High-density polyethylene compositions, method of making the same, articles made therefrom, and method of making such articles

[0001] The present invention relates to high-density polyethylene compositions, a method for its production, and articles made therefrom.

Link to Related Applications [0002] This application is a non-temporary application claiming priority from US Serial Patent Application No. 60 / 796.809, filed May 2, 2006, entitled "High Density Polyethylene Compositions and Methods of Making the Same / High Density Polyethylene Compositions and methods of producing them ", the recommendations of which are here below, as if fully reproduced.

Background of the Invention [0003] The use of polymeric materials for the production of molded articles, such as closing devices and containers, is generally known. Various methods can be used to manufacture closing devices, such as bottle-mounted closures, or containers, such as bottles. For example, such closing devices can be manufactured by compression molding or injection molding; or alternatively, the containers may be made by blow molding, injection blow molding, or stretch and blow injection. [0004] In the compression compression method, a nest having the shape of the desired molded article is provided in a two-part form. The mold is heated. The appropriate amount of molten molding composition is charged to the bottom half of the mold from the extruder. Two parts of the mold are put together under pressure. The molded composition, softened by heating, is thus bonded to a continuous mass having the shape of a mold cavity. If the molded composition is a thermosetting material, the continuous mass can be cured in the mold by further heating under pressure. If the molded composition is a thermoplastic material, the continuous mass may be cured by cooling under pressure.

[0005] In the injection molding method, the molded composition is fed to an extruder through a hopper. The extruder transports, heats, melts and holds under pressure the molded composition in the form of a molten stream. The molten stream is squeezed from the extruder through a nozzle into a relatively cool mold held in a closed position under pressure, thus filling the mold. The alloy cools and hardens until completely hardened. The mold is then opened and the formed element removed.

[0006] In the blow molding process, for example, injection blow molding, the molded composition is melted and then molded into a pipe or blow molded preform. The end of the pipe or preform is closed, except in the area in which blowing air may enter. The sealed tube or preform is inflated inside the mold, thereby adopting the shape of the mold. The molded article is cooled and then thrown out of the mold. If necessary, the molded article is then trimmed.

[0007] Generally, a closing device, such as a closure for carbonated drink bottles, should be strong enough to withstand the pressure of a carbon dioxide drink, and yet still soft enough to ensure perfect sealing of the bottle without having to using the inner liner. In addition, a closing device, such as a cap for carbonated drink bottles, should generally have good resistance to stress cracking under the influence of the environment, good impact resistance, good removal torque and good peeling torque. Various techniques have been used to provide such closing devices having acceptable properties.

[0008] For example, it is also generally well known to use polypropylene polymer as a cap closure for bottles with the necessary strength with an inner liner which may consist of soft ethylene / vinyl acetate (E / VA), polyvinyl chloride (PVC) ), butyl rubber, etc. However, this two-part construction is expensive because there is a need for an inner liner.

In addition, it would be easier and more convenient to use a one-piece closure without an insert.

[0009] In attempts to eliminate the need for a two-part construction, the use of various polymer blends has been suggested. However, there is still a need for polymer formulas from which closing devices having acceptable properties can be formed, such as no need to use an insert to facilitate sealing, acceptable odors, satisfactory stress crack resistance, and impact resistance to prevent cracking of applied closures .

Summary of the Invention [0010] The present invention includes a high density polyethylene composition, a method for its manufacture, molded articles from this composition, and a method for producing such articles. The high density polyethylene composition of the present invention includes a first component and a second component. The first component is a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to₃

0.940 g / cm³ and a melt index (I21.6) in the range of 0.5 to 10 g / 10 minutes. The second component is₃ low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g / cm³ and a melt index (I2) in the range of 50 to 1500 g / 10 minutes. High polyethylene composition₃ the density has a melt index (I2) of at least 1, a density in the range of 0.950 to 0.960 g / cm³ and g 'equal to or greater than 1. The method for producing the high-density polyethylene composition comprises the following steps: (1) introducing ethylene and one or more alpha-olefin comonomers into the first reactor; (2) (co) polymerization of ethylene in the presence of one or more alpha-olefin comonomers in the first reactor, thereby forming the first component, wherein the first component is a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 down₃

0.940 g / cm³ and a melt index (I21.6) in the range of 0.5 to 10 g / 10 minutes; (3) introducing the first component and additional ethylene into the second reactor; (4) polymerization of additional ethylene in the second reactor, thereby forming a second component, the second component being a polymer₃ low molecular weight ethylene having a density in the range of 0.965 to 0.980 g / cm³ and a melt index (I2) in the range of 50 to 1500 g / 10 minutes; and (5) to thereby produce a high density polyethylene composition, wherein the high density polyethylene composition has a speed index₃ melt flow (I2) at least 1, density in the range 0.950 to 0.960 g / cm³ and g 'equal to or greater than 1. The articles of the present invention contain the above described high density polyethylene composition we2

According to the invention, such products can be manufactured by compression molding, injection molding, injection blow molding, or stretch injection blow molding.

[0011] In one embodiment, the present invention provides a high density polyethylene composition comprising a high molecular weight polyethylene alpha-olefin copolymer having a density in the range ₃

0.915 to 0.940 g / cm³ and a melt index (I21.6) in the range of 0.5 to 10 g / 10 minutes and polymer ₃ low molecular weight ethylene having a density in the range of 0.965 to 0.980 g / cm³, and a melt index (I2) in the range 50 to 1500 g / 10 minutes, wherein the high density polyethylene composition of the invention has a melt index (I2) of at least 1 g / 10 minutes, density in ₃ range 0.950 to 0.960 g / cm³ and g 'equal to or greater than 1.

[0012] In an alternative embodiment, the present invention further provides a method for producing a high density polyethylene composition comprising the steps of: (1) introducing ethylene and one or more alpha-olefin comonomers into the first reactor; (2) (co) polymerization of ethylene in the presence of one or more alpha-olefin comonomers in the first reactor to thereby produce a copolymer₃ high molecular weight ethylene alpha-olefin having a density in the range of 0.915 to 0.940 g / cm³ and a melt index (I21.6) in the range of 0.5 to 10 g / 10 minutes; (3) introducing a high molecular weight ethylene alpha-olefin copolymer and additional ethylene into the second reactor; (4) polymerizing additional ethylene in a second reactor to thereby produce an ethylene polymer with₃ low molecular weight having a density in the range of 0.965 to 0.980 g / cm3³ and a melt index (I2) in the range of 50 to 1500 g / 10 minutes; and (5) thereby producing a high density polyethylene composition, the high density polyethylene composition having a melt flow rate₃ alloy (I2) at least 1, density in the range 0.950 to 0.960 g / cm³ and g 'equal to or greater than 1.

[0013] In another alternative embodiment, the present invention provides an article comprising the high-density polyethylene composition, wherein the high-density polyethylene composition comprises a copolymer of₃ li (ethylene alpha-olefin) with a high molecular weight, having a density in the range of 0.915 to 0.940 g / cm³ and melt index (I21.6) in the range of 0.5 to 10 g / 10 minutes, and low weight ethylene polymer₃ molecular weight, having a density in the range of 0.965 to 0.980 g / cm³ and a melt index (I2) in the range 50 to 1500 g / 10 minutes, wherein the high density polyethylene composition of the invention has a melt index (I2) of at least 1 g / 10 minutes, a density in the range 0.950 to 0.960 ₃ g / cm³ and g 'equal to or greater than 1.

[0014] In another alternative embodiment, the present invention provides a method of making an article comprising the steps of (1) providing a high density polyethylene composition comprising an ethylene copolymer ₃ with high molecular weight alpha-olefin, having a density in the range of 0.915 to 0.940 g / cm³ and a melt index (I21.6) in the range of 0.5 to 10 g / 10 minutes; and low weight ethylene polymer₃ molecular, having a density in the range of 0.965 to 0.980 g / cm³ and a melt index (I2) in the range of 50 to 1500 g / 10 minutes; wherein the high-density polyethylene composition of the invention has₃ melt flow rate (I2) at least 1 g / 10 minutes, density in the range 0.950 to 0.960 g / cm³ ig 'equal to or greater than 1; (2) carrying out compression pressing, injection molding; injection-blow molding, or stretch-blow injection molding of high density polyethylene compositions (3) and thus molding the article.

[0015] In an alternative embodiment, the present invention provides a method for producing high density polyethylene compositions in accordance with any one of the previous embodiments except that the second reactor does not contain substantially any other alpha-olefin copolymer.

[0016] In an alternative embodiment, the present invention provides a high-density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the poly (ethylene-alpha-olefin copolymer) ) about ₃ high molecular weight has a density in the range of 0.920 to 0.940 g / cm³.

[0017] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the ethylene alpha copolymer₃ high molecular weight olefin has a density in the range of 0.921 to 0.936 g / cm³.

[0018] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the high weight polyethylene alphaolefin copolymer has melt index (I21.6) in the range of 1 to 7 g / 10 minutes.

[0019] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the high weight polyethylene alphaolefin copolymer has melt index (I21.6) in the range of 1.3 to 5 g / 10 minutes.

[0020] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the low-ethylene polymer ₃ the molecular weight has a density in the range of 0.970 to 0.975 g / cm³.

[0021] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition and a method for producing such articles in accordance with any of the previous embodiments, except that the low molecular weight ethylene polymer has melt index (I2) in the range 100 to 1500 g / 10 minutes.

[0022] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition and a method for producing such articles in accordance with any of the previous embodiments, except that the low molecular weight ethylene polymer has melt index (I2) in the range 200 to 1500 g / 10 minutes.

[0023] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the high density polyethylene composition of the invention has a melt index (I2) in the range of 1 to 2 g / 10 minutes; or alternatively has a melt index (I2) of at least 2 g / 10 minutes.

[0024] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition and a method for producing such

Articles according to any one of the preceding embodiments, except that the high molecular weight ethylene alphaolefin copolymer has a molecular weight in the range 150,000 to 375,000.

[0025] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the low molecular weight ethylene polymer has molecular weight in the range of 12,000 to 40,000.

[0026] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the polyethylene alpha copolymer₃ high molecular weight olefin has a density in the range of 0.921 to 0.936 g / cm³ and a melt index (I21.6) in the range of 1.3 to 5 g / 10 minutes, and the low molecular weight ethylene polymer has ₃ density between 0.970 and 0.975 g / cm³ and a melt index (I2) in the range 200 to 1500 g / 10 minutes.

[0027] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the high weight polyethylene alphaolefin copolymer and the low molecular weight ethylene polymer generally contains no long chain branching.

[0028] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition and a method for producing such articles in accordance with any of the previous embodiments, except that the high density polyethylene composition is substantially contains no long chain branching.

