# Patent

## Title
Rotational molded articles, and method of making the same

## Abstract

The instant invention provides rotational molded articles, and method of making the same. The rotational molded articles according to the present invention comprise a polyethylene composition comprising: (a) at least 85 percent by weight of the units derived from ethylene; and (b) less than 15 percent by weight of units derived from one or more α-olefin comonomers; wherein the polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a non-provisional application claiming priority from the U.S. Provisional Patent Application No. 61/237,891, filed on Aug. 28, 2009, entitled “ROTATIONAL MOLDED ARTICLES, AND METHOD OF MAKING THE SAME,” the teachings of which are incorporated by reference herein, as if reproduced in full hereinbelow.


FIELD OF INVENTION
The instant invention relates to rotational molded articles, and method of making the same.
BACKGROUND OF THE INVENTION
The use of polyethylene compositions, such as linear low density polyethylenes and/or high density polyethylenes, in fabrication of rotational molded articles is generally known. Any conventional method, such as gas phase process, slurry process, solution process or high pressure process, may be employed to produce such polyethylene compositions.
In general, in the rotational molding process, polymeric materials are placed into a heated mold. The heated mold causes the polymeric materials to melt and form a puddle at the bottom of the mold cavity. The mold is then slowly rotated, usually around two perpendicular axes, causing the melted polymeric materials to flow into to the mold and stick to its walls. In order to maintain even thickness throughout the part, the mold continues to rotate during the cooling phase.
Various polymerization techniques using different catalyst systems have been employed to produce such polyethylene compositions suitable for rotational molding applications. However, the currently available polyethylene compositions fail to provide a stiffness/toughness balance that is required for rotational moldings applications.
Despite the research efforts in developing polyethylene compositions suitable for rotational molding, there is still a need for a polyethylene composition having a narrow molecular weight distribution, narrow composition distribution, and improved impact resistance while maintaining stiffness and processability properties. Additionally, there is a need for a method of producing such polyethylene compositions having a narrow molecular weight distribution, narrow composition distribution, and improved impact resistance while maintaining stiffness and processability properties.
SUMMARY OF THE INVENTION
The instant invention provides rotational molded articles, and method of making the same.
In one embodiment, the instant invention provides a rotational molded article comprising a polyethylene composition comprising: (a) at least 85 percent by weight of the units derived from ethylene; and (b) less than 15 percent by weight of units derived from one or more α-olefin comonomers; wherein the polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition.
In an alternative embodiment, the instant invention provides process for making an article comprising the steps of (1) selecting a polyethylene composition comprising (a) at least 85 percent by weight of the units derived from ethylene; and (b) less than 15 percent by weight of units derived from one or more α-olefin comonomers; wherein said polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of said composition; and (2) forming said polyethylene composition into an article via rotational molding process.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition has a density in the range of 0.935 to 0.945 g/cm3.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition has a melt index (I2) in the range of 1 to 10 g/10 minutes.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition has less than 2 peaks on an elution temperature-eluted amount curve determined by continuous temperature rising elution fraction method at equal or above 30° C., wherein the purge peak, which is below 30° C., is excluded.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition comprises less than 11 percent by weight of the units derived from one or more α-olefin comonomers.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition is substantially free of long chain branching.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition comprises less than 100 parts by weight of a hafnium based metallocene catalyst per one million parts of polyethylene composition.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition has a melt flow ratio (I21/I2) in the range of 12 to 23.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition has a melt index (I21 in the range of 7.5 to 400 g/10 minutes.
In another alternative embodiment, the instant invention provides a rotational molded article, and process for making such articles, in accordance with any of the preceding embodiments, except that the polyethylene composition comprises the (co)polymerization reaction product of ethylene and optionally one or more α-olefin comonomers in the presence of a hafnium based metallocene catalyst via a gas phase (co)polymerization process in a single stage reactor.


