.03
5.39 Sample# 9 10 11 12 13 14 15 Activator-Support Sulfated
Sulfated Sulfated Sulfated Sulfated Sulfated Sulfated Alumina
Alumina Alumina Alumina Alumina Alumina Alumina Feeder size (cc)
0.9 0.9 0.9 0.9 0.9 0.9 Activator-Support to reactor (rounds/hr) 42
33 34 37 34 34 34 Metallocene A to reactor based on i-C4 (ppm) 1.35
1.26 0.85 1.21 1.17 1.20 1.23 Metallocene B to reactor based on
i-C4 (ppm) 1.42 1.32 1.07 1.27 1.23 1.26 1.29 Autoclave residence
time (Min) 30 30 32 31 30 30 31 Tiba to Reactor based on i-C4 (ppm)
82.1 74.5 68.2 82.4 72.2 75.9 75.4 Rx Temp (.degree. F.) 200.8
196.5 197.2 196.8 197.1 197.1 191.8 Ethylene (mol %) 15.2 13.9 12.5
14.1 14.9 14.9 14.5 1-hexene (mol %) 0.7 0.7 0.7 0.7 0.3 0.3 0.8
H.sub.2 feed rate (lb/hr) 0.0154 0.0155 0.0154 0.0155 0.0157 0.0157
0.0155 Ethylene feed rate (lb/hr) 51.0 51.4 52.3 51.1 43.4 51.1
51.1 1-Bexene feed rate (lb/hr) 1.7 1.6 1.6 1.7 0.3 0.4 1.6 Total
i-C4 flow rate (lb/hr) 52.3 52.0 52.2 52.3 53.2 53.1 52.0 Solids
concentration (wt %) 43.8 44.3 45.3 44.3 39.6 43.8 44.3 Polymer
production (lb/hr) 47.0 47.4 49.0 47.5 39.0 46.7 47.3 Density
(pellet) (g/cc) 0.9453 0.9482 0.9479 0.9481 0.9493 0.9579 0.9513
HLMI (pellet) 5.42 11.3 11.8 10.71 6.36 5.95 41.45
[0069] The resin M.sub.w, M.sub.w/M.sub.n, Melt index (I5 and I10),
HLMI, MFR and density of these resins are presented in Table 2.
TABLE-US-00002 TABLE 2 Sample Mw I5 I10 HLMI MFR Density ID
(kg/mol) Mw/Mn (dg/min.) (dg/min.) (dg/min) (I21.6/I10) (g/cc) 1
178.9 30.8 0.64 1.63 6.4 3.9 0.9419 2 199.2 32.7 0.56 1.84 5.3 2.9
0.9409 3 190.7 34.4 0.79 1.86 7.6 4.1 0.9545 4 181.9 33.2 0.59 2.36
13.0 5.5 0.9464 5 284.4 28.8 0.14 0.77 3.4 4.4 0.9431 6 172.2 31.7
0.87 2.63 12.1 4.6 0.9495 7 185.5 34.7 0.70 3.78 22.0 5.8 0.9491 8
271.5 33.4 0.14 0.61 5.4 8.8 0.9448 9 263.3 26.1 0.18 0.97 5.4 5.6
0.9453 10 256.5 29.0 0.18 1.33 11.3 8.5 0.9482 11 259.0 27.0 0.35
1.64 11.8 7.2 0.9479 12 242.1 29.8 0.27 1.20 10.7 8.9 0.9481 13
268.2 30.2 0.32 0.75 6.4 8.5 0.9493 14 270.1 31.1 0.25 0.92 6.0 6.5
0.9579 15 221.2 29.1 0.58 3.36 41.5 12.3 0.9513
[0070] The fifteen resins from Table 2 were formed into blown films
using a 1.5'' Davis-Standard blown film with a 2-inch die, 0.035
inch die gap, at an output rate of 29 lb/hr, a 4:1 blow up ratio
(BUR), a 14 inch freeze line (neck) height an extrusion temperature
profile of 205.degree. C. to 210.degree. C. across the extruder and
die and 1.0 mil gauge. The thickness of the film may also be
referred to as the film gauge. The properties of the film were
evaluated and are presented in Table 3.