[0029] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition and a method for producing such articles in accordance with any of the previous embodiments, except that the high density polyethylene composition has a single temperature peak in ATREF, where the temperature peak in ATREF has a maximum temperature peak between 90^aboutC to 105^aboutC; and wherein the high-density polyethylene composition has a calculated high-density fraction in the range of 20 percent to 50 percent, said calculated high-density fraction being defined as [(2) X (weight ratio of high-density polyethylene that is eluted during ATREF-DV at temperatures higher than or equal to the maximum temperature peak)]; and wherein the high density polyethylene composition has a relative minimum in log relative viscosity average molecular weight in ATREF-DV at about 90^aboutC; and wherein the high-density polyethylene composition has a regression slope log relative viscosity average molecular weight as a function of viscosity in ATREF-DV as a function of temperature less than about 0, where the measured elution temperature is 70^aboutC to 90^aboutC.

[0030] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for its preparation, articles made from this composition, and a method for producing such articles in accordance with any of the previous embodiments, except that the high density polyethylene composition has comonomer in weight percent equal to or greater than ₃ [(-228,41 * density of high-density polyethylene composition) + 219.36)] * [1 (weight percent) / (g / cm³)], where ₃ density is measured in g / cm³.

[0031] In another alternative embodiment, the present invention provides a high density polyethylene composition, a method for preparing it, products made from this composition, and a method for making such products according to any of the previous embodiments, except that the polyethylene composition high-density has a high-density fraction in ATREF in percentage equal to or less than [(2750 * density 33 high-density polyethylene compositions) -2552,2] * [1 (percent) / (g / cm³)], where density is measured in g / cm³. [0032] In another alternative embodiment, the present invention provides articles and a method for making such articles in accordance with any of the previous embodiments, except that the article has an environmental stress crack resistance of at least 150 hours measured according to ASTM D1693, condition B, 10 percent Igepal or at least 300 hours measured according to ASTM D-1693, condition B, 100 percent Igepal.

[0033] In another alternative embodiment, the present invention provides articles and a method for making such articles in accordance with any of the previous embodiments, except that the article is a closing device, a cable wire sheath, an installation pipe or a bottle.

[0034] In another alternative embodiment, the present invention provides articles and a method for making such articles in accordance with any of the previous embodiments, except that the article is a compression molded article, an injection molded article, a blow molded article or article. injection molded stretch and blow molding.

[0035] In another alternative embodiment, the present invention provides a compression molded or injection molded article and a method of making the molded compression or injection molded article in accordance with any of the previous embodiments except that the article is a bottle closure.

[0036] In another alternative embodiment, the present invention provides a compression molded or injection molded article and a method for producing a compression molded or injection molded article in accordance with any one of the preceding embodiments except that the article is a closure incorporating a side shell that extends axially from the base periphery and has an internal thread for attaching the container closure.

[0037] In an alternative embodiment, the present invention provides a compression molded article and a method for producing a compression molded article in accordance with any one of the previous embodiments except that the article is a press formed molded closure comprising a side shell that extends axially. from the base periphery and has an internal thread for attaching the closure to the container.

[0038] In another alternative embodiment, the present invention provides an injection molded article and a method for producing an injection molded article according to any one of the previous embodiments except that the article is an injection molded closure comprising a side shell that extends axially from base flanges and has an internal thread for attaching the closure to the container.

[0039] In another alternative embodiment, the present invention provides a blow molded article and a method of making a blow molded article according to any of the previous embodiments except that the article is a blow molded bottle.

EP 2 016 127 B1

Brief Description of the Drawings [0040] For the purposes of illustrating the present invention, the drawings show the form that is currently recommended; it is understood, however, that the invention is not limited to the exact settings and instrumentation shown.

Fig. 1 is a graph showing the relationship between the comonomer content and the density of the high density polyethylene composition of the present invention;

Fig. 2 is a graph showing the relationship between the high density fraction measured by analytical fractionation by increasing temperature (ATREF) and the density of the high density polyethylene composition of the present invention;

Fig. 3 is a graph showing the relationship between the calculated high density fraction measured by analytical fractionation by temperature elution (ATREF) and the density of the high molecular weight polyethylene component in the high density polyethylene composition of the invention;

Fig. 4 shows how the high density fraction in ATREF was calculated in the high molecular weight polyethylene component of Example 1 according to the invention.

Detailed Description of the Invention [0041] The high density polyethylene composition of the present invention comprises a first component and a second component. The first component is preferably a high weight copolymer of ethylene alpha-olefin₃ molecular having a density in the range of 0.915 to 0.940 g / cm³ and a melt index (I21) in the range of 0.5 to 10 g / 10 minutes. The second component is preferably a low molecular weight ethylene polymer₃ having a density in the range of 0.965 to 0.980 g / cm³ and a melt index (I2) in the range of 50 to 1500 g / 10 minutes. The high-density polyethylene composition of the invention has a window indicator₃ melt bone (I2) at least 1 g / 10 minutes, density 0.950 to 0.960 g / cm³ and g 'equal to or greater than 1. The high density polyethylene composition may further contain additional ingredients, additives or auxiliaries. The high-density polyethylene composition is a bimodal polymer, or alternatively, the high-density polyethylene is a multimodal polymer.

[0042] The term "bimodal" as used herein means that the molecular weight distribution (MWD) in the Gel Chromatography (GPC) curve has two component polymers, for example two peaks, or in which one component polymer may even exist as a hump, arm or tail in relation to

MWD of another component polymer; or alternatively, for example, in which the two components can have only one single peak, without humps, arms or tails.

[0043] The term "multimodal" as used herein means that MWD in the GPC curve has more than two component polymers, for example, three or more peaks, or in which one component polymer may even exist as a hump, arm or tail relative to MWD of other polymer components; or alternatively, wherein three or more components may have only one single peak, no humps, arms or tails.

[0044] The term "polymer" is used herein to indicate a homopolymer, interpolymer (or copolymer) or terpolymer. The term "polymer" as used herein includes interpolymers such as, for example, those prepared by copolymerization of ethylene with one or more C3-C20 alpha-olefin (olefins).

[0045] The term "interpolymer" as used herein refers to polymers produced by polymerization of at least two different types of monomers. The generic term "interpolymer" thus includes copolymers, usually used to designate polymers made from two different monomers and polymers made from more than two different types of monomers.

[0046] The term "(co) polymerization" as used herein refers to the polymerization of ethylene in the presence of one or more olefin comonomers.

[0047] The first component is a polymer, for example a polyolefin. The first component is preferably an ethylene polymer; for example, the first component is preferably a high molecular weight ethylene alpha-olefin copolymer. The first component basically does not contain any long chain branches. The term "substantially free of long chain branching" as used herein refers to an ethylene polymer preferably substituted with less than about 0.1 long chain branching for a total of 1000 carbons, and more preferably less than about 0.01 long chain branching for a total of 1000 coals. The presence of long chain branches is typically determined by methods well known in the art, such as gel chromatography coupled with a small angle laser scattering detector (GPCLALLS) and gel chromatography coupled with a differential viscometer (GPC-DV) detector. ₃

The first component has a density in the range of 0.915 to 0.940 g / cm³. All individual values ​​and charts₃ ranges from 0.915 to 0.940 g / cm³ are included herein and disclosed herein; for example, the first component has a density of za₃ 0.920 to 0.940 g / cm³or, alternatively, the first component has a density in the range of 0.921 to 0.936 ₃ g / cm³. The first component has a melt index (I21.6) in the range of 0.5 to 10 g / 10 minutes.

All individual values ​​and subranges from 0.5 to 10 g / 10 minutes are included herein and disclosed herein; for example, the first component has a melt index (I21.6) in the range of 1 to 7 g / 10 minutes, or alternatively, the first component has a melt index (I21.6) in the range of 1.3 to 5 g /10 minutes. The first component has a molecular weight in the range 150,000 to 375,000. All individual values ​​and subranges from 150,000 to 375,000 are included herein and disclosed herein; for example, the first component has a molecular weight in the range of 175,000 to 375,000, or alternatively, the first component has a molecular weight in the range of 200,000 to 375,000. The first component may contain any amount of one or more alpha-olefin comonomer; for example, the first component contains about less than 10 weight percent of one or more alpha-olefin comonomers, based on the weight of the first component.

All individual values ​​and subranges less than 10 weight percent are included herein and disclosed herein. The first component may contain any amount of ethylene; for example, the first component contains at least about 90 weight percent ethylene, based on the weight of the first component. All individual values ​​and subranges above 90 weight percent are included herein and disclosed herein, for example the first component contains at least 95 weight percent ethylene, based on the weight of the first component.

[0048] Alpha-olefin comonomers typically contain no more than 20 carbon atoms. For example, alpha-olefin comonomers may preferably contain 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. Examples of alpha-olefin comonomers include, but are not limited to, but not limited to propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methyl-1-pentene. Alpha8 comonomers

The olefinic compounds are preferably selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and more preferably from the group consisting of 1-hexene and 1-octene.

[0049] The second component is a polymer of ethylene; for example, the second component is preferably a low molecular weight ethylene homopolymer. The ethylene homopolymer may contain trace amounts of contaminating comonomers, e.g., alpha-olefin comonomers. The term "ethylene homopolymer" as used herein refers to an ethylene polymer containing at least 99 percent by weight of ethylene units. The second component basically does not contain any long chain branching. The term "substantially free of long chain branching" as used herein refers to an ethylene polymer preferably substituted with less than about 0.1 long chain branching for a total of 1000 carbons, and more preferably less than about 0.01 long chain branching for a total of 1000 coals.

The presence of long chain branches is typically determined by methods well known in the art ₃ mentioned above. The second component has a density in the range of 0.965 to 0.980 g / cm³. All individual₃ values ​​and subranges from 0.965 to 0.980 g / cm³ are included herein and disclosed herein; for example, the second component has₃ density between 0.970 and 0.975 g / cm³. The second component has a melt index (I2) in the range from 50 to 1500 g / 10 minutes. All individual values ​​and subranges from 50 to 1500 g / 10 minutes are included herein and disclosed herein; for example, the second component has a melt index (I2); in the range of 200 to 1500 g / 10 minutes, or alternatively, the second component has a melt index (I2) in the range of 500 to 1500 g / 10 minutes. The second component has a molecular weight in the range of 12,000 to 40,000. All individual values ​​and subranges from 12,000 to 40,000 are included herein and disclosed herein; for example, the second component has a molecular weight in the range of 15,000 to 40,000; or alternatively, the second component has a molecular weight in the range of 20,000 to 40,000. The second component contains less than 1.00 weight percent of one or more alpha-olefin copolymers, based on the weight of the second component. All individual values ​​and subranges less than 1.00 weight percent are included herein and disclosed herein; for example, the second component may contain 0.0001 to 1.00 weight percent of one or more alpha-olefin copolymers;

the second component may contain 0.001 to 1.00 weight percent of one or more alpha-olefin copolymers. The second component contains at least about 99 weight percent ethylene, based on the weight of the second component. All individual values ​​and subranges from 99 to 100 weight percent are included herein and disclosed herein; for example, the second component contains 99.5 to 100 weight percent ethylene, based on the weight of the second component.