DETAILED DESCRIPTION OF THE INVENTION
The instant invention provides rotational molded articles, and method of making the same. In one embodiment, the instant invention provides a rotational molded article comprising a polyethylene composition comprising: (a) at least 85 percent by weight of the units derived from ethylene; and (b) less than 15 percent by weight of units derived from one or more α-olefin comonomers; wherein the polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition.
The term (co)polymerization, as used herein, refers to the polymerization of ethylene and optionally one or more comonomers, e.g. one or more α-olefin comonomers. Thus, the term (co)polymerization refers to both polymerization of ethylene and copolymerization of ethylene and one or more comonomers, e.g. one or more α-olefin comonomers.
The polyethylene composition according to instant invention has a density in the range of 0.930 to 0.945 g/cm3. All individual values and subranges from 0.930 to 0.945 g/cm3 are included herein and disclosed herein; for example, the density can be from a lower limit of 0.930, 0.931, 0.932, or 0.933 g/cm3 to an upper limit of 0.942, 0.943, 0.944, or 0.945 g/cm3. For example, the polyethylene composition may have a density in the range of 0.930 to 0.945 g/cm3; or in the alternative, the polyethylene composition may have a density in the range of 0.930 to 0.944 g/cm3; or in the alternative, the polyethylene composition may have a density in the range of 0.930 to 0.943 g/cm3; or in the alternative, the polyethylene composition may have a density in the range of 0.930 to 0.942 g/cm3.
The polyethylene composition according to the instant invention has a molecular weight distribution (Mw/Mn) (measured according to the conventional GPC method) in the range of 1.70 to 3.5. All individual values and subranges from 1.70 to 3.5 are included herein and disclosed herein; for example, the molecular weight distribution (Mw/Mn) can be from a lower limit of 1.70, 2.00, or 2.20 to an upper limit of 3.00, 3.10, 3.20, 3.30, 3.40 or 3.50. For example, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.40; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.30; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.20; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.10; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.00.; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 2.00 to 3.30; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 2.00 to 3.20; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 2.00 to 3.10; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 2.00 to 3.00; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 2.20 to 3.20; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 2.20 to 3.10; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mw/Mn) in the range of 2.20 to 3.00.
The polyethylene composition according to the instant invention has a melt index (I2) in the range of 0.5 to 20 g/10 minutes. All individual values and subranges from 0.5 to 20 g/10 minutes are included herein and disclosed herein; for example, the melt index (I2) can be from a lower limit of 0.5, 0.7, 0.9, 1.1, 2, 5, or 10 g/10 minutes, to an upper limit of 5, 10, 14, 16, 18, or 20 g/10 minutes. For example, the polyethylene composition may have a melt index (I2) in the range of 0.5 to 18 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I2) in the range of 0.7 to 18 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I2) in the range of 0.9 to 10 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I2) in the range of 1.1 to 14 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I2) in the range of 1.1 to 18 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I2) in the range of 0.9 to 14 g/10 minutes.
The polyethylene composition according to the instant invention has a melt index (I21) in the range of 7.50 to 400 g/10 minutes. All individual values and subranges from 7.50 to 400 g/10 minutes are included herein and disclosed herein; for example, the melt index (I21) can be from a lower limit of 7.50, 10, 12, 15, 20, or 25 g/10 minutes, to an upper limit of 50, 100, 160, 200, 250, 300, 350, or 400 g/10 minutes. For example, the polyethylene composition may have a melt index (I21) in the range of 7.50 to 350 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I21) in the range of 10 to 350 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I21) in the range of 12 to 300 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I21) in the range of 15 to 250 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I21) in the range of 20 to 200 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I21) in the range of 25 to 160 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I21) in the range of 25 to 200 g/10 minutes; or in the alternative, the polyethylene composition may have a melt index (I21) in the range of 15 to 160 g/10 minutes.
The polyethylene composition according to the instant invention has a melt flow ratio (I21/I2) in the range of 12 to 23. All individual values and subranges from 12 to 23 minutes are included herein and disclosed herein; for example, the melt flow ratio (I21/I2) can be from a lower limit of 12, 13, 14, or 15 to an upper limit of 20, 21, 22, or 23. For example, the polyethylene composition may have a melt flow ratio (I21/I2) in the range 12 to 22; or in the alternative, the polyethylene composition may have a melt flow ratio (I21/I2) in the range 12 to 21; or in the alternative, the polyethylene composition may have a melt flow ratio (I21/I2) in the range 13 to 22; or in the alternative, the polyethylene composition may have a melt flow ratio (I21/I2) in the range 13 to 21; or in the alternative, the polyethylene composition may have a melt flow ratio (I21/I2) in the range 14 to 21; or in the alternative, the polyethylene composition may have a melt flow ratio (I21/I2) in the range 14 to 20; or in the alternative, the polyethylene composition may have a melt flow ratio (I21/I2) in the range 15 to 20.
The polyethylene composition according to the instant invention has a molecular weight (Mw) in the range of 50,000 to 200,000 daltons. All individual values and subranges from 50,000 to 200,000 daltons are included herein and disclosed herein; for example, the molecular weight (Mw) can be from a lower limit of 50,000, 55,000, 60,000, 65,000, or 70,000 daltons to an upper limit of 150,000, 160,000, 170,000, 180,000, or 200,000. For example, the polyethylene composition may have a molecular weight (Mw) in the range of 50,000 to 190,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 50,000 to 180,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 50,000 to 170,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 55,000 to 180,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 60,000 to 170,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 55,000 to 160,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 50,000 to 150,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 55,000 to 180,000 daltons; or in the alternative, the polyethylene composition may have a molecular weight (Mw) in the range of 60,000 to 180,000 daltons.
The polyethylene composition may have molecular weight distribution (Mz/Mw) (measured according to the conventional GPC method) in the range of less than 5. All individual values and subranges from less than 5 are included herein and disclosed herein; for example, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 4.5; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 4; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 3.5; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 3.0; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 2.8; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 2.6; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 2.5; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 2.4; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 2.3; or in the alternative, the polyethylene composition may have a molecular weight distribution (Mz/Mw) in the range of less than 2.2.
The polyethylene composition may have a vinyl unsaturation of less than 0.1 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition. All individual values and subranges from less than 0.1 are included herein and disclosed herein; for example, the polyethylene composition may have a vinyl unsaturation of less than 0.08 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition; or in the alternative, the polyethylene composition may have a vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition; or in the alternative, the polyethylene composition may have a vinyl unsaturation of less than 0.05 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition; or in the alternative, the polyethylene composition may have a vinyl unsaturation of less than 0.04 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition; or in the alternative, the polyethylene composition may have a vinyl unsaturation of less than 0.03 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition.
The polyethylene composition may comprise less than 15 percent by weight of units derived from one or more α-olefin comonomers. All individual values and subranges from less than 15 weight percent are included herein and disclosed herein; for example, the polyethylene composition may comprise less than 12 percent by weight of units derived from one or more α-olefin comonomers; or in the alternative, the polyethylene composition may comprise less than 11 percent by weight of units derived from one or more α-olefin comonomers; or in the alternative, the polyethylene composition may comprise less than 9 percent by weight of units derived from one or more α-olefin comonomers; or in the alternative, the polyethylene composition may comprise less than 7 percent by weight of units derived from one or more α-olefin comonomers; or in the alternative, the polyethylene composition may comprise less than 5 percent by weight of units derived from one or more α-olefin comonomers; or in the alternative, the polyethylene composition may comprise less than 4.5 percent by weight of units derived from one or more α-olefin comonomers; or in the alternative, the polyethylene composition may comprise between 0.8 to 4.5 percent by weight of units derived from one or more α-olefin comonomers.
The α-olefin comonomers typically have no more than 20 carbon atoms. For example, the α-olefin comonomers may preferably have 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. The one or more α-olefin comonomers may, for example, be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, from the group consisting of 1-hexene and 1-octene.
The polyethylene composition may comprise from 85 to 99.2 percent by weight of units derived from ethylene. All individual values and subranges from 85 to 99.2 weight percent are included herein and disclosed herein; for example, the polyethylene composition may comprise from 90 to 99.2 percent by weight of units derived from ethylene; or in the alternative, the polyethylene composition may comprise from 92 to 99.2percent by weight of units derived from ethylene; or in the alternative, the polyethylene composition may comprise from 93 to 99.2 percent by weight of units derived from ethylene; or in the alternative, the polyethylene composition may comprise from 94 to 99.2 percent by weight of units derived from ethylene; or in the alternative, the polyethylene composition may comprise from 95 to 99.2 percent by weight of units derived from ethylene; or in the alternative, the polyethylene composition may comprise from 95.5 to 99.2 percent by weight of units derived from ethylene.
