Title of Invention

A PROCESS FOR PRODUCING A POLYMER COMPOSITION AND THE COMPOSITION PER SE

Abstract A process is provided for producing a polymer composition, said process comprising incorporating a narrow molecular weight distribution base polymer and a high molecular weight polymer component to produce said polymer composition; wherein said base polymer is an ethylene polymer having a Mw/Mn less than 5 and a melt flow index from about 0.2 g/10 min to about 20 g/10 min; and wherein said high molecular weight polymer component has a molecular weight distribution such that at least a substantial portion of its molecules have a molecular weight of greater than one million, said high molecular weight polymer component being incorporated in an amount to give 0.1 % to 10 % by weight, based on the total weight of said polymer composition, of said molecules having a molecular weight greater than one million.
Full Text PROCESS FOR PRODUCING A POLYMER COMPOSITION
Field of Invention
This invention is related to the field of processes for producing a polymer
composition.
Background of the Invention
The production of polymers is a multi-billion dollar business. This business
produces billions of pounds of polymers each year. Millions of dollars have been spent
on developing technologies that can add value to this business.
Increasing production of polymers from polymerization processes is an important
area of polymer research. In addition, discovering new polymer blends having superior
properties also is a continuing research goal. Specifically, improving optical properties,
such as haze and gloss, of such polymers blends blown into film, also is an important goal
of polymer research since film is often used in packaging and other applications.
It is desirable to provide a process for producing a polymer composition.
Again it is desirable provide the polymer composition.
Once again it is desirable to provide a process for increasing the production of
polymers from polymerization processes by increasing the bulk density of a narrow
molecular weight distribution base polymer by incorporating a high molecular weight
polymer component with the narrow molecular weight distribution base polymer to
produce a polymer composition.
Yet again it is desirable to provide a process for increasing the clarity of blown
film produced from a narrow molecular weight distribution base polymer by incorporating
a high molecular weight polymer component with the narrow molecular weight
distribution base polymer to produce a polymer composition.
Summary of the Invention
In accordance with one embodiment of this invention, a process for producing a
polymer composition is provided. The process comprises incorporating a narrow
molecular weight distribution base polymer and a high molecular weight polymer
component to produce the polymer composition;
wherein the base polymer is an ethylene polymer having a Mw/Mn less than about
5 and a melt flow index from about 0.2 g/10 min to about 20 g/10 min; and
wherein the high molecular weight polymer component has a molecular weight
distribution such that at least a substantial portion of its molecules have a molecular
weight of greater than one million, the component being incorporated is in an amount to
give about 0.1 to about 10% by weight, based on the total weight of said polymer
composition, of the molecules having a molecular weight greater than one million.
These objects, and other objects, will become more apparent to those with
ordinary skill in the art after reading this disclosure.
Detailed Description of the Invention
A process is provided for producing a polymer composition. The process
comprises incorporating a narrow molecular weight distribution base polymer and a high
molecular weight polymer component. The narrow molecular weight distribution base
polymer is hereinafter referred to as a "base polymer". When the base polymer is
incorporated with the high molecular weight polymer component, the bulk density of the
base polymer is increased, thereby, increasing the production rate. The bulk density of the
polymer composition can be increased by about 10% to about 40% over the bulk density
of the base polymer. In order to achieve the bulk density increase, the high molecular
weight polymer component must be incorporated with the base polymer while the base
polymer is produced in a polymerization zone.
Another benefit of incorporating the base polymer and the high molecular weight
polymer component is to increase the clarity of blown film produced from the base
polymer. In order to achieve this clarity increase, the incorporation of the high molecular
weight polymer component can be accomplished either while the base polymer is being
produced in the polymerization zone or after the base polymer and high molecular weight
polymer component have been produced separately. For example, the base polymer and
high molecular weight polymer component can be blended together to produce the
polymer composition. The haze of the polymer composition can be decreased by about
5% to as much as about 60% over the haze of the base polymer, and the gloss of the
polymer composition can be increased by about 10 to about 40% over the gloss of the
base polymer.
The base polymer is defined as the narrow molecular weight polymer before the
high molecular weight polymer component is added to produce the polymer composition.
The base polymer can be any narrow molecular weight distribution ethylene polymer,
either a homopolymer or copolymer, such as, for example, ethylene-hexene copolymers.
The base polymer has a Mw(weight average molecular weight)/Mn (number average
molecular weight) of less than about 5.0. Preferably, Mw/Mh of the base polymer is less
than about 4.0, and most preferably, Mw/Mn of the base polymer is less than 3.0.
Base polymers can be produced from any catalyst known in the art to produce
narrow molecular weight distribution polymers. For example, metallocene catalysts of
various types, such as described in U.S. Patents 5,436,305; 5,610,247; and 5,627,247,
herein incorporated by reference, can be used to produce the base polymer. Ziegler
catalysts containing magnesium and titanium halides, such as described in U.S. Patents
5,275,992; 5,179,178; 5,275,992; 5,237,025; 5,244,990; and 5,179,178, herein
incorporated by reference, can also be used. Chromium catalysts as described for
example in U.S. Patents 3,887,494; 3,119,569; 3,900,457; 4,981,831; 4,364,842; and
4,444,965, herein incorporated by reference, also can be utilized to produce the base
polymer. Preferably, the base polymer is produced from metallocene catalyst. Since
these catalysts are well known to produce a narrow molecular weight distribution
polymer, are very active, and often are very efficient for the incorporation of comonomer.
The base polymer can be an ethylene homopolymer or preferably, a copolymer of
ethylene and at least one other alpha-olefin, such as 1-hexene, 1-butene, or 1-octene.
Most preferably, the base polymer is an ethylene-hexene copolymer.
Generally, the density of the base polymer is in a range of about 0.900 g/cc to
about 0.975 g/cc. Preferably, the density of the base polymer is in a range of about 0.910
g/cc to about 0.940 g/cc, and most preferably, from 0.915 g/cc to 0.93 g/cc. Generally,
the base polymer has a melt flow index in a range from about 0.2 g/10 min to about 20
g/10 min. Preferably, the base polymer has a melt flow index in a range from about 0.5
g/10 min to about 10 g/10 min, and most preferably from 0.8 g/10 min to 5.0 g/10 min.
The high molecular weight polymer component can be produced from most any
known catalyst system, whether the high molecular weight polymer component is
produced simultaneously with the base polymer in the polymerization zone, or separately
and blended later. Suitable catalysts for production of the high molecular weight polymer
component include, but are not limited to, Ziegler catalysts based on titanium halides,
zirconium halides, zirconium alkyls, chromium oxide catalysts, metallocene catalysts, and
mixtures thereof .
The high molecular weight polymer component has a molecular weight
distribution, such that, a substantial portion of its molecules have a molecular weight
greater than one million. Generally, the high molecular weight polymer component being
incorporated is in an amount to give about 0.1% to about 10% by weight, based on the
total weight of the polymer composition, of the molecules having a molecular weight
greater than one million. Preferably, the high molecular weight polymer component being
incorporated is in an amount to give about 0.5% to about 5% by weight, based on the total