₃ [0050] The high-density polyethylene composition has a density in the range of 0.950 to 0.960 g / cm³. All₃ individual values ​​and subranges from 0.950 to 0.960 g / cm³ are included herein and disclosed herein. The high-density polyethylene composition has a melt index (I2) of at least 1 g / 10 minutes. All individual values ​​and subranges equal to or greater than 1 g / 10 minutes are included herein and disclosed herein; for example, the high-density polyethylene composition has a melt index (I2) in the range of 1 to 2 g / 10 minutes; or alternatively, the high-density polyethylene composition has a melt index (I2) of at least 2 g / 10 minutes. The high density polyethylene composition generally contains no long chain branching. The term "substantially free of long chain branching" as used herein refers to a polyethylene composition preferably substituted with less than about 0.1 long chain branching for a total of 1000 carbons, and more preferably less than about 0.01 long chain branching for a total of 1000 coals. The presence of long chain branches is typically determined by methods well known in the art as mentioned above. The high-density polyethylene composition has

Molecular weight distribution in the range of 6 to 25. All individual values ​​and subranges in the range of 6 to 25 are included herein and disclosed herein; for example, the high-density polyethylene composition has a molecular weight distribution in the range of 7 to 20; or alternatively the high density polyethylene composition has a molecular weight distribution in the range of 7 to 17. The term "molecular weight distribution" or "MWD" as used herein refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), i.e. (Mw / Mn), described in more detail below. The high-density polyethylene composition has an environmental stress crack resistance of at least 150 hours measured according to ASTM D-1693, condition B, 10% Igepal or preferably at least 200 hours measured according to ASTM D-1693, condition B, 10% Igepal or more preferably at least 250 hours measured in accordance with ASTM D-1693, conditions B, 10% Igepal. Alternatively, the high-density polyethylene composition has an environmental stress cracking resistance of at least 300 hours measured in accordance with ASTM D-1693, condition B, Igepal 100% or preferably at least 400 hours measured in accordance with ASTM D-1693, condition B, Igepal 100% or more preferably at least 500 hours measured in accordance with ASTM D-1693, condition B, Igepal 100%. The high-density polyethylene composition may contain any amount of the first component, second component or combinations thereof. The high-density polyethylene composition contains 40 to 60 percent by weight of the first component, based on the total weight of the first and second components. All individual values ​​and subranges in the range of 40 to 60 weight percent are included herein and disclosed herein; for example, the high-density polyethylene composition contains 42 to 55 percent by weight of the first component based on the combined weight of the first and second components. The high-density polyethylene composition further contains 40 to 60 percent by weight of the second component, based on the combined weight of the first and second components. All individual values ​​and subranges in the range of 40 to 60 weight percent are included herein and disclosed herein; for example, the high-density polyethylene composition contains 48 to 55 percent by weight of the first component based on the combined weight of the first and second components. Preferably, the high-density polyethylene composition has a single temperature peak in ATREF, wherein the temperature peak in ATREF has a maximum temperature peak between 90^aboutC a 105^aboutC, as described in more detail below. The high-density polyethylene composition still has a calculated high-density fraction in the range of 20 percent to 50 percent. All individual values ​​and subranges in the range of 20 to 50 weight percent are included herein and disclosed herein.

The calculated high-density fraction, as used herein, relates to the relationship [(2) x (weight ratio of high-density polyethylene that elutes in ATREF-DV at temperatures higher than or equal to the maximum temperature peak). In addition, the polyethylene composition high density has a relative minimum in log relative viscosity average molecular weight of about 90^aboutC in ATREFDV and the regression slope log relative viscosity average molecular weight as a function of viscosity in ATREF-DV as a function of temperature less than about 0, where the elution temperature is measured between 70^aboutC to 90^aboutC.

[0051] The high-density fraction in ATREF (percent) in the high-density polyethylene composition is calculated by integrating the area under the curve from 86^aboutC and above until there is no relative minimum on the curve. None of the inventive or comparative samples, measured and cited in the tables, had a relative minimum on the curve from 86^aboutC and at higher temperatures.

[0052] The high-density polyethylene composition has an average g 'equal to or greater than 1 measured by triple detector gel chromatography (GPC), described hereinafter in more detail below. g 'is

Expressed as the ratio of the intrinsic viscosity of the present high molecular weight polyethylene composition to the intrinsic viscosity of the linear reference polymer. If g 'is greater than or equal to 1, the sample to be analyzed is considered linear, and if g' is less than 1, it is then by definition a branched polymer compared to a linear polymer. However, current measurement methods may have errors in both precision and accuracy; thus, the right steps must be considered for such precision errors. Thus, small deviations, for example, values ​​equal to or less than 0.012, from one, i.e. 0.988 to 1.012, would still be defined as linear polymers. Alternatively, small deviations, for example values ​​equal to or less than 0.025 from one, i.e. 0.975 to 1.025 would still be defined as linear polymers.

[0053] Referring to Fig. 1, the high-density polyethylene composition has a high-density fraction in

ATREF in percent by weight equal to or less than [(2750 * density of high density polyethylene composition) -2552.2] * [1 (percent) / (g / cm³)], where density is measured in g / cm³.

[0054] Referring to Fig. 2, the high-density polyethylene composition has a comonomer content in weight percent equal to or greater than [(-228.41 * density of the high-density polyethylene composition) + 219.36)] * [1 ( weight percent) / (g / cm³)], where density is measured in g / cm³.

[0055] Referring to Fig. 3, the calculated high density fraction in percentage is equal to [(1107.4 * (density ₃ high molecular weight polyethylene component) -992.56] * [1 (percent) / (g / cm³)].

[0056] Referring to Fig. 4, Fig. 4 shows the relationship between elution temperatures w ^aboutC and mean viscosity in log [Mv (g / mol)].

[0057] The high-density polyethylene composition may further contain additional components such as other polymers, auxiliaries and / or additives. Such auxiliaries or additives include antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, crystallization nuclei and combinations thereof, but are not limited to them. The high-density polyethylene composition contains about less than 10 percent of the total weight of one or more additives, based on the weight of the high-density polyethylene composition. All individual values ​​and subranges from about less than 10 weight percent are included herein and disclosed in the present invention; for example, the high-density polyethylene composition contains about less than 5 percent of the total weight of one or more additives, based on the weight of the high-density polyethylene composition, or alternatively, the high-density polyethylene composition contains about less than 1 percent of the total weight of one or more additives, based on the weight of high-density polyethylene composition, or otherwise, the high-density polyethylene composition contains about less than 0.5 percent of the total weight of one or more additives, based on the weight of the high-density polyethylene composition. Antioxidants such as Irgafos® 168 and Irganox® 1010 are usually used to protect the polymer from thermal and / or oxidative degradation. Irganox® 1010 is tetrakis (methylene 3,5-di-tert-butyl-4-hydroxyhydrocinnamate), which is commercially available from Ciba Geigy Inc. Irgafos® 168 is tris-2,4-di-tert-butylphenyl phosphite, which is commercially available from Ciba Geigy Inc.

[0058] The high molecular weight polyethylene composition of the invention may further be mixed with other polymers. Such other polymers are generally known to those of ordinary skill in the art. The mixtures containing the high-density polyethylene compositions of the invention are prepared by any conventional means. For example, selected polymers are mixed in an alloy

EP 2 016 127 B1 by means of single or twin screw extruders, or mixers, e.g., Banbury mixer, Haake mixer, Brabender internal mixer.

[0059] Generally, mixtures containing the high density polyethylene composition of the invention contain at least 40 percent by weight of the high density polyethylene composition of the invention, based on the total weight of the mixture. All individual sizes and subranges in the range of at least 40 weight percent are included herein and disclosed in the present invention; for example, mixtures containing at least 50 percent by weight of the high density polyethylene composition of the invention, based on the total weight of the mixture; or alternatively, mixtures containing at least 60 percent by weight of the high density polyethylene composition of the invention, based on the total weight of the mixture, or alternatively, mixtures containing at least 70 percent by weight of the high density polyethylene composition of the invention, based on the total weight of the mixture, or alternatively, mixtures containing at least 80 percent by weight of the high density polyethylene composition of the invention, based on the total weight of the mixture, or alternatively, mixtures containing at least 90 percent by weight of the high density polyethylene composition of the invention, relative to the total weight of the mixture, or alternatively, mixtures containing at least 95 percent by weight of the high density polyethylene composition of the invention in relative to the total weight of the mixture, or alternatively mixtures containing at least 99.99 percent by weight of the high density polyethylene composition of the invention, based on the total weight of the mixture.

[0060] Various polymerization reactions and catalyst systems can be used to prepare the high density polyethylene compositions of the invention. Typical transition metal catalyst systems used to prepare high density polyethylene compositions are magnesium / titanium based catalyst systems, as exemplified by the catalyst systems described in US No. 4,302,565; vanadium based catalyst systems such as those described in US 4,508,842; US 5,332,793; US 5,342,907; and

US 5,410,003; and metallocene catalyst systems such as those described in US 4,937,299; US 5,317,036; and US 5,527,752. Catalyst systems that use molybdenum oxides on silicon dioxide / alumina supports are also useful. Preferred catalyst systems for producing components of the high density polyethylene compositions of the invention are Ziegler-Nattta catalyst systems and metallocene catalyst systems.

[0061] In some embodiments, the preferred catalysts used in the processes for producing high density polyethylene compositions are magnesium / titanium catalysts. In particular for gas phase polymerization, the catalyst is made from a precursor containing magnesium and titanium chlorides in an electron donor solvent. This solution is often either applied to the porous catalyst support or a filler is added which, after subsequent spray drying, provides additional mechanical strength to the particles. Solid particles, from any method of application to a support, are often suspended in a diluent to give a highly viscous mixture, which is often used as a catalyst precursor. Exemplary types of catalysts are described in US 6,187,866 and US 5,290,745, the contents of both of which are incorporated herein in their entirety. Precipitated / crystallized catalyst systems such as those described in US 6,511,935 and US

6,248,831, both of which are fully incorporated, may also be used. Such catalysts can be further modified with one precursor activator. Such further modifications are described in US Patent Publication No. US20006 / 0287445 A1.