The polyethylene composition of the instant invention is substantially free of any long chain branching, and preferably, the polyethylene composition of the instant invention is free of any long chain branching. Substantially free of any long chain branching, as used herein, refers to a polyethylene composition preferably substituted with less than about 0.1 long chain branching per 1000 total carbons, and more preferably, less than about 0.01 long chain branching per 1000 total carbons. In the alternative, the polyethylene composition of the instant invention is free of any long chain branching.
The polyethylene composition may further comprise less than or equal to 100 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition. All individual values and subranges from less than or equal to 100 ppm are included herein and disclosed herein; for example, the polyethylene composition may further comprise less than or equal to 10 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 8 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 6 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 4 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 2 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 1.5 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 1 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 0.75 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition; or in the alternative, the polyethylene composition may further comprise less than or equal to 0.5 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition the polyethylene composition may further comprise less than or equal to 0.25 parts by weight of hafnium residues remaining from the hafnium based metallocene catalyst per one million parts of polyethylene composition. The hafnium residues remaining from the hafnium based metallocene catalyst in the inventive polyethylene composition may be measured by x-ray fluorescence (XRF), which is calibrated to reference standards. The polymer resin granules are compression molded at elevated temperature into plaques having a thickness of about 3/8 of an inch for the x-ray measurement in a preferred method. At very low concentrations of metal, such as below 0.1 ppm, ICP-AES would be a suitable method to determine metal residues present in the inventive polyethylene composition. In one embodiment, the inventive polyethylene composition has substantially no chromium, zirconium or titanium content, that is, no or only what would be considered by those skilled in the art, trace amounts of these metals are present, such as, for example, less than 0.001 ppm.
The polyethylene composition in accordance with the instant invention may have less than 2 peaks on an elution temperature-eluted amount curve determined by continuous temperature rising elution fraction method at equal or above 30° C., wherein the purge peak which is below 30° C. is excluded. In the alternative, the polyethylene composition may have only 1 peak or less on an elution temperature-eluted amount curve determined by continuous temperature rising elution fraction method at equal or above 30° C., wherein the purge peak which is below 30° C. is excluded. In the alternative, the polyethylene composition may have only 1 peak on an elution temperature-eluted amount curve determined by continuous temperature rising elution fraction method at equal or above 30° C., wherein the purge peak which is below 30° C. is excluded. In addition, artifacts generated due to instrumental noise at either side of a peak are not considered to be peaks.
The inventive polyethylene composition may further comprise additional components such as other polymers and/or additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The inventive polyethylene composition may contain any amounts of additives. The inventive polyethylene composition may comprise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the inventive polyethylene composition including such additives. All individual values and subranges from about 0 to about 10 weight percent are included herein and disclosed herein; for example, the inventive polyethylene composition may comprise from 0 to 7 percent by the combined weight of additives, based on the weight of the inventive polyethylene composition including such additives; in the alternative, the inventive polyethylene composition may comprise from 0 to 5 percent by the combined weight of additives, based on the weight of the inventive polyethylene composition including such additives; or in the alternative, the inventive polyethylene composition may comprise from 0 to 3 percent by the combined weight of additives, based on the weight of the inventive polyethylene composition including such additives; or in the alternative, the inventive polyethylene composition may comprise from 0 to 2 percent by the combined weight of additives, based on the weight of the inventive polyethylene composition including such additives; or in the alternative, the inventive polyethylene composition may comprise from 0 to 1 percent by the combined weight of additives, based on the weight of the inventive polyethylene composition including such additives; or in the alternative, the inventive polyethylene composition may comprise from 0 to 0.5 percent by the combined weight of additives, based on the weight of the inventive polyethylene composition including such additives. Antioxidants, such as IrgafosTM 168 and IrganoxTM 1010, may be used to protect the inventive polyethylene composition from thermal and/or oxidative degradation. IrganoxTM 1010 is tetrakis(methylene(3,5-di-tert-butyl-4hydroxyhydrocinnamate) available from Ciba Geigy Inc. IrgafosTM 168 is tris(2,4 di-tert-butylphenyl)phosphite available from Ciba Geigy Inc.
Any conventional ethylene(co)polymerization reaction may be employed to produce the inventive polyethylene composition. Such conventional ethylene(co)polymerization reactions include, but are not limited to, gas phase polymerization process, slurry phase polymerization process, liquid phase polymerization process, and combinations thereof using one or more conventional reactors, e.g. fluidized bed gas phase reactors, loop reactors, stirred tank reactors, batch reactors in parallel, series, and/or any combinations thereof. In the alternative, the inventive polyethylene composition may be produced in a high pressure reactor via a coordination catalyst system. For example, the inventive polyethylene composition according to the instant invention may be produced via gas phase polymerization process in a single gas phase reactor; however, the instant invention is not so limited, and any of the above polymerization processes may be employed. In one embodiment, the polymerization reactor may comprise of two or more reactors in series, parallel, or combinations thereof. Preferably, the polymerization reactor is one reactor, e.g. a fluidized bed gas phase reactor. In another embodiment, the gas phase polymerization reactor is a continuous polymerization reactor comprising one or more feed streams. In the polymerization reactor, the one or more feed streams are combined together, and the gas comprising ethylene and optionally one or more comonomers, e.g. one or more α-olefins, are flowed or cycled continuously through the polymerization reactor by any suitable means. The gas comprising ethylene and optionally one or more comonomers, e.g. one or more α-olefins, may be fed up through a distributor plate to fluidize the bed in a continuous fluidization process.
In production, a hafnium based metallocene catalyst system including a cocatalyst, as described hereinbelow in further details, ethylene, optionally one or more alpha-olefin comonomers, hydrogen, optionally one or more inert gases and/or liquids, e.g. N2, isopentane, and hexane, and optionally one or more continuity additive, e.g. ethoxylated stearyl amine or aluminum distearate or combinations thereof, are continuously fed into a reactor, e.g. a fluidized bed gas phase reactor. The reactor may be in fluid communication with one or more discharge tanks, surge tanks, purge tanks, and/or recycle compressors. The temperature in the reactor is typically in the range of 70 to 115° C., preferably 75 to 110° C., more preferably 75 to 100° C., and the pressure is in the range of 15 to 30 atm, preferably 17 to 26 atm. A distributor plate at the bottom of the polymer bed provides a uniform flow of the upflowing monomer, comonomer, and inert gases stream. A mechanical agitator may also be provided to provide contact between the solid particles and the comonomer gas stream. The fluidized bed, a vertical cylindrical reactor, may have a bulb shape at the top to facilitate the reduction of gas velocity; thus, permitting the granular polymer to separate from the upflowing gases. The unreacted gases are then cooled to remove the heat of polymerization, recompressed, and then recycled to the bottom of the reactor. Once the residual hydrocarbons are removed, and the resin is transported under N2 to a purge bin, moisture may be introduced to reduce the presence of any residual catalyzed reactions with O2 before the inventive polyethylene composition is exposed to oxygen. The polyethylene composition may then be transferred to an extruder to be pelletized. Such pelletization techniques are generally known. The polyethylene composition may further be melt screened. Subsequent to the melting process in the extruder, the molten composition is passed through one or more active screens, positioned in series of more than one, with each active screen having a micron retention size of from about 2 μm to about 400 μm (2 to 4×10−5 m), and preferably about 2 μm to about 300 μm (2 to 3×10−5 m), and most preferably about 2 μm to about 70 μm (2 to 7×10−6 m), at a mass flux of about 5 to about 100 lb/hr/in2 (1.0 to about 20 kg/s/m2). Such further melt screening is disclosed in U.S. Pat. No. 6,485,662, which is incorporated herein by reference to the extent that it discloses melt screening.
In an embodiment of a fluidized bed reactor, a monomer stream is passed to a polymerization section. The fluidized bed reactor may include a reaction zone in fluid communication with a velocity reduction zone. The reaction zone includes a bed of growing polymer particles, formed polymer particles and catalyst composition particles fluidized by the continuous flow of polymerizable and modifying gaseous components in the form of make-up feed and recycle fluid through the reaction zone. Preferably, the make-up feed includes polymerizable monomer, most preferably ethylene and optionally one or more α-olefin comonomers, and may also include condensing agents as is known in the art and disclosed in, for example, U.S. Pat. Nos. 4,543,399, 5,405,922, and 5,462,999.
The fluidized bed has the general appearance of a dense mass of individually moving particles, preferably polyethylene particles, as created by the percolation of gas through the bed. The pressure drop through the bed is equal to or slightly greater than the weight of the bed divided by the cross-sectional area. It is thus dependent on the geometry of the reactor. To maintain a viable fluidized bed in the reaction zone, the superficial gas velocity through the bed must exceed the minimum flow required for fluidization. Preferably, the superficial gas velocity is at least two times the minimum flow velocity. Ordinarily, the superficial gas velocity does not exceed 1.5 m/sec and usually no more than 0.76 ft/sec is sufficient.
In general, the height to diameter ratio of the reaction zone can vary in the range of about 2:1 to about 5:1. The range, of course, can vary to larger or smaller ratios and depends upon the desired production capacity. The cross-sectional area of the velocity reduction zone is typically within the range of about 2 to about 3 multiplied by the cross-sectional area of the reaction zone.