weight of the polymer composition, of the molecules having a molecular weight greater
than one million, most preferably, 1% to 3% by weight.
It is not imperative that the additional high molecular weight polymer component
be pure. For example, a high molecular weight polymer component which also contains a
substantial amount of polymer of molecular weight lower than one million can be incor-
porated into the base polymer provided it has a sufficient amount of polymer above one
million in molecular weight to contribute the proper amount of high molecular weight
polymer component described previously.
To achieve the increase in bulk density of the polymer composition, the high
molecular weight polymer component must be incorporated with the base polymer in the
polymerization zone. Any method known in the art to incorporate the high molecular
weight polymer component with the base polymer in the polymerization zone can be
utilized.
One method of incorporating the high molecular weight polymer component is to
modify a polymerization catalyst system before it is added to the polymerization zone.
For example, a second transition metal component can be added to the polymerization
catalyst system which then is capable of generating simultaneously the base polymer and
the high molecular weight polymer component.
A second method of incorporating the high molecular weight polymer component
is to chemically modify the polymerization catalyst system while it is in the poly-
merization zone, such as by adding a second component which will react with a catalyst
in the polymerization catalyst system to create the high molecular weight polymer
component For example, a metallocene catalyst system can be modified to include a
titanium or chromium component, either before the metallocene catalyst system is
introduced into the polymerization zone, or while it is in the polymerization zone. A
halided, titanium-containing solid oxide compound or fluorided, chromium-containing
solid oxide compound can be utilized as the titanium or chromium component.
The halided, titanium-containing solid oxide compound comprises at least one
halogen, titanium, and a solid oxide compound. The halogen is at least one selected from
the group consisting of chlorine, bromine, and fluorine. Generally, the solid oxide
compound is selected from the group consisting of alumina, silica, aluminophosphate,
aluminosilicates, aluminoborates, silica-zirconia, silica-titania, and mixtures thereof.
Preferably, the solid oxide compound is silica-alumina or alumina. The solid oxide
compound can be produced by any method known in the art, such as, for example, by
gelling, co-gelling, impregnation of one compound onto another, and flame hydrolysis.
When silica-titania is used, the content of titania can be about 1 to about 15% by
weight titanium based on the total weight of the silica-titania, preferably, about 2.5 to
about 12% by weight, and most preferably, 4 to 10% by weight, with the remainder being
primarily silica. The silica-titania can be produced by any method known in the art.
Such processes are disclosed in U.S. Patents 3,887,494; 3,119,569; 4,405,501; 4,436,882;
4,436,883; 4,392,990; 4,081,407; 4,152,503; 4,981,831; 2,825,721; 3,225,023; 3,226,205;
3,622,521; and 3,625,864; the entire disclosures of which are hereby incorporated by
reference. The silica-titania can be made by cogellation of aqueous materials, or by
cogellation in an organic or anhydrous solution, or by coating the surface of silica with a
layer of titania such as, for example, by reaction of silanol groups with titanium
isopropoxide followed by calcining.
Aluminophosphate can be made by any method known in the art, such as, for
example, those methods disclosed in U.S. Patents 4,364,842; 4,444,965; 4,364,855;
4,504,638; 4,364,854; 4,444,964; 4,444,962; 4,444,966; and 4,397,765; the entire
disclosures of which are hereby incorporated by reference.
Silica-alumina can be made by any method known in the art. The amount of
alumina in the silica-alumina can range from about 2 to about 50% by weight based on
the total weight of the silica-alumina, preferably, from about 5 to about 30% by weight,
and most preferably, 8 to 20% by weight. Commercial grade silica-alumina is available
as MS 13-110 from W. R. Grace and commercial grade alumina as Ketjen Grade B or
Ketjen Grade L from Akzo Nobel.
Generally, the specific surface area of the solid oxide compound is from about 100
to about 1000 m2/g, preferably, from about 200 to about 800 m2/g, and most preferably,
from 250 to 600 m2/g after calcining at 500°C.
The specific pore volume of the solid oxide compound is typically greater than
about 0.5 cm3/Vg, preferably, greater than about 0.8 cm3/Vg, and most preferably, greater
than 1.0 cm3/Vg.
The halided, titanium-containing solid oxide compound can be produced when the
solid oxide compound is contacted with at least one titanium-containing compound and at
least one halogen-containing compound. The order of contacting the solid oxide
compound with the titanium-containing compound and the halogen-containing compound
can vary.
To produce the halided, titanium-containing solid oxide compound, at least one
titanium-containing compound is contacted with the solid oxide compound by any means
known in the art to produce a titanium-containing solid oxide compound. Titanium can
be added to the solid oxide compound before, during, or after calcining. Generally, the
amount of titanium present in the titanium-containing solid oxide compound is in a range
of about 0.01 to about 10 weight percent titanium where the weight percent is based on
the weight of the titanium-containing solid oxide compound. Preferably, the amount of
titanium present in the titanium-containing solid oxide compound is in a range of about
0.1 to about 5 weight percent titanium based on the weight of the titanium-containing
solid oxide compound. Most preferably, the amount of titanium present in the titanium-
containing solid oxide compound is in a range of 0.5 to 2 weight percent titanium based
on the weight of the titanium-containing solid oxide compound.
In one method of producing a titanium-containing solid oxide compound, the solid
oxide compound can be contacted with an aqueous or organic solution of the titanium-
containing compound before calcining. For example, the titanium can be added to the
solid oxide compound by forming a slurry of the solid oxide compound in a solution of
the titanium-containing compound and a suitable solvent such as alcohol or water.
Particularly suitable are one to three carbon atom alcohols because of their volatility and
low surface tension. Titanium alkoxides, Ti(OR)4, where R is an alkyl or aryl group
having 1 to about 12 carbons, is particularly suitable as a titanium source. A suitable
amount of the solution is utilized to provide the desired concentration of titanium after
drying. Drying can be effected by any method known in the art For example, said drying
can be completed by suction filtration followed by evaporation, vacuum drying, spray
drying, or flash drying. This method is exemplified by U.S. Patents 4,294,724;
4,382,022; 4,402,864; 4,405,768; and 4,424,320; the entire disclosures of which are
herein incorporated by reference.
In a second method, the titanium can be cogelled into the solid oxide compound
when the solid oxide compound is being produced as exemplified by U.S. Patents
3,887,494; 3,119,569; 4,405,501, and 4,436,882, the entire disclosures of which are
herein incorporated by reference.
If the titanium is added before calcination, any water soluble or organic soluble
titanium-containing compound is suitable that can impregnate the solid oxide compound
with titanium. In a coprecipitation method, a titanium compound such as titanium
halides, titanium nitrates, titanium sulfates, titanium oxalate, or alkyl titanates, for
example, is incorporated with an acid or a silicate. Titanyl sulfate (TiOSO4) dissolved in
sulfuric acid is a particularly suitable compound. If the titanium is deposited onto the
surface of an already formed solid oxide compound, titanium halides, TiX4 where X is
chloride or bromide, or alkyl titanates, Ti(OR)4 where R is an alkyl or aryl group
containing 1 to about 12 carbons are preferred.
If the titanium is added during calcining, one convenient method is to vaporize a
volatile titaniurn-containing compound, such as titanium tetrachloride or titanium tetra-
fluoride, or an alkyl titanate (Ti(OR)4 where R is an alkyl or aryl group containing 1 to
about 12 carbons, into a gas stream used to contact the solid oxide compound.
If the titanium is added after calcining, a preferred method is to impregnate the
solid oxide compound with a hydrocarbon solution of the titanium-containing compound,