[0062] Preferably, the catalyst precursor has the formula MgdTi (OR) eXf (ED) g, wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR ', where R' is aliphatic or aromatic a hydrocarbon radical having 1 to 14 carbon atoms; each of the OR groups is the same or different; each X is independently chlorine, bromine or iodine; ED means electron donor; d is 0.5 to 56; e is 0, 1 or 2; f is 2 to 116; ag is> 2 and up to 1.5 * d + 3. It is made of a titanium compound, a magnesium compound and an electron donor.

[0063] The electron donor is an organic Lewis base, liquid at temperatures in the range of 0^aboutC to 200^aboutC, in which the titanium and magnesium compounds are soluble. Electron donor compounds are sometimes referred to as Lewis bases. The electron donor may be an aliphatic or aromatic carboxylic acid alkyl ester, an aliphatic ketone, an aliphatic amine, an aliphatic alcohol, an alkyl or cycloalkyl ether, or mixtures thereof, each of the electron donors having from 2 to 20 carbon atoms. Among these electron donors, alkyl and cycloalkyl ethers containing 2 to 20 carbon atoms are preferred; dialkyl, diaryl and alkyl aryl ketones containing 3 to 20 carbon atoms; and alkyl, alkoxy and alkylalkoxy esters of alkyl and aryl carboxylic acids having 2 to 20 carbon atoms. The most preferred electron donor is tetrahydrofuran. Other examples of suitable electron donors are methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethanol, 1-butanol, ethyl formate, methyl acetate, ethyl p-methoxybenzoate, ethylene carbonate, tetrahydropyran and ethyl propionate.

[0064] While a large excess of electron donor can be used initially to provide the reaction product of the titanium compound and the electron donor, the final catalyst precursor contains about 1 to about 20 moles of the electron donor per mole of the titanium compound, and preferably, about 1 to about 10 moles of the electron donor per mole of the compound titanium.

[0065] Since the catalyst will act as a matrix for polymer growth, it is important that the catalyst precursor be converted to a solid. It is also important that the solid obtained has a particle size and shape suitable to produce polymer particles with a relatively narrow size distribution, small amount of fine particles, and good fluidization properties. Although this solution of Lewis base, magnesium and titanium compounds can be a saturated porous support and dried to form a solid catalyst; it is preferred that the solution is converted into a solid catalyst by means of spray drying. Each of these methods thus forms a "supported catalyst precursor".

[0066] The spray dried catalytic product is then preferably placed in suspension in mineral oil. The viscosity of the hydrocarbon diluent from the slurry is low enough that the slurry can be conveniently pumped through the pre-activation apparatus and optionally into the polymerization reactor. The catalyst is fed through a catalyst suspension feeder. Industrial reaction systems typically use a chamber flow pump, such as a Moyno pump, while a dual syringe piston pump is typically used in pilot-3 -9-3 reaction systems where catalyst flows are less than or equal to 10 cm³/ hour (2.78 x 10^-9 m³/ s) suspensions.

[0067] The cocatalyst or activator is also fed into the polymerization reactor. Complete activation with an additional cocatalyst is required for full activity. Complete activation normally takes place in the polymerization reactor, although the technologies referred to in EP 1,200,483 can also be used.

[0068] Cocatalysts, which are reducing agents, conventionally used, consist of aluminum compounds, but also lithium, sodium and potassium compounds, alkaline earth metals, as well as compounds of earth metals other than aluminum. The compounds are usually hydrides, organometallic compounds or halides. Butyllithium and dibutylmagnesium are examples of useful non-aluminum compounds.

[0069] The activator compound, which is usually used with any titanium-based catalyst precursor, may have the formula AlRaXbHc, wherein each X is independently chlorine, bromine or iodine, or OR '; each R and R 'is independently a saturated aliphatic hydrocarbon radical having 1 to 14 carbon atoms; b is 0 to 1.5; c is 0 or 1; and a + b + c = 3. Preferred activators include alkyl aluminum mono- and dichlorides in which each alkyl radical contains 1 to 6 carbon atoms and trialkylaluminum compounds. Examples are diethylaluminum chloride and tri-n-hexylaluminum chloride. About 0.10 to 10 moles, and preferably 0.15 to 2.5 moles of activator is used per mole of electron donor. The molar ratio of activator to titanium is in the range of 1: 1 to 10: 1 and is preferably in the range of 2: 1 to 5: 1.

[0070] The aluminum cocatalyst containing a hydrocarbon radical may be represented by the formulas R3Al or R2AlX, wherein each R is independently alkyl, cycloalkyl, aryl or hydrogen; wherein at least one R is hydrocarbon; and two or three R radicals may be joined to form a heterocyclic structure. Each R which is a hydrocarbon radical may contain 1 to 20 carbon atoms and preferably has 1 to 10 carbon atoms. X is halogen, preferably chlorine, bromine or iodine. Examples of aluminum compounds with a hydrocarbon radical are: triisobutylaluminum, tri-n-hexylaluminum, di-isobutylaluminum hydride, dihexylaluminum hydride, diisobutylhexylaluminum, isobutyl dihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, tripropylaluminum, , tribenzylogaluminum, triphenylaluminum, trinaftyluminum, tritoluylaluminum, dibutylaluminum chloride, diethylaluminum chloride and ethylaluminium sesqui chloride. Cocatalyst compounds can also serve as activators and modifiers.

[0071] Activators may be added to the precursor before and / or during polymerization. In one procedure, the precursor is fully activated before polymerization. In another procedure, the precursor is partially activated before polymerization and activation is completed in the reactor. Where a modifier is used instead of an activator, the modifiers are usually dissolved in an organic solvent such as isopentane and, when a support is used, it is impregnated with a modifier after impregnation with a titanium compound or complex, after which the supported catalyst precursor is dried. Otherwise, the modifier solution is added as such directly to the reactor. The modifiers have a similar chemical structure and perform a function similar to activators, which are cocatalysts. For variations, see, for example, US No. 5,106,926, which is incorporated herein in its entirety as a bound material. The cocatalyst is preferably added separately as such or in the form of a solution in an inert solvent such as isopentane to the polymerization reactor at the time the ethylene flow begins.

[0072] In those embodiments that utilize the support, the precursor is applied to an inorganic oxide support such as silica, aluminum phosphate, alumina, silica / alumina mixtures, silica that has been modified with an organoaluminium compound such as triethylaluminum and diethylzin modified silica. . In some embodiments, silica is the preferred support. A typical support is a solid, particulate, porous material substantially inert to polymerization. It is used as a dry powder having an average particle size of 10 to 250 mm, preferably 30 to 100 mm; with a specific surface area of ​​2 -10 at least 200 m²/ g, and preferably at least 250 m²/ G; and pore dimensions of at least 100 x 10^-10-10 m, preferably at least 200 x 10^-10 m. Generally, the amount of carrier used is such as to provide

EP 2 016 127 B1

0.1 to 1.0 mmol of titanium per gram of carrier, and preferably 0.4 to 0.9 mmol of titanium per gram of carrier. The impregnation of the silica support with the aforementioned catalyst precursor can be carried out by mixing the precursor and the silica gel in an electron donor solvent or other solvent followed by removal of the solvent under reduced pressure. When a support is undesirable, the catalyst precursor can be used in liquid form.

[0073] In another embodiment, metallocene catalysts with one active site with limited geometry may be used in the practice of the present invention. Generally, catalytic metallocene compounds include half or fully sandwich compounds having one or more p-linked ligands, including cyclopentadienyl type structures, or other similar acting structures such as pentadiene, cyclooctatetraendiyl and imides. Typical compounds are generally described as containing one or more ligands capable of forming a p bond with a transition metal atom, usually, ligands or units derived from cyclopentadienyl, in combination with a transition metal selected from groups 3 to 8, preferably 4, 5 or 6, or a number of lanthanides and actinides of the Periodic Table.

[0074] Examples of metallocene-type catalytic compounds are described, for example, in US Patent Nos. 4,530,914; 4,871,705; 4,937,299; 5,017,714; 5,055,438; 5,096,867; 5,120,867; 5,124,418; 5,198,401; 5,210,352; 5,229,478; 5,264,405; 5,278,264; 5,278,119; 5,304,614; 5,324,800; 5,347,025; 5,350,723; 5,384,299; 5,391,790; 5,391,789; 5,399,636; 5,408,017; 5,491,207; 5,455,366; 5,534,473; 5,539,124; 5,554,775; 5,621,126; 5,684,098; 5,693,730; 5,698,634; 5,710,297; 5,712,354; 5,714,427; 5,714,555; 5,728,641; 5,728,839; 5,753,577; 5,767,209; 5,770,753 and 5,770,664; European publications: EP-A0 591 756; EP-A-0 520 732; EP-A-0 420 436; EP-A-0 485 822; EP-A-0 485 823; EP-A-0 743 324; EP-A0 518 092; and PCT publications: WO 91/04257; WO 92/00333; WO 93/08221; WO 93/08199; WO 94/01471; WO 96/20233; WO 97/15582; WO 97/19959; WO 97/46567; WO 98/01455; WO 98/06759 and WO 98/11144.

[0075] Suitable catalysts for use in the present invention, preferably include limited geometry catalysts as disclosed in US Patent Nos. 5,272,236 and 5,278,272.

[0076] Transition metal monocyclopentadienyl catalysts for olefin polymerization as defined in US Patent No. 5,026,798 are also suitable as catalysts for the present invention.

[0077] The aforementioned catalysts may be further described as comprising a metal coordination complex comprising a metal of groups 3-10 or from a series of lanthanides of the Periodic Table of Elements and a delocalized unit bound by a bond p substituted with a unit causing limited geometry. Such a complex has limited geometry around a metal atom. The catalyst additionally contains an activating cocatalyst.

[0078] Any conventional ethylene homopolymerization or (co) polymerization reaction can be used to prepare the high density polyethylene compositions of the invention. Such conventional homopolymerization or (co) polymerization reactions include, but are not limited to, gas phase polymerization, suspension polymerization, liquid phase polymerization and combinations thereof, using conventional reactors, e.g. gas phase reactors loop, stirred tank reactors and batch reactors in series or in series and in parallel. The polymerization system of the present invention is a dual sequential polymerization system or a multi-sequential polymerization system. Examples of dual sequential polymerization include, but are not limited to, gas phase polymerization / gas phase polymerization

EP 2 016 127 B1; gas phase polymerization / liquid phase polymerization; liquid phase polymerization / gas phase polymerization; liquid phase polymerization / liquid phase polymerization; suspension polymerization / suspension polymerization, liquid phase polymerization / suspension polymerization; slurry polymerization / liquid phase polymerization; slurry polymerization / gas phase polymerization and gas phase polymerization / suspension polymerization. Multi-sequential polymerization systems include at least three polymerization reactions. The catalyst system described above may also be a conventional catalyst system. The high molecular weight polyethylene composition of the invention is preferably produced by a double gas phase polymerization process, for example gas phase polymerization / gas phase polymerization; however, the present invention is not so limited and any of the above combinations can be used.