The velocity reduction zone has a larger inner diameter than the reaction zone, and can be conically tapered in shape. As the name suggests, the velocity reduction zone slows the velocity of the gas due to the increased cross sectional area. This reduction in gas velocity drops the entrained particles into the bed, reducing the quantity of entrained particles that flow from the reactor. The gas exiting the overhead of the reactor is the recycle gas stream.
The recycle stream is compressed in a compressor and then passed through a heat exchange zone where heat is removed before the stream is returned to the bed. The heat exchange zone is typically a heat exchanger, which can be of the horizontal or vertical type. If desired, several heat exchangers can be employed to lower the temperature of the cycle gas stream in stages. It is also possible to locate the compressor downstream from the heat exchanger or at an intermediate point between several heat exchangers. After cooling, the recycle stream is returned to the reactor through a recycle inlet line. The cooled recycle stream absorbs the heat of reaction generated by the polymerization reaction.
Preferably, the recycle stream is returned to the reactor and to the fluidized bed through a gas distributor plate. A gas deflector is preferably installed at the inlet to the reactor to prevent contained polymer particles from settling out and agglomerating into a solid mass and to prevent liquid accumulation at the bottom of the reactor as well to facilitate easy transitions between processes that contain liquid in the cycle gas stream and those that do not and vice versa. Such deflectors are described in the U.S. Pat. Nos. 4,933,149 and 6,627,713.
The hafnium based catalyst system used in the fluidized bed is preferably stored for service in a reservoir under a blanket of a gas, which is inert to the stored material, such as nitrogen or argon. The hafnium based catalyst system may be added to the reaction system, or reactor, at any point and by any suitable means, and is preferably added to the reaction system either directly into the fluidized bed or downstream of the last heat exchanger, i.e. the exchanger farthest downstream relative to the flow, in the recycle line, in which case the activator is fed into the bed or recycle line from a dispenser. The hafnium based catalyst system is injected into the bed at a point above distributor plate. Preferably, the hafnium based catalyst system is injected at a point in the bed where good mixing with polymer particles occurs. Injecting the hafnium based catalyst system at a point above the distribution plate facilitates the operation of a fluidized bed polymerization reactor.
The monomers can be introduced into the polymerization zone in various ways including, but not limited to, direct injection through a nozzle into the bed or cycle gas line. The monomers can also be sprayed onto the top of the bed through a nozzle positioned above the bed, which may aid in eliminating some carryover of fines by the cycle gas stream.
Make-up fluid may be fed to the bed through a separate line to the reactor. The composition of the make-up stream is determined by a gas analyzer. The gas analyzer determines the composition of the recycle stream, and the composition of the make-up stream is adjusted accordingly to maintain an essentially steady state gaseous composition within the reaction zone. The gas analyzer can be a conventional gas analyzer that determines the recycle stream composition to maintain the ratios of feed stream components. Such equipment is commercially available from a wide variety of sources. The gas analyzer is typically positioned to receive gas from a sampling point located between the velocity reduction zone and heat exchanger.
The production rate of inventive polyethylene composition may be conveniently controlled by adjusting the rate of catalyst composition injection, activator injection, or both. Since any change in the rate of catalyst composition injection will change the reaction rate and thus the rate at which heat is generated in the bed, the temperature of the recycle stream entering the reactor is adjusted to accommodate any change in the rate of heat generation. This ensures the maintenance of an essentially constant temperature in the bed. Complete instrumentation of both the fluidized bed and the recycle stream cooling system is, of course, useful to detect any temperature change in the bed so as to enable either the operator or a conventional automatic control system to make a suitable adjustment in the temperature of the recycle stream.
Under a given set of operating conditions, the fluidized bed is maintained at essentially a constant height by withdrawing a portion of the bed as product at the rate of formation of the particulate polymer product. Since the rate of heat generation is directly related to the rate of product formation, a measurement of the temperature rise of the fluid across the reactor, i.e. the difference between inlet fluid temperature and exit fluid temperature, is indicative of the rate of polyethylene composition formation at a constant fluid velocity if no or negligible vaporizable liquid is present in the inlet fluid.
On discharge of particulate polymer product from reactor, it is desirable and preferable to separate fluid from the product and to return the fluid to the recycle line. There are numerous ways known to the art to accomplish this separation. Product discharge systems which may be alternatively employed are disclosed and claimed in U.S. Pat. No. 4,621,952. Such a system typically employs at least one (parallel) pair of tanks comprising a settling tank and a transfer tank arranged in series and having the separated gas phase returned from the top of the settling tank to a point in the reactor near the top of the fluidized bed.
In the fluidized bed gas phase reactor embodiment, the reactor temperature of the fluidized bed process herein ranges from 70° C., or 75° C., or 80° C. to 90° C., or 95° C., or 100° C., or 110° C., or 115° C., wherein a desirable temperature range comprises any upper temperature limit combined with any lower temperature limit described herein. In general, the reactor temperature is operated at the highest temperature that is feasible, taking into account the sintering temperature of the desired polyethylene composition within the reactor and fouling that may occur in the reactor or recycle line(s).
The process of the present invention is suitable for the production of homopolymers comprising ethylene derived units, or copolymers comprising ethylene derived units and at least one or more other α-olefin(s) derived units.
In order to maintain an adequate catalyst productivity in the present invention, it is preferable that the ethylene is present in the reactor at a partial pressure at or greater than 160 psia (1100 kPa), or 190 psia (1300 kPa), or 200 psia (1380 kPa), or 210 psia (1450 kPa), or 220 psia (1515 kPa).
The comonomer, e.g. one or more α-olefin comonomers, if present in the polymerization reactor, is present at any level that will achieve the desired weight percent incorporation of the comonomer into the finished polyethylene. This is expressed as a mole ratio of comonomer to ethylene as described herein, which is the ratio of the gas concentration of comonomer moles in the cycle gas to the gas concentration of ethylene moles in the cycle gas. In one embodiment of the polyethylene composition production, the comonomer is present with ethylene in the cycle gas in a mole ratio range of from 0 to 0.1 (comonomer:ethylene); and from 0 to 0.05 in another embodiment; and from 0 to 0.04 in another embodiment; and from 0 to 0.03 in another embodiment; and from 0 to 0.02 in another embodiment.
Hydrogen gas may also be added to the polymerization reactor(s) to control the final properties (e.g., I21 and/or I2) of the inventive polyethylene composition. In one embodiment, the ratio of hydrogen to total ethylene monomer (ppm H2/mol % C2) in the circulating gas stream is in a range of from 0 to 60:1; in another embodiment; from 0.10:1 (0.10) to 50:1 (50); in another embodiment; from 0 to 35:1 (35); in another embodiment, from 0 to 25:1 (25); in another embodiment, from 7:1 (7) to 22:1 (22).
In one embodiment, the process for producing a polyethylene composition according to the instant invention comprises the steps of: (1) (co)polymerizing ethylene and optionally one or more α-olefin comonomer in the presence of a hafnium based metallocene catalyst via a gas phase (co)polymerization process in a single stage reactor; and (2) thereby producing the polyethylene composition, wherein the polyethylene composition has a density in the range of 0.907 to 0.975 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.62, a melt index (I2) in the range of 2 to 1000 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, and a vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of the composition.
In one embodiment, the process for producing a polyethylene composition according to the instant invention comprises the steps of: (1) (co)polymerizing ethylene and optionally one or more α-olefin comonomer in the presence of a hafnium based metallocene catalyst via a gas phase (co)polymerization process in a single stage reactor; and (2) thereby producing the inventive polyethylene composition, wherein the polyethylene composition has a density in the range of 0.950 to 0.954 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 2.9 to 3.5, a melt index (I2) in the range of 34 to 46 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.2, and a vinyl unsaturation of less than 0.01 vinyls per one thousand carbon atoms present in the backbone of the composition.
In one embodiment, the process for producing a polyethylene composition according to the instant invention comprises the steps of: (1) (co)polymerizing ethylene and optionally one or more α-olefin comonomer in the presence of a hafnium based metallocene catalyst via a gas phase (co)polymerization process in a single stage reactor; and (2) thereby producing the inventive polyethylene composition, wherein the polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of the polyethylene composition.
The hafnium based catalyst system, as used herein, refers to a catalyst capable of catalyzing the polymerization of ethylene monomers and optionally one or more α-olefin co monomers to produce polyethylene. Furthermore, the hafnium based catalyst system comprises a hafnocene component. The hafnocene component may comprise mono-, bis- or tris-cyclopentadienyl-type complexes of hafnium. In one embodiment, the cyclopentadienyl-type ligand comprises cyclopentadienyl or ligands isolobal to cyclopentadienyl and substituted versions thereof. Representative examples of ligands isolobal to cyclopentadienyl include, but are not limited to, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or “H4Ind”) and substituted versions thereof. In one embodiment, the hafnocene component is an unbridged bis-cyclopentadienyl hafnocene and substituted versions thereof. In another embodiment, the hafnocene component excludes unsubstituted bridged and unbridged bis-cyclopentadienyl hafnocenes, and unsubstituted bridged and unbridged bis-indenyl hafnocenes. The term “unsubstituted,” as used herein, means that there are only hydride groups bound to the rings and no other group. Preferably, the hafnocene useful in the present invention can be represented by the formula (where “Hf” is hafnium):