preferably a titanium halide or titanium alkoxyhalide, such as TiCl4, TiORCl3,
Ti(OR)2Cl2, and the like, where R is an alkyl or aryl group having 1 to about 12 carbons.
Calcining is conducted at various steps in the production of the halided, titanium-
containing solid oxide compound. Generally, calcining is conducted for about 1 minute
to about 100 hours, preferably from about 1 hour to about 50 hours, and most preferably,
from 3 to 20 hours. Generally, the calcining is conducted at a temperature in a range of
about 200°C to about 900°C, preferably from about 300°C to about 700°C, and most
preferably, from 350°C to 600°C. The calcining can be conducted in any suitable
atmosphere. Generally, the calcining can be completed in an inert atmosphere.
Alternatively, the calcining can be completed in an oxidizing atmosphere, such as, oxygen
or air, or a reducing atmosphere, such as, hydrogen or carbon monoxide.
To produce the halided, titanium-containing solid oxide compound, the solid
oxide compound is also contacted with at least one halogen-containing compound. The
halogen-containing compound is at least one selected from the group consisting of
chlorine-containing compounds, bromine-containing compounds, and fluorine-containing
compounds. The halogen-containing compound can be in a liquid phase, or preferably, a
vapor phase. Optionally, the solid oxide compound can be calcined at about 100°C to
about 900°C before being contacted with the halogen-containing compound.
Any method of fluoriding the solid oxide compound known in the art can be used
in this invention. A common method is to impregnate the solid oxide compound with an
aqueous solution of a fluoride-containing salt before calcining, such as ammonium
fluoride [NH4F], ammonium bifluoride [NH4HF2], hydrofluoric acid [HF], ammonium
silicofluoride [(NH4)2SiF6], ammonium fluoroborate [NH4BF4], ammonium
fluorophosphate [NH4PF6], and mixtures thereof.
In a second method, the fluorine-containing compound can be dissolved into an
organic compound, such as an alcohol, and added to the solid oxide compound before
calcining to minimize shrinkage of pores during drying. Drying can be accomplished by
an method known in the art, such as, for example, vacuum drying, spray drying, flashing
drying, and the like.
In a third method, the fluorine-containing compound can be incorporated into the
gel formed when producing a solid oxide compound by adding it to at least one of the
solutions before gellation. Alternatively, the fluorine-containing compound can be added
to the gel before drying. Gellation methods to produce a solid oxide compound were
discussed previously in this disclosure.
In a fourth method, the fluorine-containing compound can be added during
calcining. In this technique, the fluorme-containing compound is vaporized into the gas
stream used to fluidize the solid oxide compound so that it is fluorided from the gas
phase. In addition to some of the fluorine-containing compounds described previously,
volatile organic fluorides can be used at temperatures above their decomposition points,
or at temperatures high enough to cause reaction. For example, perfluorohexane,
perfluorobenzene, trifluoroacetic acid, trifluoroacetic anhydride, hexafluoroacetyl-
acetonate, and mixtures thereof can be vaporized and contacted with the solid oxide
compound at about 300°C to about 600°C in air or nitrogen. Inorganic fluorine-
containing compounds can also be used, such as hydrogen fluoride or even elemental
fluorine.
The amount of fluorine present on the halided, titanium-containing solid oxide
compound is about 2 to about 50 weight percent fluorine based on the weight of the
halided, titanium-containing solid oxide compound before calcining or the amount added
to a precalcined solid oxide compound. Preferably, it is about 3 to about 25 weight
percent, and most preferably, it is 4 to 20 weight percent fluorine based on the weight of
the halided, titanium-containing solid oxide compound before calcining or the amount
added to a precalcined solid oxide compound.
Any method of contacting the solid oxide compound with the chlorine-containing
compound or the bromme-containing compound known in the art can be used in this
invention. Generally, the contacting is conducted during or after calcining, preferably
during calcining. Any suitable chlorine-containing compound or bromine-containing
compound that can deposit chlorine or bromine or both on the solid oxide compound can
be used. Suitable chlorine-containing compounds and bromine-containing compound
include volatile or liquid organic chloride or bromide compounds and inorganic chloride
or bromide compounds. Organic chloride or bromide compounds can be selected from
the group consisting of carbon tetrachloride, chloroform, dichloroethane, hexachloro-
benzene, trichloroacetic acid, bromoform, dibromomethane, perbromopropane, phosgene,
and mixtures thereof. Inorganic chloride or bromide compounds can be selected from the
group consisting of gaseous hydrogen chloride, silicon tetrachloride, tin tetrachloride,
titanium tetrachloride, aluminum trichloride, boron trichloride, thionyl chloride, sulfuryl
chloride, hydrogen bromide, boron tribromide, silicon tetrabromide, and mixtures thereof.
Additionally, chlorine and bromine gas can be used. Optionally, a fluorine-containing
compound can also be included when contacting the zirconium-containing solid oxide
compound with the chlorine-containing compound or bromine-containing compound to
achieve higher activity in some cases.
If an inorganic chlorine-containing compound or bromine-containing compound is
used, such as titanium tetrachloride, aluminum trichloride, or boron trichloride, it can also
be possible to achieve the chloriding or bromiding after calcining, either by vapor phase
deposition or even by using an anhydrous solvent
The amount of chlorine or bromine used can be from about 0.01 to about 10 times
the weight of the halided, titanium-containing solid oxide compound before calcining or
the amount added to a precalcined solid oxide compound, preferably it is from about 0.05
to about 5 times, most preferably from 0.05 to 1 times the weight of the halided, titanium-
containing solid oxide compound before calcining or the amount added to a precalcined
solid oxide compound.
Generally, the solid oxide compound is contacted with the chlorine-containing
compound or bromine-containing compound at a temperature in the range of about 25°C
to about 1000°C, preferably from about 200°C to 700°C, and most preferably from 300°C
to 600°C.
In another embodiment of this invention, an additional compound can be added to
the halided, titanium-containing solid oxide compound to enhance the activity of the
organometal compound. For example, an additional metal, such as, zinc, silver, copper,
antimony, gallium, tin, nickel, tungsten, and mixtures thereof, can be added by contacting
the halided, titanium-containing solid oxide compound with a metal-containing
compound. This is especially useful if the solid oxide compound is to be chlorided during
calcining. When used, these metals are added in an amount of about 0.01 to about 10
millimoles per gram of halided, titanium-containing solid oxide compound, preferably
about 0.1 to about 5 millimoles per gram, and most preferably from 0.5 to 3 millimoles of
metal per gram of halided, titanium-containing solid oxide compound.
Preferably, magnesium is added to the halided, titanium-containing solid oxide
compound to increase the activity of the titanium component of the catalyst composition
by contacting the halided, titanium-containing solid oxide compound with a magnesium-
containing compound. The amount of magnesium used can be from about 0.01 to about
10 millimoles per gram of halided, titanium-containing solid oxide compound, preferably
from about 0.1 to about 5 millimoles per gram, most preferably from 0.1 to 1 millimoles
per gram of halided, titanium-containing solid oxide compound. If magnesium is added,
it can be added before or after calcining. One preferred method of adding magnesium is
to contact an organomagnesium compound in a hydrocarbon solution with the halided,
titanium-containing solid oxide compound. Examples of such compounds include, but
are not limited to, dialkyl magnesium, alkyl magnesium halide, magnesium alkoxide or
aryloxides, and the like.
The fluorided, chromium-containing solid oxide compound comprises fluorine,
chromium, and a solid oxide compound. The solid oxide compounds discussed
previously can be utilized to produce the fluorided, chromium-contarning solid oxide
compound. The fluorine can be added to the solid oxide compound as discussed