[0079] In production, a dual sequential polymerization system connected in series as described above can be used. The first component, which is a high molecular weight ethylene polymer, can be produced in the first stage of the dual sequential polymerization system, and the second component, which is a low molecular weight ethylene polymer, can be produced in the second stage of the dual sequential polymerization system. Alternatively, the second component, which is a low molecular weight ethylene polymer, may be produced in the first stage of the dual sequential polymerization system, and the first component, which is a high molecular weight ethylene polymer, may be produced in the second stage of the dual sequential polymerization system.

[0080] For the purposes of this disclosure, the reactor in which the conditions are set to produce the first component is referred to as the first reactor. Alternatively, the reactor in which the conditions are set to produce the second component is referred to as the second reactor.

[0081] During production, a catalyst system comprising cocatalyst, ethylene, one or more alpha-olefin comonomers, hydrogen and optionally gases and / or inert liquids, for example N2, isopentane and hexane, are fed continuously into the first reactor, which is connected to the second reactor in series; the first component / active catalyst mixture is then continuously transferred, for example, in portions from the first reactor to the second reactor. Ethylene, hydrogen, cocatalyst and possibly inert gases and / or inert liquids, e.g. N2, isopentane, hexane, are continuously fed into the second reactor and the final product, which is the high-density polyethylene composition according to the invention, is constantly removed, on example, in portions from a second reactor. The preferred method is to take specific amounts of the first component from the first reactor and transport them to the second reactor using the pressure difference generated by the recycle gas compression system. The high-density polyethylene composition of the invention is then transferred to a purification compartment under an inert atmosphere. Then, residual hydrocarbons are removed and moisture is introduced to remove any residual alkylaluminum and any catalyst residue before exposing the high density polyethylene composition of the present invention to oxygen. The high-density polyethylene composition of the invention is then transferred to an extruder and granulated. Such pelleting technologies are generally known. The high-density polyethylene composition of the present invention may be further subjected to passage through a molten mesh. After the melting process in the extruder, the molten composition is passed through one or more active sieves (arranged in series when there is more than one sieve) with each active sieve having the dimensions of retained particles

-5 -5 in microns from 2 to 400 (2 to 4 x 10^-5 m), preferably 2 to 300 (2 to 3 x 10^-5 m) and most preferably

EP 2 016 127 B1 to 70 (2 to 7 x 10^-6 m), with a mass flow of 5 to 100 pounds / h / inch² (1.0 to about 20 kg / s / m²). Such further melt screening is disclosed in US Patent No. 6,485,662, to the extent that it discloses melt screening.

[0082] In alternative production, a multi-sequential polymerization system connected in series and in parallel can be used as described above. In one embodiment of the present invention, a catalyst system comprising cocatalyst, ethylene, one or more alpha-olefin comonomers, hydrogen and optionally inert gases and / or inert liquids, e.g. N2, isopentane and hexane, are continuously introduced into the first reactor, which is connected to a second reactor and which second reactor is connected to the third in series; the first component / active catalyst mixture is then continuously transported, for example, in portions from the first reactor to the second reactor and then to the third reactor. Ethylene, hydrogen, cocatalyst and optionally inert gases and / or inert liquids, for example, N2, isopentane, hexane, are constantly introduced into the second reactor and the third reactor and the final product, which is the high-density polyethylene composition according to the invention, is constantly removed. for example, in portions, from a third reactor. The preferred method is to collect specific amounts of the first component from the first reactor and transport them to the second reactor, followed by withdrawing portions from the second reactor and transferring them to the third reactor using the pressure difference generated by the recycle gas compression system. Alternatively, the first reactor can feed both the second reactor and the third reactor in parallel and the product from the first reactor can be transferred to either the second or the third reactor. The high-density polyethylene composition of the invention is then transferred to a purification compartment under an inert atmosphere. Then, residual hydrocarbons are removed and moisture can be introduced to remove any residual alkylaluminum and any catalyst residues before exposing the high density polyethylene composition of the present invention to oxygen. The high-density polyethylene composition of the invention is then transferred to an extruder and granulated. Such pelleting technologies are generally known. The high-density polyethylene composition of the present invention may be further subjected to passage through a molten mesh. After the melting process in the extruder, the molten composition is passed through one or more active sieves (placed in series when there is more than one sieve), each active sieve having retained particle dimensions in microns of from 2 to 400 (2 to 4 x - 5 -5 -6

10^-5 m) and preferably 2 to 300 (2 to 3 x 10^-5 m), and most preferably 2 to 70 (2 to 7 x 10^-6 m), at a mass flow of 5 to 100 pounds / h / inch² (1.0 to about 20 kg / s / m²). Such further melt screening is disclosed in US Patent No. 6,485,662, to the extent that it discloses melt screening. [0083] In another alternative production, the high-density polyethylene composition of the invention may be made from polymers prepared in two or more independent reactors (each using the same or different catalysts) with subsequent mixing after the reaction.

[0084] In use, the high density polyethylene composition of the invention can be used to make shaped articles. Such articles may include closing devices such as bottle closures, cable wire casings, plumbing pipes or blow molded articles. Various methods can be used to manufacture articles such as cap closures for bottles, cable wire casings, plumbing pipes or injection molded articles, for example bottles manufactured by blow molding.

Suitable processing technologies include wire coating, pipe extrusion, blow molding, co-welding

Blow molding, injection molding, blow molding, stretch blow molding, compression, extrusion, continuous compression and calendering, but are not limited to these. Such technologies are well known. Preferred processing technologies include wire coating, pipe extrusion, blow molding, compression and injection.

[0085] In the compression compression method, the two-part mold provides a cavity having the shape of the desired molded article. The mold is heated. A suitable amount of the high density polyethylene composition of the invention, preferably in molten form, is charged into the bottom half of the mold. Two parts of the mold are put together under pressure. The high-density polyethylene composition of the invention, softened by heating, is thus bonded to a continuous mass having the form of a mold cavity. The continuous mass is cured by cooling, under pressure, in a mold, thereby forming a compressed article, for example, a bottle closure. The pressed closure closure may include a sheath that extends axially from the periphery of the base and may further include an internal thread for attaching the closure closure to the container.

[0086] In the injection molding method, the high density polyethylene composition of the invention is fed to an extruder through a hopper. The extruder transports, heats, melts and holds under pressure the high-density polyethylene composition of the invention in the form of a molten stream. The molten stream is squeezed from the extruder through a nozzle into a relatively cool, closed mold maintained under pressure, thus filling the mold. The alloy cools and hardens until completely cured. The mold is then opened and the molded element is removed, e.g. a bottle closure. The injection molded closure may include a sheath that extends axially from the periphery of the base and may further include an internal thread for attaching the applied closure to the container.

[0087] In the blow molding process, for example, injection molding, the high density polyethylene composition of the invention is melted and then formed into a pipe or blow molded preform by injection molding. The ends of the pipe or preform are sealed, except for the area where blowing air may enter. The closed pre-formed pipe or fitting is inflated inside the mold so that it assumes the shape of the mold. The molded article, e.g. a bottle, is cooled and then ejected from the mold. If necessary, the molded article is then trimmed.

[0088] Closure devices, such as cap-on bottle closures, comprising the high-density polyethylene composition of the invention show improved resistance to stress cracking under the influence of the environment. Such attachable bottle closures are adapted to withstand the pressure of carbonated beverages. Such applied bottle closures further facilitate closing and sealing of the bottle, i.e. the optimal moment exerted by the machine for screwing the cap on the bottle, or unscrewing from the bottle, i.e. the optimal moment exerted by a person when unscrewing the applied closure from the bottle.

Examples [0089] It is understood that the present invention can be practiced in the absence of any component that is not specifically disclosed. The following examples are provided to further illustrate the invention and should not be construed as limiting.

EP 2 016 127 B1

Examples of the invention 1-6 [0090] Examples 1-6 of the invention were prepared according to the following procedures: a dual sequential polymerization system was provided, for example, a first gas phase polymerization reactor and a second gas phase polymerization reactor operating in series. Ethylene, one or more alpha-olefin comonomers, hydrogen, catalyst, e.g. Ziegler-Natta catalyst, in suspension in mineral oil, N2 and isopentane were continuously fed to the first reactor. Then, a cocatalyst, e.g., triethylaluminum (TEAL), was continuously fed into the first reactor to activate the catalyst. The first ethylene polymerization reaction was carried out in the presence of 1-hexene in the first reactor under the conditions set out below in Table 1, thereby producing the first component-catalyst complex. Complex of the first component with the catalyst continuously transferred to the second reactor. Additional ethylene, hydrogen, cocatalyst, for example TEAL, N2 and isopentane, were constantly fed into the second reactor. No additional catalyst was introduced into the second reactor. The second ethylene polymerization reaction was carried out under the second reactor under the conditions shown in Table 1 below, thereby producing the first component-catalyst-second component complex. This first component-catalyst-second component complex was continuously removed in portions from the second reactor into the product chamber, where it was purged to remove residual hydrocarbons, and then sent to a fiber filled drum. The drum with fiber filling was constantly flushed with moist nitrogen. The polymer, which is the high-density polyethylene composition of the invention, was further processed in a mixer / granulator. Additional additives as shown in Table III were added to the polymer, i.e. the high-density polyethylene composition of the invention. The polymer, which is the high-density polyethylene composition of the invention, was melted in the mixer and the additives were dispersed in the polymer, i.e., the high-density polyethylene composition of the invention as a matrix. The high-density polyethylene composition of the invention was extruded through a nozzle plate, granulated, and cooled. The resin samples of examples 1-6 according to the invention were tested for properties on granules or after forming into the shape of test plates according to ASTM D4703-00, and then tested for properties. These properties are shown in Tables I and II and in Figures 1-4.