CpnHfXp   (1)

wherein n is 1 or 2, p is 1, 2 or 3, each Cp is independently a cyclopentadienyl ligand or a ligand isolobal to cyclopentadienyl or a substituted version thereof bound to the hafnium; and X is selected from the group consisting of hydride, halides, C1 to C10 alkyls and C2 to C12 alkenyls; and wherein when n is 2, each Cp may be bound to one another through a bridging group A selected from the group consisting of C1 to C5 alkylenes, oxygen, alkylamine, silyl-hydrocarbons, and siloxyl-hydrocarbons. An example of C1 to C5 alkylenes include ethylene (—CH2CH2—) bridge groups; an example of an alkylamine bridging group includes methylamide (—(CH3)N—); an example of a silyl-hydrocarbon bridging group includes dimethylsilyl (—(CH3)2Si—); and an example of a siloxyl-hydrocarbon bridging group includes (—O—(CH3)2Si—O—). In one particular embodiment, the hafnocene component is represented by formula (1), wherein n is 2 and p is 1 or 2.
As used herein, the term “substituted” means that the referenced group possesses at least one moiety in place of one or more hydrogens in any position, the moieties selected from such groups as halogen radicals such as F, Cl, Br, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1 to C10 alkyl groups, C2 to C10 alkenyl groups, and combinations thereof. Examples of substituted alkyls and aryls includes, but are not limited to, acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof. More preferably, the hafnocene component useful in the present invention can be represented by the formula:

(CpR5)2HfX2   (2)

wherein each Cp is a cyclopentadienyl ligand and each is bound to the hafnium; each R is independently selected from hydrides and C1 to C10 alkyls, most preferably hydrides and C1 to C5 alkyls; and X is selected from the group consisting of hydride, halide, C1 to C10 alkyls and C2 to C12 alkenyls, and more preferably X is selected from the group consisting of halides, C2 to C6 alkylenes and C1 to C6 alkyls, and most preferably X is selected from the group consisting of chloride, fluoride, C1 to C5 alkyls and C2 to C6 alkylenes. In a most preferred embodiment, the hafnocene is represented by formula (2) above, wherein at least one R group is an alkyl as defined above, preferably a C1 to C5 alkyl, and the others are hydrides. In a most preferred embodiment, each Cp is independently substituted with from one two three groups selected from the group consisting of methyl, ethyl, propyl, butyl, and isomers thereof.
In one embodiment, the hafnocene based catalyst system is heterogeneous, i.e. the hafnocene based catalyst may further comprise a support material. The support material can be any material known in the art for supporting catalyst compositions; for example an inorganic oxide; or in the alternative, silica, alumina, silica-alumina, magnesium chloride, graphite, magnesia, titania, zirconia, and montmorillonite, any of which can be chemically/physically modified such as by fluoriding processes, calcining or other processes known in the art. In one embodiment the support material is a silica material having an average particle size as determined by Malvern analysis of from 1 to 60 mm; or in the alternative, 10 to 40 mm.
The hafnocene based catalyst system may further comprise an activator. Any suitable activator known to activate catalyst components towards olefin polymerization may be suitable. In one embodiment, the activator is an alumoxane; in the alternative methalumoxane such as described by J. B. P. Soares and A. E. Hamielec in 3(2) POLYMER REACTION ENGINEERING 131 200 (1995). The alumoxane may preferably be co-supported on the support material in a molar ratio of aluminum to hafnium (Al:Hf) ranging from 80:1 to 200:1, most preferably 90:1 to 140:1.
Such hafnium based catalyst systems are further described in details in the U.S. Pat. Nos. 6,242,545 and 7,078,467, incorporated herein by reference.
In application, the inventive polyethylene composition may be used to manufacture shaped articles. Such articles may include, but are not limited to, rotational molded articles such as fuel tanks, furniture, tilt trucks, industrial containers, storage tanks, portable outhouses, modular bathrooms, telephone booths, boat hulls, garbage cans, light globes, ice buckets, appliance housings, toys, and the like. Different methods may be employed to manufacture such articles. Suitable conversion techniques include, but are not limited to, rotational molding process. Such techniques are generally well known.
In rotational molding process, the product is formed from the polyethylene composition described above inside a closed mold or cavity while the mold is rotating biaxially in a heating chamber. To obtain this mold rotation in two planes perpendicular to each other, the spindle is turned on a primary axis, while the molds are rotated on a secondary axis.
Rotational molding is best suited for large, hollow products requiring stress-free strength, complicated curves, a good finish, a variety of colors, and uniform wall thickness. There are essentially four basic steps in rotational molding: loading, molding or curing, cooling, and unloading.
In the loading stage, the polyethylene composition is charged into a hollow mold. The mold halves then are clamped shut and moved into an oven where the loaded mold spins biaxially. Rotation speeds should be infinitely variable at the heating station, ranging up to 40 rpm on the minor axes and 12 rpm on the major axes. A 4:1 rotation ratio generally is used for symmetrically shaped objects, but a wide variety of ratios are necessary for molding unusual configurations.
In the oven, the heat penetrates the mold, causing the polyethylene composition, preferably in the powder form to become tacky and sticky to the mold surface. On most units, the heating is done either by air (as in a gas-fired hot-air oven) or by a liquid of high specific heat, such as molten salt; where jacketed molds are used, heating is done with a hot liquid medium, such as oil.
Because the molds continue to rotate while the heating is continued, the polyethylene composition gradually becomes distributed evenly on the mold cavity walls through gravitational force (centrifugal force is not a factor). As the cycle continues, the polyethylene composition melts completely, forming a homogeneous layer of molten polyethylene composition.
When the parts have been formed, the molds move to a cooling chamber where cooling is accomplished by a cold water spray and/or a cool liquid circulating inside the mold. The mold continues to rotate during the cooling cycle so as to ensure that the part does not sag away from the mold surface, causing distortion.
Finally, the molds are opened and the parts removed. This can be done manually or by using forced air or mechanical means to eject the part.
Cycle times typically range from 7 to 15 minutes, but can be as short as 5 minutes or as long as 30 minutes for very large parts. The wall thickness of the parts affects the cycle time, but not in a direct ratio. Normally, the cycle times increase by 30 seconds for each 25 mils of added thickness up to 1⁄4 inch. Beyond 1⁄4 inch the heat-insulating effect of the walls increases cycle time disproportionately for any further increase in thickness, and cycle times usually have to be determined experimentally.
The process for making an article according to the instant invention comprises the steps of (1) selecting a polyethylene composition comprising (a) at least 85 percent by weight of the units derived from ethylene; and (b) less than 15 percent by weight of units derived from one or more α-olefin comonomers; wherein said polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (Mw/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of said composition; and (2) forming said polyethylene composition into an article via rotational molding process.
The rotational molded articles according to the instant invention may have a energy to maximum force normalized to thickness, measured at −20° C., greater than 10 J/mm; for example greater than 15 J/mm; or in the alternative, greater than 17 J/mm; or in the alternative, greater than 20 J/mm, as measured by the ISO 6603-2 Instrumented Impact testing method. The rotational molded articles according to the instant invention may have an energy ductility at 90 percent of greater than 15 percent; for example greater than 17 percent; or in the alternative greater than 20 percent as measured by ISO 6603-2.
EXAMPLES
The following examples illustrate the present invention but are not intended to limit the scope of the invention. The examples of the instant invention demonstrate that the inventive polyethylene composition has a narrow molecular weight distribution, narrow composition distribution, and improved low and room temperature impact resistance while maintaining stiffness and processability properties.
Inventive Examples
Catalyst Component Preparation
The hafnocene component can be prepared by techniques known in the art. For example, HfCl4 (1.00 equiv.) can be added to ether at −30° C. to −50° C. and stirred to give a white suspension. The suspension can then be re-cooled to −30° C. to −50° C., and then lithium propylcyclopentadienide (2.00 equiv.) added in portions. The reaction will turn light brown and become thick with suspended solid on adding the lithium propylcyclopentadienide. The reaction can then be allowed to warm slowly to room temperature and stirred 10 to 20 hours. The resultant brown mixture can then be filtered to give brown solid and a straw yellow solution. The solid can then be washed with ether as is known in the art, and the combined ether solutions concentrated to under vacuum to give a cold, white suspension. Off-white solid product is then isolated by filtration and dried under vacuum, with yields of from 70 to 95%.
Catalyst Composition Preparation
The catalyst compositions should be made at a Al/Hf mole ratio of from about 80:1 to 130:1 and the hafnium loading on the finished catalyst should be from about 0.6 to 0.8 wt % Hf using the following general procedure. Methylaluminoxane (MAO) in toluene should be added to a clean, dry vessel and stirred at from 50 to 80 rpm and at a temperature in the range of 60 to 100° F. Additional toluene can then be added while stiffing. The hafnocene can then be dissolved in an amount of toluene and placed in the vessel with the MAO. The metallocene/MAO mixture can then be stirred at for from 30 min to 2 hours. Next, an appropriate amount of silica (average particle size of from 22 to 28 μm, dehydrated at 600° C.). can be added and stirred for another hour or more. The liquid can then be decanted and the catalyst composition dried at elevated temperature under flowing nitrogen while being stirred.
Polymerization Process
Ethylene/1-hexene copolymer was produced in accordance with the following general procedure. The catalyst composition comprised a silica supported bis(n-propylcyclopentadienyl) hafnium dichloride with methalumoxane, the Al:Hf ratio being from about 80:1 to 130:1. The catalyst composition was injected dry into a fluidized bed gas phase polymerization reactor. More particularly, polymerization was conducted in a 7-9 ft ID diameter gas-phase fluidized bed reactor operating at approximately 220-300 psig total pressure. The reactor bed weight was approximately 35,000-50,000 lbs. Fluidizing gas was passed through the bed at a velocity of approximately 1.5 to 2.5 ft per second. The fluidizing gas exiting the bed entered a resin disengaging zone located at the upper portion of the reactor. The fluidizing gas then entered a recycle loop and passed through a cycle gas compressor and water-cooled heat exchanger. The shell side water temperature was adjusted to maintain the reaction temperature to the specified value. Ethylene, hydrogen, 1-hexene and nitrogen were fed to the cycle gas loop just upstream of the compressor at quantities sufficient to maintain the desired gas concentrations. Gas concentrations were measured by an on-line vapor fraction analyzer. Product (the inventive polyethylene particles) was withdrawn from the reactor in batch mode into a purging vessel before it was transferred into a product bin. Residual catalyst and activator in the resin was deactivated in the product drum with a wet nitrogen purge. The catalyst was fed to the reactor bed through a stainless steel injection tube at a rate sufficient to maintain the desired polymer production rate. Polymerization conditions are reported in the Table I. Tables II-IV summarize the properties of the abovementioned polyethylene composition as well as the inventive rotational molded article.
Comparative Examples
Comparative sample 1 is an ethylene octene copolymer, having a density of approximately 0.939 g/cm3 according to ASTM-D 792 and a melt index I2 of approximately 3.76 according to ASTM-D 1238, which is commercially available under the tradename DOWLEXTM NG 2432 UE from The Dow Chemical Company. Tables II-IV summarize the properties of the abovementioned polyethylene composition as well as the comparative rotational molded article
Test Methods
Test methods include the following:
Density (g/cm3) was measured according to ASTM-D 792-03, Method B, in isopropanol. Specimens were measured within 1 hour of molding after conditioning in the isopropanol bath at 23° C. for 8 min to achieve thermal equilibrium prior to measurement. The specimens were compression molded according to ASTM D-4703-00 Annex A with a 5 min initial heating period at about 190° C. and a 15° C./min cooling rate per Procedure C. The specimen was cooled to 45° C. in the press with continued cooling until “cool to the touch.”
Melt index (I2) was measured at 190° C. under a load of 2.16 kg according to ASTM D-1238-03.
Melt index (I21) was measured at 190° C. under a load of 21.6 kg according to ASTM D-1238-03.
Weight average molecular weight (Mw) and number average molecular weight (Mn) were determined according to methods known in the art using triple detector GPC, as described herein below.
The molecular weight distributions of the ethylene polymers were determined by gel permeation chromatography (GPC).
According to conventional gel permeation chromatography (GPC), the conventional molecular weight and molecular weight distribution data were obtained from a high temperature gel permeation chromatography system consisted of a Polymer Laboratories Model PL-220. The column and carousel compartments were operated at 140° C. Three Polymer Laboratories 10-μm Mixed-B columns were used with a solvent of 1,2,4-trichlorobenzene. The samples were prepared at a concentration of 0.1 g of polymer in 50 mL of solvent. The solvent used to prepare the samples contained 200 ppm of the antioxidant butylated hydroxytoluene (BHT). Samples were prepared by agitating lightly for 4 hours at 160° C. The injection volume used was 100 microliters and the flow rate was 1.0 mL/min. Calibration of the GPC column set was performed with twenty one narrow molecular weight distribution polystyrene standards purchased from Polymer Laboratories. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using