previously for the halided, titanium-containing solid oxide compound. The chromium can
be added to the solid oxide compound as discussed previously for titanium. Examples of
chromium-containing compounds include, but are not limited to, chromium trioxide
(CrO3), ammonium chromate ((NH4)2CrO4), ammonium dichromate ((NH4)2Cr2O7),
chromic acetate (Cr2H3O3), chromic nitrate (Cr(NO3)3), chromous chloride (CrCl2), bis-
benzene chromium(0) ((C6H6)2Cr), chromocene ((C5H5)2Cr), and mixtures thereof. The
amount of chromium present is in the range of about 0.01 to about 10% by weight,
preferably, about 0.5 to about 5% by weight, and most preferably, from 0.8% to 3% by
weight, where the weight percents are based on the weight of the chromium-containing
solid oxide compound before calcining.
A third method to incorporate the high molecular weight polymer component is to
produce a metallocene catalyst system comprising two metallocene components with a
first metallocene component producing the base polymer and a second metallocene
component producing the high molecular weight polymer component. Again, this can be
accomplished before introduction into the polymerization zone or while in the poly-
merization zone.
To achieve improvements in the clarity of blown films made from the base
polymer, the high molecular weight polymer component can be incorporated as described
previously through catalyst system modification, or it can also be incorporated after
production in the polymerization zone, such as, by melt blending the base polymer and
the high molecular weight polymer component together. Preferably, the clarity
improvement is obtained through catalyst modification since no blending is required.
Polymerization can be carried out in any manner known in the art, such as, for
example, gas phase, solution or slurry conditions, to effect polymerization. Any
polymerization zone known in the art to produce ethylene polymers can be utilized. For
example, a stirred reactor can be utilized for a batch process, or the reaction can be carried
out continuously in a loop reactor or in a continuous stirred reactor. Processes that can
polymerize monomers into polymers using the catalyst systems of this invention are
known in the art, such as, for example, slurry polymerization, gas phase polymerization,
solution polymerization, and multi-reactor combinations thereof.
A preferred polymerization technique is that which is referred to as a particle
form, or slurry process, wherein the temperature is kept below the temperature at which
the polymer swells or goes into solution. A loop reactor is particularly preferred. Such
polymerization techniques are well known in the art and are disclosed, for instance, in
Norwood, U.S. 3,248,179, the disclosure of which is hereby incorporated by reference.
Furthermore, it is even more preferred to use isobutane as a diluent in a slurry poly-
merization. Examples of such technology can be found in U.S. Patents 4,424,341;
4,501,885; 4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which are
hereby incorporated by reference.
The preferred temperature in the particle form process is within a range of about
185°F to about 230°F (about 85°C to about 110°C), although higher or lower
temperatures can be used. Two preferred polymerization methods for the slurry process
are those employing a loop reactor of the type disclosed in Norwood and those utilizing a
plurality of stirred reactors either in series, parallel or combinations thereof wherein the
reaction conditions can be different in the different reactors.
Monomers useful in this invention are unsaturated hydrocarbons having from 2 to
about 20 carbon atoms. Currently, it is preferred when the monomer is selected from the
group consisting of ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-
methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene,
1-nonene, 1-decene, and mixtures thereof. However, when a homopolymer is desired, it
is most preferred to use ethylene, or propylene, as the monomer. Additionally, when a
copolymer is desired, it is most preferred to use ethylene and hexene as the monomers.
The polymer density can be controlled by varying the comonomer to monomer ratio in the
polymerization zone.
The molecular weight of the polymer composition can be controlled by various
means known in the art, such as, for example, adjusting the temperature (higher
temperature giving lower molecular weight), introducing or varying the amount of
hydrogen to alter the molecular weight, and varying the catalyst components in the
catalyst system.
EXAMPLES
Polymerization Procedures
Ethylene copolymers were prepared in a continuous particle form process (also
known as a slurry process) by contacting a catalyst system with ethylene and 1-hexene
monomers. The catalyst system consisted of bis(n-butylcyclopentadienyl)zirconium
dichloride, a cocatalyst, and Catalyst A, B, or C, which are described subsequently in this
disclosure. The medium and temperature were selected such that the copolymer was
produced as solid particles and was recovered in that form. Ethylene that had been dried
over activated alumina was used as the monomer. Isobutane that had been degassed by
fractionation and dried over alumina was used as the diluent. Ethylene copolymers were
prepared in a continuous particle form process (also known as a slurry process) by
contacting a first catalyst with ethylene and 1-hexene monomers. The medium and
temperature were selected such that the copolymer was produced as solid particles and
was recovered in that form. Ethylene that had been dried over activated alumina was used
as the monomer. Isobutane that had been degassed by fractionation and dried over
alumina was used as the diluent.
A liquid full 15.2 cm diameter pipe loop having a volume of 23 gallons (87 liters)
was utilized as a reactor. Liquid isobutane was used as the diluent, and occasionally some
hydrogen was added to regulate the molecular weight of the ethylene copolymer. The
reactor pressure was about 4 Mpa (about 580 psi). The reactor temperature was 80°C.
The reactor was operated to have a residence time of 1.25 hours. Catalyst was added
through a 0.35 cc circulating ball-check feeder. At steady state conditions, the isobutane
feed rate was about 46 liters per hour, the ethylene feed rate was about 30 lbs/hr, and the
1-hexene feed rate was varied to control the density of the ethylene copolymer. Ethylene
concentration in the diluent was 8-12 mole percent Catalyst concentrations in the reactor
ranged from 0.001 to about 1 weight percent based on the weight of the reactor contents.
Ethylene copolymer was removed from the reactor at the rate of about 25 lbs per hour and
recovered in a flash chamber. A Vulcan dryer was used to dry the ethylene copolymer
under nitrogen at about 60-80°C.
A cocatalyst, triethylaluminum (TEA), also was added as indicated in a
concentration of about 10 to 100 parts per million by weight based on the weight of the
diluent. To prevent static buildup in the reactor, a small amount ( commercial antistatic agent sold as Stadis® 450 usually was added. Bis(n-
butylcyclopentadienyl) zirconium dichloride was added to the reactor as a solution in
isobutane to yield a reactor concentration of 0.5 to 1.5 parts per million based on the
weight of the diluent. The metallocene, TEA cocatalyst, and Catalyst A, B, or C were
added into a precontacting vessel where they were allowed to contact each other for about
10 minutes before being introduced into the reactor and contacted with the monomers.
Polymerization runs also were made in a 2.2 liter steel autoclave reactor equipped
with a marine stirrer running at 400 revolutions per minute (rpm). The reactor was
surrounded by a steel jacket containing boiling methanol with a connection to a steel
condenser. The boiling point of the methanol was controlled by varying nitrogen pressure
applied to the condenser and jacket, which permitted precise temperature control to within
half a degree Celsius, with the help of electronic control instruments.
Unless otherwise stated, first, a small amount (0.01 to 0.10 grams normally) of
Catalyst A, B, or C was charged under nitrogen to the dry reactor. Next, 2.0 milliliters of
a toluene solution containing 0.5 percent by weight of bis(n-butylcyclopentadienyl)
zirconium dichloride were added, followed by 0.6 liter of isobutane liquid. Then, 1.0
milliliter of a 1.0 molar solution of triethylaluminum in heptane (TEA) was added,
followed by another 0.6 liter of isobutane liquid. Then, the reactor was heated up to the
specified temperature, generally 90°C, and finally ethylene was added to the reactor to
equal a fixed pressure, typically 550 psig to produce a reaction mixture.