Comparative Examples AE [0091] Comparative Example A is commercially available under the trade name Borstar® MB6561 from Borealis AIS, Denmark. Comparative Example B is commercially available under the trade name Rigidex® HD 5130 EA-B from BP Solvay Polyethylene. Comparative Example C is commercially available under the trade name XZ 89719.01 from Dow Chemical Company, USA. Comparative Example D is commercially available under the trade name Hostaen® GX4027 from Basell, Germany. Comparative Example E is commercially available under the trade name XZ 89719.00 from the Dow Chemical Company, USA. Resin samples from Comparative Examples AE were tested for properties on granules or after forming test plates in accordance with ASTM D-4703-00, and then tested for properties. Resin samples from comparative examples AE and plates made of these resins were subjected to property tests. These properties are shown in Tables IV.

Test methods

[0092] Unless otherwise stated, the amounts quoted herein were determined according to the following test methods.

[0093] Density (g / cm³) measured according to ASTM-D 792-03, method B, in isopropanol. Samples were measured within 1 hour of molding after conditioning in an isopropanol bath at 23^aboutC for 8 min for thermal equalization before measurement. Samples were pressed according to ASTM D-4703-00 annex A with a period of 5 min of initial heating at about 190^aboutC and cooling rate 15^aboutC / min according to procedure C. Samples were cooled to 45^aboutC in the press and cooling continued until "cool to touch".

[0094] Melt index (I2) was measured at 190^aboutC under a load of 2.16 kg according to ASTM D-1238-03.

[0095] Melt index (I5) was measured at 190^aboutC under 5.0 kg load according to ASTM

D-1238-1203.

[0096] Melt index (I10) was measured at 190^aboutC under a load of 10.0 kg according to

ASTM D-1238-03.

[0097] Melt index (I21.6) was measured at 190^aboutC under a load of 21.6 kg according to

ASTM D-1238-03.

[0098] The weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by methods known in the art using conventional GPC as described herein below.

[0099] The molecular weight distribution of ethylene polymers was determined by gel permeation chromatography (GPC). The chromatography system consisted of a high temperature gel chromatograph at 150^aboutC Waters (Milliford, MA), equipped with a 2-angle laser light scattering detector Precision Detectors Model 2040 (Amherst, MA). For calculation purposes, a 15-degree laser light scattering detector was used^about. Data collection was performed using Viscotek TriSEC version 3 software and the 4-channel Viscotek DM400 data management program. The system was equipped with an on-line solvent degassing device from Polymer Laboratories. The carousel compartment worked in

140^aboutC, and the column compartment worked in 150^aboutC. The columns used were four Shodex HT 806M 300mm, 13mm columns and one Shodex HT803M 150mm, 12mm column. The solvent used was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 g polymer in 50 milliliters of solvent.

The chromatographic solvent and the sample preparation solvent contained 200 mg / g of butylated hydroxytoluene (BHT). Both solvent sources were sparged with nitrogen. Polyethylene samples were gently mixed in 160^aboutC for 4 hours. An injection amount of 200 microliters was used and the flow rate was 0.67 milliliters / min. Calibration of the GPC column set was carried out using 21 polystyrene standards with a narrow molecular weight distribution, with molecular weights in the range from 580 to 8 400,000 g / mol, which were arranged in 6 "cocktail" mixtures with at least a decimal interval between individual molecular weights. Standards were provided by Polymer Laboratories (Shropshire, UK). Polystyrene standards were prepared in portions of 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000 g / mol and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g / mol. Polystyrene standards were dissolved in 80^aboutC with gentle stirring for 30 minutes. Mixtures of narrow standards were released first and to reduce the component with the highest molecular weight to reduce degradation. The molecular weights of the polystyrene standards peaks are 20

EP 2 016 127 B1 was shaped for the molecular weight of polyethylene using the following equation (as described in the publication

Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

_B

Mpolythene = A (Mpolystyrene)^B, where M is the molecular weight, A is 0.41 and B is 1.0. System approximation to determine multi-detector data shift was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chapter 12 (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13 (1992)) by optimizing the results of a double detector log from results for wide polystyrene 1683 Dow to narrow calibration column results from a narrow standard calibration curve using proprietary software. Molecular weight data for determining data shift was obtained in a manner consistent with the method published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NJ. (1987)). All injected concentration used for molecular weight determination was obtained from the refractive index field of the sample and the refractive index calibration for the detector for a linear polyethylene homopolymer with a molecular weight of 11,5000 g / mol, which was measured relative to the NIST 1475 polyethylene homopolymer standard. Sufficiently low chromatographic concentrations were assumed to eliminate effects related to the 2nd virial coefficient (concentration effect on molecular weight). Molecular weight calculations were performed using proprietary software. Calculations of the number average molecular weight, weight average molecular weight and z-average molecular weight were performed according to the following equations, assuming that the signal from the refractometer is directly proportional to the mass fraction. The refractometer signal with the reference line subtracted can be directly replaced by the mass fraction in the equations as below. It should be noted that the molecular weight can be obtained from a conventional calibration curve or the absolute molecular weight from the ratio of light scattering to refraction. A better approximation of the average molecular weight, the light scattering signal with the baseline subtracted, can be replaced by the product of the average weight molecular weight and mass fraction in equation (2) below:

<img file="PL2016127T3_D0001.tif" />

[0100] The bimodality of the distributions was characterized according to the mass fraction of the peak with the highest temperature in the fractionation data by elution with increasing temperature (typically abbreviated

EP 2 016 127 B1 as "TREF") as described, for example, in Wild et al., Journal of Polymer Science. published by: Poly. Phys.,

Ed., Vol. 20, p. 441 (1982) in US 4,798,081 (Hazlitt and Inn.) Or in US 5,089,321 (Chum and Inn.), The disclosure of which is fully incorporated herein by reference. In analytical fractionation analysis by elution with increasing temperature (as described in US 4,798,081 and abbreviated herein as "ATREF") the composition to be analyzed is dissolved in a suitable hot solvent (e.g. 1,2,4-trichlorobenzene) and allowed to crystallization in a column containing an inert support (e.g., stainless steel shot) by slowly decreasing the temperature. The column was equipped with both an infrared detector and a differential viscometer (DV) detector. The 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 more detail in WO 99/14271, the disclosure of which is hereby incorporated herein by reference.

[0101] The high density fraction (percent) was determined by analytical fractionation analysis by elution at increasing temperature (as described in US 4,798,081 and abbreviated as "ATREF"), which is then described in more detail. Analytical fractionation analysis with elution at increasing temperature was carried out according to the method described in US Patent No. 4,798,081 and publication Wilde, L; Ryle, TR; Knobeloch, DC; Peat, IR; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20 441-455 (1982), which we include here in full. 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^aboutC with a cooling rate of 0.1^aboutC / min. The column was equipped with an infrared detector. The ATREF chromatogram curve was then generated by eluting the crystallized polymer sample from the column by slowly increasing the elution solvent (trichlorobenzene) temperature from 20 to 120^aboutC at a rate of 1.5^aboutC / min.

[0102] Branch distributions were determined by crystallization fractionation analysis (CRYSTAF); described here below. Fractionation by crystallization (CRYSTAF) analysis was performed using a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain. Samples were dissolved in

1,2,4-trichlorobenzene in 160^aboutC (0.66 mg / ml) for 1 hour and stabilized at 95^aboutC for 45 minutes. Sampling temperatures ranged from 95 to 30^aboutC with a cooling rate of 0.2 ^aboutC / min. An infrared detector was used to measure the concentrations of the polymer solutions. The cumulative solute concentration during polymer crystallization was measured while the temperature was reduced. Analytical differentiation of the cumulative profile reflects the distribution of short chain branches in the polymer.

[0103] The CRYSTAF temperature peak and surface are identified by the peak analysis module included in the CRYSTAF software (version 2001.b, PolymerChar, Valencia, Spain). The data procedure for the CRYSTAF peak identifies the temperature peak as the maximum on the dW / dT curve and the area between the largest positive inflections on either side of the identified peak in the differential curve. For the calculation of the CRYSTAF curve, the preferred processing parameters are the temperature limit of 70^aboutC and smoothing parameters above the temperature limit of 0.1 and below the temperature limit of 0.3.

[0104] The solubility distribution width index (SDBI) is the statistical width value from the CRYSTAF method, which is calculated using the following formulas:

EP 2 016 127 B1

SDBf = -year_in)⁴ In (T) dT t_in = jr *_in(r) dr faryjr = and in which T is the temperature, W is the mass fraction and Tw is the average mass temperature.

[0105] Long chain branches were determined by methods known in the art, such as gel chromatography coupled with a small angle laser scattering detector (GPC-LALLS) and gel chromatography coupled with a differential viscometer (GPC-DV) detector.

[0106] The resin stiffness was characterized by measuring the flexural modulus at 5 percent and secant modules at 1 percent and 2 percent at a test speed of 0.5 inch / min (13 mm / min) according to ASTM D 790-99 method B.

[0107] The tensile strength at the flow limit and elongation at break were measured according to

ASTM D-638-03 using Type IV samples at 2 inches / minute (50 mm / min).

[0108] Stress cracking resistance under environmental conditions (ESCR) was measured in accordance with ASTM-D 1693-01, condition B. The susceptibility of the resin to mechanical damage by cracking was measured under constant stress and in the presence of a crack accelerating agent such as soaps, agents wetting, etc. Measurements were carried out on notched samples in an Igepal CO-630 aqueous solution (salesman Rhone-Poulec, NJ) at a concentration of 10 percent by volume, kept at 50^aboutC and an aqueous solution of Igepal CO-630 (sold by Rhone-Poulec, NJ) at a concentration of 100 percent by volume, kept at 50^aboutC. The ESCR value was reported as F50, calculated 50 percent failure time from the probability plot and Fo, where there was no destruction of the sample in the experiment.

[0109] The short chain branching distribution and comonomer content was measured using C13 NMR as discussed in Randall, Rev. Macromol. Chem. Chys. C29 (2 &amp; 3) pp. 285-297 and US 5,292,845, the disclosures of which are incorporated herein by reference in the scope for such measurement. Samples were prepared by adding about 3 g of a 50/50 mixture of tetrachloroethane-d2 / orthodichlorobenzene, which was 0.025M in chromium acetylacetonate (relaxation agent) to 0.4 g of the sample in a 10 mm NMR tube. Samples were dissolved and homogenized by heating the tube with its contents to 150^aboutC. Data was collected using a JEOL Eclipse 400 MHz NMR spectrometer corresponding to a 13C 100.6 MHz resonance frequency. Acquisition parameters were selected to ensure quantitative 13C data acquisition in the presence of a relaxation agent. Data were collected using 1H gated decoupling, 4000 passes through the data set, 4.7 sec relaxation delay and 1.3 seconds acquisition time, 24200 Hz spectral width and 64K data point collection size, the sample head being heated to 130^aboutC. The spectra were compared to the methylene peak at 30 ppm. The results were calculated according to the ASTM D5017-91 method.