Mpolyethylene=A(Mpolystyrene)B 

where M is the molecular weight, A has a value of 0.4316 and B is equal to 1.0 (T. Williams and I. M. Ward, Polymer Letters, Vol. 6, PP. 621-624 (1968)). A third order polynomial was determined to build the logarithmic molecular weight calibration as a function of elution volume. Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSEC software Version 3.0. The precision of the weight-average molecular weight Mw,2s was excellent at <2.6%.

Monomodal distribution was characterized according to the weight fraction of the highest temperature peak in temperature rising elution fractionation (typically abbreviated as “TREF”) data as described, for example, in Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), in U.S. Pat. No. 4,798,081 (Hazlitt et al.), or in U.S. Pat. No. 5,089,321 (Chum et al.), the disclosures of all of which are incorporated herein by reference. In analytical temperature rising elution fractionation analysis (as described in U.S. Pat. No. 4,798,081 and abbreviated herein as “ATREF”), the composition to be analyzed is dissolved in a suitable hot solvent (for example, 1,2,4 trichlorobenzene), and allowed to crystallized in a column containing an inert support (for example, stainless steel shot) by slowly reducing the temperature. The column was equipped with both an infra-red detector and a differential viscometer (DV) detector. An ATREF-DV chromatogram curve was then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (1,2,4 trichlorobenzene). The ATREF-DV method is described in further detail in WO 99/14271, the disclosure of which is incorporated herein by reference.
Long Chain Branching was determined according to the methods known in the art, such as gel permeation chromatography coupled with low angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography coupled with a differential viscometer detector (GPC-DV).
Analytical temperature rising elution fractionation (ATREF) analysis was conducted according to the method described in U.S. Pat. No. 4,798,081 and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982), which are incorporated by reference herein in their entirety. The composition to be analyzed was dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) by slowly reducing the temperature to 20° C. at a cooling rate of 0.1° C./min. The column was equipped with an infrared detector. An ATREF chromatogram curve was then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120° C. at a rate of 1.5° C./min.
Comonomer content was measured using C13 NMR, as discussed in Randall, Rev. Macromol. Chem. Chys., C29 (2&3), pp. 285-297, and in U.S. Pat. No. 5,292,845, the disclosures of which are incorporated herein by reference to the extent related to such measurement. The samples were prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene that was 0.025M in chromium acetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 150° C. The data was collected using a JEOL Eclipse 400 MHz NMR spectrometer, corresponding to a 13C resonance frequency of 100.6 MHz. Acquisition parameters were selected to ensure quantitative 13C data acquisition in the presence of the relaxation agent. The data was acquired using gated 1H decoupling, 4000 transients per data file, a 4.7 sec relaxation delay and 1.3 second acquisition time, a spectral width of 24,200 Hz and a file size of 64K data points, with the probe head heated to 130° C. The spectra were referenced to the methylene peak at 30 ppm. The results were calculated according to ASTM method D5017-91.
Melt temperature and crystallization temperature were measured via Differential Scanning Calorimetry (DSC). All of the results reported here were generated via a TA Instruments Model Q1000 DSC equipped with an RCS (refrigerated cooling system) cooling accessory and an auto sampler. A nitrogen purge gas flow of 50 ml/min was used throughout. The sample was pressed into a thin film using a press at 175° C. and 1500 psi (10.3 MPa) maximum pressure for about 15 seconds, then air-cooled to room temperature at atmospheric pressure. About 3 to 10 mg of material was then cut into a 6 mm diameter disk using a paper hole punch, weighed to the nearest 0.001 mg, placed in a light aluminum pan (ca 50 mg) and then crimped shut. The thermal behavior of the sample was investigated with the following temperature profile: The sample was rapidly heated to 180° C. and held isothermal for 3 minutes in order to remove any previous thermal history. The sample was then cooled to −40° C. at 10° C./min cooling rate and was held at −40° C. for 3 minutes. The sample was then heated to 150° C. at 10° C./min heating rate. The cooling and second heating curves were recorded.
Vinyl unsaturations were measured according to ASTM D-6248-98.
Trans unsaturations were measured according to ASTM D-6248-98.
Methyl groups were determined according to ASTM D-2238-92.
Rotomolder Datome model RB 1200, described in further details below, was used to produce samples for the testing of warpage, bubble rating and instrumented dart impact testing. Technical data for Rotomolder Datome model RB 1200
Clam Shell model with Infrared heating system.
Internal Air Cooling system (Fan unit utilizing the surrouding Air.)
Biaxial rotation, Siemens SPS process control.
Rotolog software for In Mold temperature measurement.
2 Cube molds approximately 250×250×250 mm.
Warpage was determined according to the following process. 2 cubes with the dimensions 250×250×250 mm (height x width x length) were molded, using 1.3 kg of resin powder. Temperature in the mold is measured with the integrated Rotolog temperature sensor and control unit. The resin powder is filled into the 2 cold molds (room temperature). The mold is then placed in the rotomolding clam shell. At the start of the machine, the molds are then heated via IR heaters. The Rotolog control unit controls measures the temperatures inside the mold.
Molding times are indicated in the table IV. This is the time the mold is heated by IR. After the molding time, there is a 2 minute holding time (heater switched off), followed by a 20 minute forced air cooling (air temperature is room temperature), using an internal fan. The molded articles are then removed from the molds. The molded samples are allowed to crystallize for at least 48 hrs, before the warpage is measured.
For warpage measurement, one side panel is cut out of the cube with a band saw. For consistency, always the same side panel is cut out from the cubes. The cut out panel is placed on a flat surface and the distortion of the edges from the horizontal is measured with a water-level or water-gauge—measured in the diagonal between 2 corners. The deformation can be convex or concave, as indicated in table IV.
The bubble rating was determined according to the following procedure. The rotomolded cubes are visually inspected for bubbles. A qualitative rating of 1 (few), 2 (more), or 3(most) is made based on the number of bubbles present.
Instrumented impact testing was performed on the rotomolded articles according to ISO 6603/2.
The present invention may be embodied in other forms without departing from the spirit and the essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.