The reaction mixture was allowed to stir for usually about one hour. As ethylene
was consumed, more ethylene flowed in to maintain the pressure. The activity was noted
by recording the flow of ethylene into the reactor to maintain the set pressure.
After the allotted time, the ethylene flow was stopped, and the reactor slowly
depressurized and opened to recover a granular polymer powder. In all cases, the reactor
was clean with no indication of any wall scale, coating or other forms of fouling. The
polymer powder was then removed and weighed. Activity was specified as grams of
polymer produced per gram of Catalyst A, B, or C charged per hour.
Feedstocks and Diluent
The ethylene utilized was polymerization grade ethylene obtained from Union
Carbide Corporation. The ethylene then was purified further through a column of ¼ inch
beads of Alcoa A201 alumina mat had been activated at 250°C in nitrogen. The isobutane
utilized was polymerization grade obtained from Phillips Petroleum Co., Borger, Texas.
It was purified further by distillation, and it then was passed through a column of ¼ inch
beads of Alcoa A201 alumina that had been activated at 250°C in nitrogen. The 1-hexene
was polymerization grade obtained from Chevron. Chemicals. It was purified further by
nitrogen purging and storage over 13X molecular sieve that had been activated at 250°C.
Catalyst Preparation
Catalyst A
A silica-alumina was obtained from W.R. Grace as MS 13-110 containing 13% by
weight alumina and 87% by weight silica. The silica-alumina had a pore volume of about
1.2 cc/g and a surface area of about 450 square meters per gram. 800 grams of the silica-
alumina were impregnated with 1500 milliliters of an aqueous solution containing 80
grams of ammonium bifluoride to produce a mixture. The mixture then was dried in a
vacuum oven overnight at 110°C, pushed through a 35 mesh screen, and activated by
calcination in dry air at 450°C for six hours to produce a fluorided silica-alumina.
Catalyst B
470.83 grams of the same silica-alumina used for Catalyst A were calcined in air
at 300°C for twelve hours to produce a calcined silica-alumina. Afterward, the calcined
silica-alumina was impregnated just beyond the point of incipient wetness with a solution
containing 169 grams of titanium ethoxide (or about 6% by weight Ti) in 500 mls of
heptane to produce a first mixture. The first mixture was shaken thoroughly to ensure
uniform wetness then dried in a vacuum oven at 140°C with a slight nitrogen purge
overnight. Then, a solution of 47 grams of ammonium bifluoride in 500 mls of water was
added to the first mixture to produce a second mixture. The second mixture was dried
under vacuum at 140°C overnight to produce a dried second mixture. The dried second
mixture contained about 6% by weight titanium and 10% by weight ammonium
bifluoride. The dried second mixture then was calcined in dry air for 6 hours at 450°C to
produce a fluorided, titanium-containing silica-alumina.
Catalyst C
750 grams of silica-alumina described previously were impregnated with 1500 mL
of an aqueous solution containing 38 grams of ammonium bifluoride and 30 grams of
chromium trioxide to equal 2% by weight chromium on the silica-alumina to produce a
mixture. After being dried in a vacuum oven overnight at 110°C, the mixture was
activated by calcination in dry air at 600°C for five hours in a fluidized bed to produce a
fluorided, chromium-containing silica-alumina.
Film Blowing
Films were made from the polymer compositions of this invention and other
polymers for comparison purposes using one of two blown film processing lines or a cast
film line. One blown film processing line used a 1.5 inch diameter Davis-Standard
extruder with a L/D of 24:1, having a barrel temperature of 190°C to 200°C, a screw speed
of 115 RPM, and an output of 60 pounds per hour. The David-Standard extruder fed a 4
inch diameter Sano die having a 0.060 inch die gap. Films of typically 0.001-0.0005 inch"
(1 to 0.5 mil) thickness were blown on a 2.5:1 blow-up ratio and a production rate of 805
ft/min. Frostline heights were usually in the range of 6-12 inches. Cooling was
accomplished using a Dual Lip Air Ring using laboratory (ambient) air at about 75-80°F.
After cooling, the film passed through a wooden take-up tower and nip roll assembly,
with a resultant flattened or layflat width of 15.7 inches. These particular processing
conditions were chosen since the film properties so obtained are representative of those
obtained from larger, commercial scale film blowing conditions.
The second blown processing line used an Egan extruder with a 3.5 inch diameter
24:1 L/D Egan smooth barrel without grooves having a 2-stage screw with Dulmage
mixing section. The Egan extruder fed a Sano 8-inch diameter die with 60 mil die gap.
Thus, a 50 inch bubble was blown with a 2:1 blow-up ratio and 24 inch frostline height.
Bubble layflat was 50 inches. Typical melt temperatures ranged from 210°C to 250°C.
The cast films were made on a Randcastle Microtruder CF [Model RC-0625]
which consisted of a table-top 5/8 inch (16 mm) single screw extruder. The extruder was
fitted with a 5 inch (127 mm) wide slot die with a die gap of 0.020 inches (0.5 mm). The
extruder and die temperatures were maintained at 204°C (400°F) and 215°C (420°F),
respectively, resulting in a melt temperature of 196°C (385°F). The screw speed was
adjusted to maintain a constant output rate of about 520 g/hr. The melt as it exited the die
was quenched using a pair of high velocity air-knives, held 1 inch (25 mm) above and
below the melt and at a distance of 4 inches (100 mm) downstream of the die exit. The
film, subsequent to crystallization and solidification, was taken up through a pair of
primary and secondary rollers onto a film winder. The take-up speed was adjusted to
maintain a nominal film thickness of 3 mils (75 microns) for all samples.
Polymer Tests
Bulk density was determined in lbs/ft by weighing a 100 ml graduated cylinder in
which polymer fluff had been lightly tapped.
Polymer density was determined in grams per cubic centimeter (g/cc) on a
compression molded sample, cooled at about 15°C per hour, and conditioned for about 40
hours at room temperature in accordance with ASTM D1505-68 and ASTM D1928,
procedure C.
Melt Flow Index (MI) in grams of polymer per ten minutes was determined in
accordance with ASTM D1238, condition 190/2, at 190°C with a 2,160 gram weight.
High load melt index (HLMI, g/10 min) was determined in accordance with
ASTM D1238, Condition 190/2.16, at 190°C with a 21,600 gram weight.
Molecular weights and molecular weight distributions were obtained using a
Waters 150 CV gel permeation chromatograph (GPC) with trichlorobenzene (TCB) as the
solvent, with a flow rate of 1 mL/minute at a temperature of 140°C. BHT (2,6-di-tert-
butyl-4-methylphenol) at a concentration of 1.0 g/L was used as a stabilizer in the TCB.
An injection volume of 220 microliters was used with a nominal polymer concentration of
0.3 g/1 (at room temperature). Dissolution of the sample in stabilized TCB was carried
out by heating at 160-170°C for 20 hours with occasional, gentle agitation. The column
was two Waters HT-6E columns (7.8 x 300mm). The columns were calibrated with a
broad linear polyethylene standard (Phillips Marlex® polyethylene BHB 5003) for which
the molecular weight had been determined.
Haze was determined in accordance with ASTMD-1003. A Gardner XL211
hazeguard/hazemeter system was utilized.
Gloss was determined in accordance with ASTMD-2457.
EXAMPLE 1
The fiuorided, titanium-containing silica-alumina (Catalyst B) was tested for
polymerization activity in the 2.2 liter autoclave reactor with 1 mL of TEA, but no metal-
locene. It produced 53 grams of polymer per gram of fiuorided, titanium-containing
silica-alumina per hour. The polymer had a zero melt index, a zero HLMI, and a viscosity
average molecular weight of 2.4 million. Therefore, the fiuorided, titanium-containing
silica-alumina produced a high molecular weight polymer component that can be utilized
to produce the polymer composition of this invention.
The fluorided, titanium-containing silica-alumina then was retested for poly-
merization activity as conducted previously, except that a metallocene was added to the
reactor also to produce a polymer composition. A much improved activity of 4680 grams
of polymer per gram of fluorided, titanium-containing silica-alumina per hour was
observed. Thus, the polymer composition obtained was a combination of a very small
amount (about 1.1%) of an extremely high molecular weight polymer component from the
fluorided, titanium-containing silica-alumina and a majority of lower molecular weight