[0110] Resin rheology was measured on an ARES I (Advanced Rheometric Expansion System) rheometer. ARES I was a controlled deformation rheometer. A rotary actuator (servomotor) applied shear deformation in the form of deformations to the sample. In response, the sample generated a moment that was measured

EP 2 016 127 B1 through the transducer. For the calculation of dynamic properties, such as modulus and viscosity, strain and moment were used. The viscoelastic properties of the samples were measured in the alloy using a set of parallel plates with a diameter of 25 mm, with constant deformation (5 percent) and temperature (190^aboutC) with N2 purge and in -1 variable frequency function (0.01 to 500 s^-1). The real component of the complex module, loss module, tan delta and resin complex viscosity were determined using the Rheometric Orchestrator software (ver-1 -1 sja 6.5.8). The viscosity ratio ((0.1 rad ^ s / 100 rad ^ s) was determined as the ratio of the viscosity measured at a shear rate of 0.1 rad / s to the viscosity measured at a shear rate of 100 rad / s.

[0111] Vinyl type unsaturations were measured according to ASTM D-6248-98.

[0112] Low-shear rheological characteristics were determined on a Rheometrics SR5000 instrument in a controlled tension manner using a special grip for 25 mm parallel plates. This type of geometry is recommended for the cone and plate method because it requires only minimal crushing flow during sample loading, thus reducing residual stress.

[0113] Mean g 'was determined according to the following procedure. The chromatographic system consisted of a chromatograph operating at a high temperature of 150^aboutC Waters (Miliford, MA) equipped with Precision detectors (Amherst, MA), 2-angle model 2040 laser light scattering detector, IR4 infrared detector from PolymerChar (Valencia, Spain) and 150R-4 Viscotek capillary viscometer (Houston, TX) ). A 15 degree light scattering detector was used for the calculation. Data collection was performed using the Viscotek TriSEC software version, 3 and 4-channel Viscotek DM400 data management program. The system was equipped with an online solvent degassing device from Polymer Laboratories. The carousel compartment worked in 140^aboutC, and the column compartment worked in 150^aboutC. Four mixed-bed 20 micron columns, light scattered "Mixed A-LS" from Polymer Laboratories were used. The solvent used was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 g polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent contained 200 ppm butylated hydroxytoluene (BHT). Both solvent sources were sparged with nitrogen. Polyethylene samples were gently mixed at 160 degrees Celsius for 4 hours. An injection volume of 200 microliters was used and the flow rate was 1 milliliter / min.

[0114] Calibration of a set of GPC columns was carried out using 21 polystyrene standards with a narrow molecular weight distribution with molecular weights in the range from 580 to 8400000 g / mol, which were arranged in 6 "cocktail" mixtures with at least a decimal interval between individual molecular weights. Standards were provided by Polymer Laboratories (Shopshire, UK). Polystyrene standards were prepared in portions of 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000g / mol and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g / mol. Polystyrene standards were dissolved in 80^aboutC with gentle stirring for 30 minutes. Mixtures of narrow standards were released first and to reduce the component with the highest molecular weight to minimize degradation. The peak molecular weights of polystyrene standards were converted to the polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

_B

Mpolythene = A (Mpolystyrene)^B,

Where M is the molecular weight, A is 0.43 and B is 1.0.

[0115] System approximation to determine multi-detector data shift was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chapter 12 (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13 (1992)) by optimizing the log results (MW and IV) for a triple detector from 1683 Dow wide polystyrene results to narrow column calibration results from a narrow standard calibration curve using proprietary software. Molecular weight data for determining data shift was obtained in a manner consistent with the method published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NJ.

(1987)). All injected concentration used for molecular weight determination was obtained from the field for the refractive index of the sample and calibration of the refractive index for the detector for a linear polyethylene homopolymer with a molecular weight of 115,000 g / mol. Sufficiently low chromatographic concentrations were assumed to eliminate effects related to the 2nd virial coefficient (concentration effect on molecular weight).

[0116] The average g 'for the samples was calculated as follows:

1. Light scattering, viscosity and concentration detectors were calibrated using a NBS 1475 polyethylene homopolymer (or equivalent reference sample);

2. The shifts of the light scattering detector and viscometer data relative to the concentration detector were corrected as described in the calibration section;

3. Reference lines and subtraction ranges were subtracted from the light scattering, viscometer and concentration chromatograms to ensure integration of all low molecular weight retention volume ranges in the scattered light chromatogram that could be observed in a refractometer chromatogram;

4. A Mark-Houwink reference line was established for a linear polyethylene homopolymer by injecting a standard with a polydispersity of at least 3.0 and the data set (from the calibration method above) was calculated and the intrinsic viscosity and molecular weight were recorded from the data corrected for the constant mass for each chromatographic slice;

5. The HDPE sample in question was injected and the data set calculated (from the above calibration method) and the intrinsic viscosity and molecular weight were recorded from the corrected mass constant data for each chromatographic slice;

6. The reference intrinsic viscosity of the linear homopolymer was shifted by the following factor: IV = IV + 1 / (1 + 2 * SCB) / 1000C * length of branching points) where IV is the intrinsic viscosity of the HDPE sample in question, SCB / 100C was determined from C13 NMR , and the length of the branching sites is 2 for butene, 4 for hexene and 6 for octene);

7. The average g 'was calculated from the following equation

EP 2 016 127 B1

Highest Μ

Σ when Μ&gt; 40Ο0Ο

<td></td><td>(ir, Ί</td><td></td>

<td>C, X</td><td></td><td></td>

<td>J</td><td>with hand ,.</td><td></td>

<td></td><td>V ^LJ)</td><td>M</td>

Highest Μ. Σ-, j = Lowest Μ

When M&gt; 40,000

Σ^ε&gt;

j— Lowest Μ where c is the slice concentration, IV is the intrinsic viscosity of HDPE, and IVL is the intrinsic viscosity of the reference sample of the linear polyethylene homopolymer (corrected for the SCB of the HDPEo sample it is about) with the same molecular weight (M). The ratio IV was assumed to be one for molecular weights less than 40,000, taking into account the natural dispersion in the light scattering data. [0117] When indicating the scope of the invention, reference should be made to the appended claims and not to the above description.

Table 1

<td></td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 4</td><td>Example 5</td><td>Example 6</td>

<td>Comonomer type</td><td>1-hexene</td><td>1-hexene</td><td>1-hexene</td><td>1-hexene</td><td>1-hexene</td><td>1-hexene</td>

<td>Catalyst</td><td>Ziegler-Natta</td><td>Ziegler-Natta</td><td>Ziegler-Natta</td><td>Ziegler-Natta</td><td>Ziegler-Natta</td><td>Ziegler-Natta</td>

<td>cocatalyst</td><td>2.5% TEAL</td><td>2.5% TEAL</td><td>2.5% TEAL</td><td>2.5% TEAL</td><td>2.5% TEAL</td><td>2.5% TEAL</td>

<td>Type of first reactor</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td>

<td>Type of 2nd reactor</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td><td>In phase gas</td>

<td>1st reaction temperature (^aboutC)</td><td> 85</td><td> 85</td><td> 85</td><td> 85</td><td> 85</td><td> 85</td>

<td>2nd reaction temperature (^aboutC)</td><td> 109,9</td><td> 110</td><td> 110</td><td> 110</td><td> 110</td><td> 110</td>

<td>1st response pressure (psi)</td><td> 349</td><td> 349</td><td> 349</td><td> 349</td><td> 348</td><td> 348</td>

<td>2nd reaction pressure (psi)</td><td> 403</td><td> 405</td><td> 405</td><td> 402</td><td> 404</td><td> 394</td>

<td>Partial pressure C₂ in the 1st reactor (psi)</td><td> 23,2</td><td> 22,6</td><td> 26,3</td><td> 24,9</td><td> 20,7</td><td> 26,1</td>

<td>Partial pressure C₂ in the 2nd reactor (psi)</td><td> 93,7</td><td> 97,2</td><td> 100,6</td><td> 100,8</td><td> 104,1</td><td> 81,1</td>

<td>H molar ratio₂/ C₂ in the first reactor</td><td> 0,082</td><td> 0,060</td><td> 0,093</td><td> 0,080</td><td> 0,052</td><td> 0,115</td>

<td>H molar ratio₂/ C₂ in the 2nd reactor</td><td> 1,80</td><td> 1,802</td><td> 1,805</td><td> 1,127</td><td> 1,799</td><td> 1,799</td>

<td>C ^ C molar ratio₂ in the first reactor</td><td> 0,062</td><td> 0,1049</td><td> 0,0253</td><td> 0,0635</td><td> 0,0918</td><td> 0,0463</td>

EP 2 016 127 B1

<td>C molar ratio₆/ C₂ in the 2nd reactor</td><td> 0,004</td><td> 0,0051</td><td> 0,0050</td><td> 0,0036</td><td> 0,0021</td><td> 0,0029</td>

<td>Angle entry speed₃lollipop (cm³/ h) (only the first reactor)</td><td> 3,2</td><td> 5,2</td><td> 5,7</td><td> 5,4</td><td> 7,2</td><td> 6</td>

<td>Isopentane in the 1st reactor (mol%)</td><td> 8,6</td><td> 8,7</td><td> 8,0</td><td> 7,4</td><td> 7,4</td><td> 8,8</td>

<td>Isopentane in the 2nd reactor (mol%)</td><td> 4,0</td><td> 4,4</td><td> 3,5</td><td> 2,8</td><td> 2,6</td><td> 3,4</td>

Table II

<td></td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 4</td><td>Example 5</td><td>Example 6</td>

<td>Distribution (1st reactor / 2nd reactor)</td><td> 0,448/0552</td><td> 0,472/0,528</td><td> 0,484/0,516</td><td> 0,460/0,540</td><td> 0,427/0,573</td><td> 0,559/0,441</td>

<td>Speed input cocatalyst (cm³/ h) (1st reactor / 2nd reactor)</td><td> 161/161</td><td> 161/158</td><td> 162/154</td><td> 162/154</td><td> 171/170</td><td> 162/134</td>

<td>Production capacity (pounds / h) (1st reactor / 2nd reactor)</td><td> 24,0/21,3</td><td> 24/21</td><td> 24/21</td><td> 24/23</td><td> 25/17</td><td> 25/17</td>

<td>Bed mass (pounds) (1st reactor / 2nd reactor)</td><td> 75,6/135,7</td><td> 76/122</td><td> 75/119</td><td> 75/120</td><td> 76/120</td><td> 78/137</td>