TABLE I







Inventive


Measurement
Units
1

















Reactor Temperature
° C.
77.0


Isopentane %
mol %
5.0


Ethylene Partial
psia
234


Pressure




C6/C2 molar ratio
unitless
0.0065


Hydrogen Vapor
ppm
309


Concentration




H2/C2
H2
3.51



ppm/C2




mol %





















TABLE II









Inventive
Comparative



Measurement
Units
1
1





















Density
g/cm3
0.9408
0.9392



I2
g/10 min
5.81
3.76



I5
g/10 min
14.78




I10
g/10 min
33.62
25.38



I21
g/10 min
102




I10/I2
—
5.79
6.75



I21/I2
—
17.6




ESCR 10%/F50
h
283
94



ESCR 100%/F50
h
1360
>1100



Conventional GPC


—



Mn
g/mol
27500
—



Mw
g/mol
72700
—



Mz
g/mol
142200
—



Mw/Mn
unitless
2.64
—



Mz/Mw
unitless
1.96
—



methyls
per 1000
2.04
—




C's





trans
per 1000
0.067
—




C's





vinyls
per 1000
0.023
—




C's




















TABLE III







Inventive
Comparative


Measurement
Units
1
1







T (crystallization)
° C.
114.3
—


DSC





T (melt) DSC
° C.
126.3
—


Heat of Fusion
J/g
185.3
—


(DSC)



















TABLE IV





Measurement
Units
Inventive 1
Comparative 1
























Molding Time
Min
10
11
13
15
10
11
13
15


Max Temp/Rotolog
C. °
160
173
202
227
162
173
201
229


Instrument Impact


Testing (ISO 6603/2)


23° C.


Avg. sample thickness
mm
4.57
4.64
4.44
4.32
4.39
4.33
4.2
4.31


Peak force
N/mm
1236
1209
1226
1276
1127
1113
1188
1232


E. to Max. Force/
J/mm
10.76
10.45
10.74
11.01
8.91
13.59
13.58
16.28


thickness


E. total/thickness
J/mm
17.3
17.52
20.22
20.49
13.59
13.58
16.28
19.33


E. Ductility at 90%
%
22.8
24.8
26.2
28.2
18.6
18.2
22.3
26.3


Failure Type
YD
5
5
5
5
1
2
5
5



YS
—
—
—
—
4
3
—
—



YU
—
—
—
—
—
—
—
—



NY
—
—
—
—
—
—
—
—


−20° C.


Avg. sample thickness
mm
4.19
4.07
4.02
3.97
4.09
4.08
4.02
4.02


Peak force
N/mm
1690
1733
1879
502
1486
1474
1507
455


E. to Max. Force/
J/mm
12.97
13.77
15.84
1.55
8.90
8.27
8.81
1.41


thickness


E. total/thickness
J/mm
21.48
23.41
27.98
1.71
12.72
11.43
12.39
1.97


E. Ductility at 90%
%
21.0
24.5
26.8
2.1
7.8
5.7
9.4
1.7


Failure type
YD
3
5
5
—
—
—
—
—



YS
2
—
—
—
—
—
1
—



YU
—
—
—
—
4
5
2
—



NY
—
—
—
5
1
—
2
5


Warpage measured on
mm


−2 mm

2 mm
2 mm
2 mm
3 mm


left side of plate mold



convex

Concave
Concave
CC/CV
Convex


Bubbles Rating


1 (few) 2 (more) 3(most)

2-3
2
none
none
3
3
2
none

## Claims

1. A rotational molded article comprising:
a polyethylene composition comprising;
at least 85 percent by weight of the units derived from ethylene;
less than 15 percent by weight of units derived from one or more α-olefin comonomers;

wherein said polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (MW/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (Mz/Mw) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of said composition, wherein said rotational molded article has an energy to maximum force normalized to thickness, measured at −20° C., greater than 10 J/mm as measured by the ISO 6603-2 Instrumented Impact testing method.

2. The rotational molded article according to claim 1, wherein said polyethylene composition has a density in the range of 0.935 to 0.945 g/cm3.

3. The rotational molded article according to claim 1, wherein said polyethylene composition has a melt index (I2) in the range of 1 to 10 g/10 minutes.

4. The rotational molded article according to claim 1, wherein said polyethylene composition has less than 2 peaks on an elution temperature-eluted amount curve determined by continuous temperature rising elution fraction method at equal or above 30° C., wherein the purge peak which is below 30° C. is excluded.

5. The rotational molded article according to claim 1, wherein said polyethylene composition comprises less than 11 percent by weight of the units derived from one or more α-olefin comonomers.

6. The rotational molded article according to claim 1, wherein said polyethylene composition is substantially free of long chain branching.

7. The rotational molded article according to claim 1, wherein said polyethylene composition comprises less than 100 parts by weight of a hafnium based metallocene catalyst per one million parts of polyethylene composition.

8. The rotational molded article according to claim 1, wherein said polyethylene composition has a melt flow ratio (I21/I2) in the range of 12 to 23.

9. The rotational molded article according to claim 1, wherein said polyethylene composition has a melt index I21 in the range of 7.5 to 400 g/10 minutes.

10. The rotational molded article according to claim 1, wherein said polyethylene composition comprises the (co)polymerization reaction product of ethylene and optionally one or more α-olefin comonomers in the presence of a hafnium based metallocene catalyst via a gas phase (co)polymerization process in a single stage reactor.

11. A process for making an article comprising the steps of:
selecting a polyethylene composition comprising:
at least 85 percent by weight of the units derived from ethylene;
less than 15 percent by weight of units derived from one or more α-olefin comonomers; wherein said polyethylene composition has a density in the range of 0.930 to 0.945 g/cm3, a molecular weight distribution (MW/Mn) in the range of 1.70 to 3.50, a melt index (I2) in the range of 0.5 to 20 g/10 minutes, a molecular weight distribution (MZ/MW) in the range of less than 2.5, vinyl unsaturation of less than 0.06 vinyls per one thousand carbon atoms present in the backbone of said composition; and forming said polyethylene composition into an article via rotational molding process, wherein said rotational molded article has an energy to maximum force normalized to thickness, measured at −20° C., greater than 10 J/mm as measured by the ISO 6603-2 Instrumented Impact testing method.