TABLE-US-00003 TABLE 3 Spencer Sample Dart Impact MD Tear TD Tear
Haze Clarity ID (g) (J) (g) (g) % % 1 481 1.22 119 964 14.0 85.3 2
371 1.52 100 677 15.6 80.9 3 189 0.62 55 968 23.6 81.4 4 311 1.04
56 987 40.7 58.6 5 409 2.04 32 448 71.8 13.9 6 NA NA NA NA 78.0
22.5 7 217 0.90 38 832 84.0 10.7 8 590 2.08 34 606 85.5 8.5 9 592
2.07 31 585 88.6 7.5 10 499 2.04 36 617 91.8 6.4 11 360 1.44 42 607
93.0 6.6 12 NA NA NA NA 93.2 6.4 13 399 1.25 58 450 93.3 6.5 14 366
1.56 59 471 93.4 6.2 15 189 0.87 27 734 95.4 5.8
[0071] Comparison of size exclusion chromatography of a low haze
example (sample 2) and a high haze example (sample 7) is shown in
FIG. 1. Deconvolution of the SEC of samples 1-15 provided the
fraction of LMW component present in each sample in the addition to
the MWD of both the LMW and HMW components. This data is presented
in Table 4 and shown in FIGS. 2 and 3.
TABLE-US-00004 TABLE 4 ID Number LMW Fraction LMW MWD HMW MWD 1
0.34 5.20 2.35 2 0.39 8.25 2.09 3 0.39 6.42 2.55 4 0.45 5.13 2.40 5
0.50 4.59 2.00 6 0.56 5.89 2.35 7 0.56 5.89 2.33 8 0.51 5.18 2.01 9
0.52 4.67 2.03 10 0.61 4.38 2.00 11 0.65 5.28 2.00 12 0.60 4.24
2.07 13 0.55 4.76 2.26 14 0.56 4.64 2.11 15 0.70 4.42 2.00
[0072] The experimentally determined haze and clarity for samples
1-15 were compared to the haze and clarity determined using
Equations 3 and 4 respectively. Table 5 presents the fraction of
the LMW component, MWD of the LMW and HMW components and the
measured and predicted haze. The data are plotted in FIGS. 4 and 5.
Table 6 presents the weight fraction of the LMW component, MWD of
the LMW and HMW components and the measured and predicted clarity.
The data are plotted in FIGS. 6 and 7.
TABLE-US-00005 TABLE 5 Haze LMW Measured Predicted Sample ID
Fraction LMW MWD HMW MWD (%) (%) 1 0.34 5.20 2.35 14.0 14.1 2 0.39
8.25 2.09 15.6 15.8 3 0.39 6.42 2.55 23.6 18.2 4 0.45 5.13 2.40
40.7 43.9 5 0.50 4.59 2.00 93.0 93.3 6 0.56 5.89 2.35 85.5 88.2 7
0.56 5.89 2.33 88.6 86.9 8 0.51 5.18 2.01 93.3 79.9 9 0.52 4.67
2.03 93.4 88.8 10 0.61 4.38 2.00 78.0 91.3 11 0.65 5.28 2.00 71.8
73.2 12 0.60 4.24 2.07 91.8 93.7 13 0.55 4.76 2.26 93.2 80.9 14
0.56 4.64 2.11 84.0 86.6 15 0.70 4.42 2.00 95.4 85.2
TABLE-US-00006 TABLE 6 LMW LMW HMW Clarity (%) Sample fraction MWD
MWD Measured Predicted 1 0.34 5.2 2.4 85 80 2 0.39 8.3 2.1 81 80 3
0.39 6.4 2.6 81 88 4 0.45 5.1 2.4 59 51 5 0.50 4.6 2.0 14 3 6 0.56
5.9 2.4 23 10 7 0.56 5.9 2.3 11 3 8 0.51 5.2 2.0 9 10 9 0.52 4.7
2.0 8 10 10 0.61 4.4 2.0 6 12 11 0.65 5.3 2.0 7 6 12 0.60 4.2 2.1 6
3 13 0.55 4.8 2.3 6 10 14 0.56 4.6 2.1 6 3 15 0.70 4.4 2.0 6 15
[0073] The data demonstrate the medium to high density PE polymers
with a characteristic bimodal architecture of this disclosure
display the typical film properties of medium to high density HMW
PE resins (e.g., dart and Elmendorf tear strength) but
uncharacteristically display high clarity and low haze, generally
associated with lower density materials.