polymer produced from the metallocene catalyst. The fluorided, titanium-containing
silica-alumina thus contributed a high molecular weight polymer component equal to
about 1% of the bimodal polymer composition. The polymer composition had a high
load melt index of 3.67 and a melt index of 0.22. These results are shown in Table 1.
* Activity - grams of polymer per gram of fluorided, titanium-containing silica-
alumina per hour.
EXAMPLE 2
Both catalysts A and B then were used in the 23 gallon loop reactor with bis(n-
butylcyclopentadienyl) zirconium dichloride to produce linear low density polyethylene
(LLDPE). Both catalyst A and B had similar activity. In this back-to-back progression, it
is easy to see the effect of the high molecular weight polymer component produced by
Catalyst B. These results are shown in Table 2. Notice that although the HLMI/MI ratio
did not change noticeably, there is a substantial rise in the bulk density of the polymer
from about 20 lbs/ft to about 25 lbs/ft. This increase in bulk density allows for an
increase in polymer production.
EXAMPLE 3
Both catalyst A and catalyst C were used in the 23 gallon loop reactor described
previously with bis(n-butylcyclopentadienyl) zirconium dichloride at 80°C with 1-hexene
as comonomer to make grades of linear low density film polymer. These polymers are
shown in Table 3.
GPC analysis of the polymers using a viscometer detector showed that the
polymer produced from Catalyst C contained high molecular weight polymer component.
Careful inspection revealed that the polymer from catalyst C contained about 2.8% of its
polymer above a molecular weight of one million, whereas the polymer produced from
catalyst A contained almost none.
The polymer from Catalyst A and the inventive polymer composition produced
using Catalyst C were successfully blown into 1 mil thick film on the second processing
line described previously. The film produced using the inventive polymer composition
had improved melt strength. The melt index of film produced using catalyst A was 0.78
g/10 min, 0.90 g/10 mm, and 0.94 g/10 min while the film produced using the inventive
polymer composition produced from catalyst C had a melt index of 1.16 g/10 min and
2.03 g/10 min.
The optical properties of the film also are shown in Table 3. The high molecular
polymer produced by Catalyst C contained in the polymer composition resulted in
improved optical properties. The haze of the film using polymer produced from Catalyst
A was 9.92%, 15.13%, and 12.7%, while the haze of the film using the inventive polymer
composition from Catalyst C was 7.83% and 6.6%. The gloss of the film using the
polymer composition produced from Catalyst C also was improved over the film
produced from polymer produced from Catalyst A.
EXAMPLE 4
Another demonstration of improved properties from the polymer composition can
be seem from the following blending study. A metallocene-based LLDPE, commercially
available from Phillips Petroleum Company as grade D143, was blended with varying
amounts of another low density polyethylene polymer, also sold commercially through
Phillips Petroleum Company as D257. D143 was used as the base polymer and had a
melt index of 1.3 g/10 min, density of 0.916 g/cc, polydispersity (Mw/Mn) of 2.3, and by
GPC determination, contained almost no polymer having a molecular weight above one
million. D257 was utilized as the high molecular weight polymer component. D257 is a
chromium-based, broad molecular weight distribution, low density polymer containing a
high molecular weight polymer component. It had a melt index of 0.2 g/10 min and a
density of 0.923 g/cc. By GPC analysis, it was estimated that D257 contained about
10.3% by weight of polymer having a molecular weight greater than one million.
These two polymers were blended together during film blowing on the second
processing line described previously, then blown into 1 mil thick film. The smallest
increment of D257 added was 20% of the polymer composition, which equates to about
2.1% by weight of the polymer contained in the polymer composition having a molecular
weight greater than one million. This amount provided a reduction in the already low haze
value. The results of mis study are shown in Table 4.
EXAMPLE 5
Another blending study was conducted in which D257 was blended with another
metallocene derived base polymer. This base polymer had a melt index of about 1 g/10
min, a density of 0.926 g/cc, and a polydispersity (Mw/Mn) of 2.4. Only 3% of D257 was
blended with 97% of the base polymer, so that the polymer composition contained about
0.3 % of polymer having a molecular weight greater than one million. It was then
converted into 1 mil film using the case film processing line described previously. Even
this small quantity of added high molecular polymer component yielded a significant
improvement in clarity. These data are summarized in Table 5.
While this invention has been described in detail for the purpose of illustration, it
is not intended to be limited thereby but is intended to cover all changes and
modifications within the spirit and scope thereof.
EXAMPLE 6
Another blending study was conducted in which D257 was blended with yet
another metallocene derived base polymer. This base polymer had a melt index of about
1 g/10 min, a density of 0.920 g/cc, and a polydispersity (Mw/Mn) of 2.4. Only 5% of
D257 was blended with 95% the base polymer, so that the polymer composition contained
about 0.5% of polymer having a molecular weight greater than one million. It was then
converted into 1 mil film using the first blow film processing line described previously.
Even this small quantity of added high molecular weight polymer component yielded a
significant improvement in optical properties as may be seen from the reduction in haze.
These data are summarized in Table 6.
While this invention has been described in detail for the purpose of illustration, it
is not intended to be limited thereby but is intended to cover all changes and
modifications within the spirit and scope thereof.
We claim:
1. A process for producing a polymer composition, said process
comprising incorporating a narrow molecular weight distribution
base polymer and a high molecular weight polymer component to
produce said polymer composition;
wherein said base polymer is an ethylene polymer having a
Mw/Mn less than 5 and a melt flow index from 0.2 g/10 min to 20
g/10 min; and
wherein said high molecular weight polymer component has a
molecular weight distribution such that at least a substantial
portion of Its molecules have a molecular weight of greater than
one million, said high molecular weight polymer component being
incorporated in an amount to give 0.1 % to 10 % by weight,
based on the total weight of said polymer composition, of said
molecules having a molecular weight greater than one million.
2. A process for increasing the clarity of blown film from a narrow
molecular weight distribution base polymer, said process
comprising incorporating with said base polymer a high molecular
weight polymer component to produce said polymer composition;
wherein said base polymer is an ethylene polymer having a
Mw/Mn less than 5 and melt flow index from 0.2 g/10 min to 20
g/10 min; and
wherein sold high molecular weight polymer component has a
molecular weight distribution such that al least a substantial
portion of Its molecules have a molecular weight of greater than
one million, said high molecular weight polymer component being
incorporated in an amount to give 0.1 to 10 % by weight, based
on the total weight of said polymer composition, of said molecules
having a molecular weight greater than one million.
3. A process for increasing the bulk density of a narrow molecular
weight distribution base polymer, said process comprising
Incorporating with said base polymer a high molecular weight
polymer component to produce said polymer composition;
wherein said base polymer is an ethyiene polymer having a
Mw/Mn less than 5 and a melt flow index from 0.2 g/10 min to 20
g/10 min;
wherein said high molecular weight polymer component has a
molecular weight distribution such that at least a substantial
portion of Its molecules have a molecular weight of greater than
one million, said high molecular weight polymer component being
incorporated in an amount to give 0.1 to 10 % by weight, based
on the total weight of said polymer composition, of said molecules
having a molecular weight greater than one million;
wherein said Incorporating of said high molecular weight polymer
component and said base polymer occurs in a polymerization zone
by modifying a polymerization catalyst system before or after said
polymerization catalyst system is added to said polymerization
zone,