ADDITIONAL DISCLOSURE
[0074] The following enumerated embodiments are provided as
non-limiting examples.
[0075] A first embodiment which is a bimodal polymer having a
weight fraction of a lower molecular weight (LMW) component ranging
from about 0.25 to about 0.45, a weight fraction of a higher
molecular weight (HMW) component ranging from about 0.55 to about
0.75 and a density of from about 0.931 g/cc to about 0.955 g/cc
which when tested in accordance with ASTM D1003 using a 1 mil test
specimen displays a haze characterized by equation: %
Haze=2145-2216*Fraction.sub.LMW-181*a molecular weight distribution
of the LMW component (MWD.sub.LMW)-932*a molecular weight
distribution of the HMW component
(MWD.sub.w)+27*(Fraction.sub.LMW*MWD.sub.LMW)+1019*(Fraction.sub.LMW*MWD.-
sub.HMW)+73*(MWD.sub.LMW*MWD.sub.HMW) wherein fraction refers to
the weight fraction of the component in the polymer as a whole.
[0076] A second embodiment which is the polymer of the first
embodiment which when tested in accordance with ASTM D1746 displays
a clarity characterized by equation: %
Clarity=1934*Fraction.sub.LMW+139*(MWD.sub.LMW)+709*(MWD.sub.HMW)-60*(Fra-
ction.sub.LMW*MWD.sub.LMW)-819*(Fraction.sub.LMW*MWD.sub.HMW)-47*(MWD.sub.-
LMW*MWD.sub.HMW)-1632.
[0077] A third embodiment which is the polymer of any of the first
through second embodiments having a molecular weight distribution
of from about 20 to about 40.
[0078] A fourth embodiment which is the polymer of any of the first
through third embodiments wherein the LMW component has a molecular
weight distribution of from about 4.5 to about 10.
[0079] A fifth embodiment which is the polymer of any of the first
through fourth embodiments wherein the HMW component has a
molecular weight distribution of from about 2 to about 4.
[0080] A sixth embodiment which is the polymer of any of the first
through fifth embodiments having a high load melt index of from
about 5 dg/min. to about 15 dg/min.
[0081] A seventh embodiment which is the polymer of any of the
first through sixth embodiments which when tested in accordance
with ASTM D882 has a 1% secant modulus in the transverse direction
of from about 100,000 psi to about 300,000 psi.
[0082] An eighth embodiment which is the polymer of any of the
first through seventh embodiments which when tested in accordance
with ASTM D882 has a 1% secant modulus in the machine direction of
from about 90,000 psi to about 160,000 psi.
[0083] A ninth embodiment which is the polymer of any of the first
through eighth embodiment which when tested in accordance with ASTM
D1709 has a dart drop strength ranging from about 100 g to about
500 g.
[0084] A tenth embodiment which is the polymer of any of the first
through ninth embodiments which when tested in accordance with ASTM
D1922 has an Elmendorf tear strength in the machine direction
ranging from about 40 g to about 150 g.
[0085] An eleventh embodiment which is the polymer of any of the
first through tenth embodiments which when tested in accordance
with ASTM D1922 has an Elmendorf tear strength in the transverse
direction ranging from about 500 g to about 1200 g.
[0086] A twelfth embodiment which is the polymer of any of the
first through eleventh embodiments which when tested in accordance
with ASTM D3420 has Spencer impact of from about 0.5 J to about 1.8
J.
[0087] A thirteenth embodiment which is the polymer of any of the
first through twelfth embodiments which when tested in accordance
with ASTM D882 has a yield strength in the transverse direction
ranging from about 3500 psi to 6500 psi.
[0088] A fourteenth embodiment which is the polymer of any of the
first through thirteenth embodiments which when tested in
accordance with ASTM D882 has a yield strength in the machine
direction ranging from about 2500 psi to about 4500 psi.
[0089] A fifteenth embodiment which is the polymer of any of the
first through fourteenth embodiments which when tested in
accordance with ASTM D882 has a break strength in the transverse
direction ranging from about 8000 psi to about 10000 psi.
[0090] A sixteenth embodiment which is the polymer of any of the
first through fifteenth embodiments which when tested in accordance
with ASTM D882 has a break strength in the machine direction
ranging from about 9000 psi to about 12000 psi.
[0091] A seventeenth embodiment which is the polymer of any of the
first through sixteenth embodiments which when tested in accordance
with ASTM D882 has a break strain in the transverse direction
ranging from about 500% to about 700%.
[0092] An eighteenth embodiment which is the polymer of any of the
first through seventeenth embodiments which when tested in
accordance with ASTM D882 has a break strain in the machine
direction ranging from about 350% to about 450%.
[0093] A nineteenth embodiment which is the polymer of any of the
first through eighteenth embodiments which when tested in
accordance with ASTM D3985 has an oxygen transmission rate of from
about 215 cc/100 in.sup.2/day to about 140 cc/100 in.sup.2/day.
[0094] A twentieth embodiments which is the polymer of any of the
first through nineteenth embodiments which when tested in
accordance with ASTM F1249 has a moisture vapor transmission rate
of from about 0.6 g-mil/100 in.sup.2/day to about 0.35 g-mil/100
in.sup.2/day.
[0095] A twenty-first embodiment which is the polymer of any of the
first through twentieth embodiments which when tested in accordance
with ASTM D2457 has a gloss 60.degree. of from about 20 to about
60.
[0096] A twenty-second embodiment which is the polymer of any of
the first through twenty-first embodiments which when tested in
accordance with ASTM D1003 has a percentage haze less than about
40%.
[0097] Without further elaboration, it is believed that one skilled
in the art can, using the description herein, utilize the present
invention to its fullest extent. While inventive aspects have been
shown and described, modifications thereof can be made by one
skilled in the art without departing from the spirit and teachings
of the invention. The embodiments and examples described herein are
exemplary only, and are not intended to be limiting. Many
variations and modifications of the invention disclosed herein are
possible and are within the scope of the invention. Where numerical
ranges or limitations are expressly stated, such express ranges or
limitations should be understood to include iterative ranges or
limitations of like magnitude falling within the expressly stated
ranges or limitations (e.g., from about 1 to about 10 includes, 2,
3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use
of the term "optionally" with respect to any element of a claim is
intended to mean that the subject element is required, or
alternatively, is not required. Both alternatives are intended to
be within the scope of the claim. Use of broader terms such as
comprises, includes, having, etc. should be understood to provide
support for narrower terms such as consisting of, consisting
essentially of, comprised substantially of, etc.
[0098] Accordingly, the scope of protection is not limited by the
description set out above but is only limited by the claims which
follow, that scope including all equivalents of the subject matter
of the claims. Each and every claim is incorporated into the
specification as an embodiment of the present invention. Thus, the
claims are a further description and are an addition to the
embodiments of the present invention. The disclosures of all
patents, patent applications, and publications cited herein are
hereby incorporated by reference, to the extent that they provide
exemplary, procedural or other details supplementary to those set
forth herein.
* * * * *