4. A process as claimed in any one of preceding claims 1-3, wherein
said Mw/Mn of said base polymer is less than 4.0.
5. A process as claimed in claim 4, wherein said melt flow index of
said base polymer is in a range from 0.5 g/10 min to 10 g/10 min,
6. A process as claimed In claim 5, wherein said base polymer is
produced by a catalyst selected from the group constating of
metallocene catalyst, Ziegler catalysts containing magnesium and
titanium halides, and chromium catalyst.
7. A process as claimed in claim 6, wherein said Mw/Mn of said base
polymer is less than 3.0.
8. A process as claimed in claim 7, wherein said melt flow index of
said base polymer is in a range from 0.8 g/10 min to 5.0 g/10 min.
9. A process as claimed In claim 8, wherein said base polymer has a
density in a range of 0.910 g/cc to 0.940 g/cc
10. A process as claimed in claim 9, wherein said base polymer has
a density in a range of 0.915 g/cc to 0.93 g/cc.
11. A process as claimed in any one of preceding claims 1-3,
wherein said high molecular weight polymer component being
incorporated is in an amount to give 05 % to 5 % by weight,
based on the total weight of said polymer composition, of said
molecules having a molecular weight greater than one million.
12. A process as claimed in claim 11, wherein said high molecular
weight polymer component Is produced from a catalyst consisting
of Ziegier catalysts based on titanium halides, zirconium halides,
zirconium alkyls, chromium oxide catalysts, metallocene catalysts,
and mixtures thereof.
13. A process as claimed in claim 12, wherein said high molecular
weight polymer component being incorporated is in an amount to
give 1 % to 3 % by weight, based on the total weight of said
polymer composition, of said molecules having a molecular weight
greater than one million.
14. A process as claimed in claim 13, wherein said high molecular
weight polymer component also contains a substantial amount of
polymer of molecular weight lower than one million provided said
high molecular weight polymer component has a sufficient amount
of polymer above one million in molecular weight to contribute the
proper amount of high molecular weight polymer component
15. A process as claimed in any one of preceding claims 1-3, wherein
said incorporating of said high molecular weight polymer
component with said base polymer occurs in a polymerization zone
by modifying a polymerization catalyst system before or after said
polymerization catalyst system is added to said polymerization
zone to produce said base polymer and said high molecular weight
polymer component
16. A process as claimed in claim 15, wherein said modifying of said
polymerization catalyst system is achieved by adding a second
transition metal component to said polymerization catalysts
system which then is capable of generating simultaneously said
base polymer and said high molecular weight polymer component
17. A process as claimed in claim 15, wherein polymerization catalyst
system comprises two metallocene components with a first
rnetallocene component producing said base polymer and a
second metallocene component producing said high molecular
weight polymer component
18. A process as claimed in claim 16, wherein modifying said
polymerization catalyst system occurs while it is In said
polymerization zone by adding said second transition metal
component which will react with said polymerization catalyst
system to produce high molecular weight polymer component
19. A process as claimed in claim 18, wherein said polymerization
catalyst system comprises a metallocene and wherein said
second transition metal component is a titanium or chromium
component
20. A process as claimed in claim 19, wherein said seclond transition
metal component is a fluorided, titanium-containing silica-
alumina or a fluorided, chromium-containing silica-alumina.
21. A process as claimed in claim 1 or 2, wherein said Incorporating of
said high molecular weight polymer component and said base
polymer to improve the clarity of blown film of said base polymer
occurs by blending said high molecular weight polymer component
and said base polymer after said high molecular weight polymer
component sand base polymer are produced separately.
22. A process as claimed in claim 2 wherein said base polymer and
said high molecular weight polymer component are produced by a
process comprising contacting ethylene, 1-hexene, bis (n-
butylcyclopentadlenyl) zirconium dichloride, a fluorided,
chromium-containing silica-alumina, and triethylaluminum in a
polymerization zone under polymerization conditions.
23. A process as claimed in claim 3, wherein said base polymer and
said high molecular weight polymer component are produced by a
process comprising contacting ethylene, 1-hexene, bis (n-
butylcyclopentadlenyl) zirconium dichloride, a fluorided, titanium-
containing silica-alumina, and triethylaluminum in a polymerization
zone under polymerization conditions.
24. A polymer composition obtainable by the process as claimed in
any one of preceding claims 1-23.
25. A polymer composition comprising a narrow molecular weight
distribution base polymer and a high molecular weight polymer
component;
wherein said base polymer is an ethyiene polymer having a
Mw/Mn less than 5 and a melt flow index from 0.2 of 10 min to 20
g/10 min;
wherein said high molecular weight polymer component has a
molecular weight distribution such that at least a substantial
portion of its molecules have a molecular weight of greater than
one million, said component being Incorporated in an amount to
give 0.1 to 10 % by weight based on the total weight of said
polymer composition, of said molecules having a molecular weight
greater than one million.
26. A composition as claimed in claim 25, wherein said Mw/Mn of
said base polymer is less than 4.0.
27. A composition as claimed in claim 26, wherein said melt flow
index of said base polymer is in a range from 0.5 g/10 min to 10
g/10 min.
28. A composition as claimed in claim 27, wherein said base polymer
is produced by a catalyst selected from the group consisting of
metallocene catalyst, Zlegler catalysts containing magnesium and
titanium halldes, and chromium catalyst
29. A composition as claimed in claim 28, wherein said Mw/Mn of
said base polymer is less than 3.0.
30. A composition as claimed in claim 29, wherein said melt flow
index of said base polymer is in a range from 0.8 g/10 min to 5.0
g/10 min.
31. A composition as claimed In claim 30, wherein said base polymer
has a density in a range of 0.910 g/cc to 0.940 g/cc.
32. A composition as claimed in claim 31, wherein said base polymer
has a density in a range of 0.915 g/cc to 0.93 g/cc.
33. A composition as claimed in claim 32, wherein said high
molecular weight polymer component being incorporated is in an
amount to give 05 to 5 % by weight, based on the total weight
of said polymer composition, of said molecules having a
molecular weight greater than one million.
34. A composition as claimed in claim 33, wherein said high
molecular weight polymer component is produced from a catalyst
consisting of Ziegler catalysts based on titanium halldes,
zirconium halldes, zirconium alkyls, chromium oxide catalysts,
chromocene catalysts, metallocene catalysts, and mixtures
tnereof.
35. A composition as claimed in claim 34, wherein said high
molecular weight polymer component being incorporated is in an
amount to give 1 % to 3 % weight, based on the total weight of
said polymer composition, of said molecules having a molecular
weight greater than one million.
36. A process as claimed in claim 34, wherein said high molecular
weight polymer component also contains a substantial amount of
polymer of molecular weight lower than one million provided said
high molecular weight polymer component has a sufficient
amount of polymer above one million in moiecuiar weight to
continue the proper amount of high molecular weight polymer
component.
A process for producing a polymer composition, said process
comprising incorporating a narrow molecular weight distribution base
polymer and a high molecular weight polymer component to produce
said polymer composition; wherein said base polymer is an ethylene
polymer having a Mw/Mn less than 5 and a melt flow Index from 0.2
g/10 min to 20 g/10 min; and wherein said high molecular weight
polymer component has a molecular weight distribution such that at
least a substantial portion of its molecules have a molecular weight of
greater than one million, said high molecular weight polymer
component being incorporated in an amount to give 0.1 % to 10 %
by weight, based on the total weight of said polymer composition, of
said molecules having a molecular weight greater than one million.

Documents:

in-pct-2002-01376-kol-granted-abstract.pdf

in-pct-2002-01376-kol-granted-claims.pdf

in-pct-2002-01376-kol-granted-correspondence.pdf

in-pct-2002-01376-kol-granted-description (complete).pdf

in-pct-2002-01376-kol-granted-form 1.pdf

in-pct-2002-01376-kol-granted-form 18.pdf

in-pct-2002-01376-kol-granted-form 2.pdf

in-pct-2002-01376-kol-granted-form 3.pdf

in-pct-2002-01376-kol-granted-form 5.pdf

in-pct-2002-01376-kol-granted-gpa.pdf

in-pct-2002-01376-kol-granted-letter patent.pdf

in-pct-2002-01376-kol-granted-reply to examination report.pdf

in-pct-2002-01376-kol-granted-specification.pdf


Patent Number 212741
Indian Patent Application Number IN/PCT/2002/01376/KOL
PG Journal Number 50/2007
Publication Date 14-Dec-2007
Grant Date 12-Dec-2007
Date of Filing 06-Nov-2002
Name of Patentee PHILLIPS PETROLEUM COMPANY
Applicant Address 4TH AND KEELER, BARTLESVILLE, OK 74004
Inventors:
# Inventor's Name Inventor's Address
1 COLLINS, KATHY S. 3915 SILVER LAKE, DRIVE BARTLESVILLE, OK, 74006
2 MCDANIEL, MAX P. 1601 MELMART DRIVE, BARTLESVILE, OK, 74006
3 EATON, ANTHONY P. 450 WILLIAMS LANDING, DR. SUGAR LAND, TX 77479
4 BENHAM, ELIZABETH A. 9310 KATIE GRACE CIRCLE SPRING, TX 77379
5 KENNEDY, SHAWN R. 522 LILLY DRIVE SOLDOTNA, AR 99669
6 SUKHADIA, ASHISH M. 1605 CHEROKEE PLACE, BARTLESVILLE, OK, 74003
7 KRISHNASWAMY, RAJENDRA K. 5221 NOWATA ROAD, APT. D-101 BARTLESVILLE, OK, 74006
PCT International Classification Number C 08 L 23/00
PCT International Application Number PCT/US01/16798
PCT International Filing date 2001-05-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/577,952 2000-05-24 U.S.A.