<td>FBD (pounds /₃foot³) (1st) reactor / 2nd reactor)</td><td> 11,1/16,3</td><td> 11,1/16,4</td><td> 11,7/17,4</td><td> 11,3/16,5</td><td> 11,1/17,0</td><td> 11,6/16,4</td>

<td>Bed volume₃(foot³) (1st) reactor / 2nd</td><td> 6,8/8,3</td><td> 6,8/7,4</td><td> 6,4/6,8</td><td> 6,7/7,3</td><td> 6,8/7,1</td><td> 6,8/8,3</td>

EP 2 016 127 B1

<td>reactor)</td><td></td><td></td><td colspan="2"></td><td></td><td></td>

<td>Residence time in the reactor (h) (1st reactor / 2nd reactor)</td><td> 3,1/3.0</td><td> 3,2/2,7</td><td> 3,1/2,6</td><td> 3,1/2,6</td><td> 3,1/2,3</td><td> 3,1/3,3</td>

<td>JAN (Lb / hr / ft³) (1st reactor / 2nd reactor)</td><td> 3,5/2,6</td><td> 3,5/2,8</td><td> 3,7/3,1</td><td> 3,6/3,2</td><td> 3,6/3,8</td><td> 3,7/2,0</td>

<td>Melt flow rate (I21) (1st ingredient) (~) (g / 10 minutes)</td><td> 2,28</td><td> 2,25</td><td> 2,04</td><td> 2,41</td><td> 1,36</td><td> 3,96</td>

<td>Density (first component) (~) (g / cm³)</td><td> 0,9282</td><td> 0,9221</td><td> 0,9360</td><td> 0,9292</td><td> 0,9227</td><td> 0,9336</td>

<td>Ti residue (ppm) (1st component / 2nd component)</td><td> 3,76/1,63</td><td> 3,15/1,61</td><td> 3,66/1,61</td><td> 3,33/1,52</td><td> 3,99/1,56</td><td> 3,66/1,99</td>

<td>Residue Al (ppm) (1st component / 2nd component)</td><td> 9,5/48,2</td><td> 99,63/58,37</td><td> 101,00/49,25</td><td> 94,30/49,42</td><td> 105,69/48,22</td><td> 102,34/56,70</td>

<td>Al / Ti molar residue Ti (ppm) (1st component / 2nd component)</td><td> 47,4/52,8</td><td> 56/65</td><td> 49/55</td><td> 51/54</td><td> 47/56</td><td> 50/51</td>

<td>Bulk density (Lb / ft³) Ti residue (ppm) (1st component / 2nd component)</td><td> 17,8/25,0</td><td> 16,7/24.1</td><td> 20,1/25,6</td><td> 17,6/24,5</td><td> 17,0/24,8</td><td> 18,3/24,8</td>

<td>Melt flow rate</td><td> 1,48</td><td> 1,46</td><td> 1,39</td><td> 1,66</td><td> 1,31</td><td> 1,58</td>

EP 2 016 127 B1

<td>composition HD (I2) polyethylene (2.16 g / 10 minutes)</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Melt flow rate composition HD polyethylene (I5) (5.0 g / 10 minutes)</td><td> 5,89</td><td> 5,99</td><td> 4,96</td><td> 6,06</td><td> 5,69</td><td> 5,58 8</td>

<td>Melt flow rate composition HD polyethylene (I10) (10.0 g / 10 minutes)</td><td> 26,3</td><td> 23,5</td><td> 20,1</td><td> 20,6</td><td> 23,5</td><td> 19,6</td>

<td>Melt flow rate composition HD polyethylene (I21.6) (21.6 g / 10 minutes)</td><td> 139,7</td><td> 162,0</td><td> 133,6</td><td> 108,6</td><td> 179,5</td><td> 108,0</td>

<td>Melt flow rate ratio for HD polyethylene composition (MI21 / MI2)</td><td> 94,2</td><td> 111,0</td><td> 96,5</td><td> 65,3</td><td> 137,1</td><td> 68,5</td>

<td>Melt flow rate ratio for HD polyethylene composition (MI21 / MI5)</td><td> 23,7</td><td> 27,0</td><td> 26,9</td><td> 17,9</td><td> 31,5</td><td> 19,3</td>

<td>Melt flow rate ratio for HD polyethylene composition (MI10 / MI2)</td><td> 17,7</td><td> 16,1</td><td> 14,5</td><td> 12,4</td><td> 17,9</td><td> 12,5</td>

EP 2 016 127 B1

<td>HD polyethylene composition density (g / m2³) according to ASTM, slowly cooled</td><td> 0,9548</td><td> 0,9506</td><td> 0,9591</td><td> 0,9548</td><td> 0,9546</td><td> 0,955</td>

<td>Content hexene according to C13 NMR (weight percentage)</td><td> 1,5</td><td> 2,9</td><td> 0,9</td><td> 1,3</td><td> 1,8</td><td> 1,4</td>

<td>Composition HD polyethylene (Mn)</td><td> 8125</td><td> 8920</td><td> 9310</td><td> 14500</td><td> 10500</td><td> 11700</td>

<td>Composition HD polyethylene (Mw)</td><td> 124600</td><td> 133300</td><td> 135000</td><td> 136000</td><td> 130400</td><td> 133000</td>

<td>Composition HD polyethylene (Mw / Mn)</td><td> 15,3</td><td> 14,9</td><td> 14,5</td><td> 9,4</td><td> 12,4</td><td> 11,4</td>

<td>g '</td><td> 1,007</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td>HD fraction in ATREF (%)</td><td> 70,8</td><td> 58,4</td><td> 74,1</td><td> 67,4</td><td> 55,9</td><td> 71</td>

<td>Calculated HD fraction in ATREF (%)</td><td> 36,8</td><td> 28,9</td><td> 43,3</td><td> 36,7</td><td> 27,7</td><td> 41,3</td>

<td>Elution fraction in ATREF (%)</td><td> 15,2</td><td> 21,4</td><td> 21</td><td> 27,4</td><td> 19,6</td><td> 18,3</td>

<td>SCBD fraction in ATREF (%) (27 to 86^aboutC)</td><td> 14</td><td> 20,2</td><td> 4,9</td><td> 5,2</td><td> 24,5</td><td> 10,7</td>

<td>Average Mv according to ATREF</td><td> 58100</td><td> 53800</td><td> 63000</td><td> 63400</td><td> 49400</td><td> 56700</td>

<td>SCBD for Mv according to ATREF</td><td> 58100</td><td> 56600</td><td> 68600</td><td> 68400</td><td> 51100</td><td> 60400</td>

<td>Mv washed out at ATREF</td><td> 58050</td><td> 43600</td><td> 41800</td><td> 46700</td><td> 42750</td><td> 40200</td>

EP 2 016 127 B1

<td>Viscosity at shear rate 10-2sec^-1 (Crimson)</td><td> 11580</td><td> 13700</td><td> 12900</td><td> 11200</td><td> 17000</td><td> 11200</td>

<td>Viscosity at shear rate 10 + 2 sec^-1 (Crimson)</td><td> 805</td><td> 834</td><td> 903</td><td> 918</td><td> 828</td><td> 952</td>

<td>The ratio of 102/10 + 2</td><td> 14,4</td><td> 16,4</td><td> 14,3</td><td> 12,2</td><td> 20,5</td><td> 11,8</td>

<td>Tg delta @ 10 2</td><td> 7,6</td><td> 6,98</td><td> 7,6</td><td> 8,1</td><td> 5,67</td><td> 8,51</td>

<td>Tg delta @ 10 + 2</td><td> 0,828</td><td> 0,79</td><td> 0,81</td><td> 0,94</td><td> 0,76</td><td> 0,88</td>

<td>Alloy strength according to Rheotens (cN)</td><td> 2,5</td><td> 2,5</td><td> 2,5</td><td> 2,5</td><td> 3</td><td> 2,5</td>

<td>Melt strength according to Rheotens (speed in mm / s)</td><td> 212</td><td> 200</td><td> 210</td><td> 205</td><td> 170-200</td><td> 225</td>

<td>Flexural modulus (0.5 inch / min) (psi)</td><td> 218000</td><td> 187000</td><td> 243000</td><td> 217000</td><td> 221000</td><td> 236000</td>

<td>standard deviation (+/-)</td><td> 7723</td><td> 9400</td><td> 15000</td><td> 10000</td><td> 13400</td><td> 10000</td>

<td>Secant module 2% (psi)</td><td> 163000</td><td> 138000</td><td> 169000</td><td> 157000</td><td> 157000</td><td> 160000</td>

<td>standard deviation (+/-)</td><td> 3470</td><td> 5660</td><td> 3300</td><td> 6900</td><td> 1900</td><td> 4400</td>

<td>Secant module 1% (psi)</td><td> 193500</td><td> 164000</td><td> 203000</td><td> 186400</td><td> 188000</td><td> 193000</td>

<td>standard deviation (+/-)</td><td> 5246</td><td> 8570</td><td> 5700</td><td> 9550</td><td> 1500</td><td> 5250</td>

<td>Tensile properties (average thickness, mils)</td><td></td><td></td><td></td><td></td><td></td><td></td>

EP 2 016 127 B1

<td>Tensile Strength (psi)</td><td> 2600</td><td> 2500</td><td> 2550</td><td> 3250</td><td> 3050</td><td> 2650</td>

<td>standard deviation (+/-)</td><td> 307</td><td> 160</td><td> 260</td><td> 630</td><td> 440</td><td> 100</td>

<td>Elongation at break (%)</td><td> 510</td><td> 480</td><td> 720</td><td> 720</td><td> 630</td><td> 740</td>

<td>standard deviation (+/-)</td><td> 227</td><td> 145</td><td> 200</td><td> 225</td><td></td><td> 85</td>

<td>Strength at the flow point (psi)</td><td> 3535</td><td> 3048</td><td> 3750</td><td> 3500</td><td> 3600</td><td> 3600</td>

<td>standard deviation (+/-)</td><td> 135</td><td> 160</td><td> 150</td><td> 140</td><td> 220</td><td> 105</td>

<td>Elongation at the yield point (%)</td><td> 3,44</td><td> 3,89</td><td> 3,58</td><td> 3,68</td><td> 3,36</td><td> 3,67</td>

<td>standard deviation (+/-)</td><td> 0,68</td><td> 0,41</td><td> 0,33</td><td> 0,41</td><td> 0,49</td><td> 0,28</td>

<td>Test Data ESCR</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 50^aboutC; Igepal 10%, 75 mils plate, 12 mil cuts (F50 hours)</td><td>F50 = 509</td><td>F0&gt; 1188</td><td>F50 = 239.9</td><td>F50 = 329.4</td><td>F0&gt; 1188</td><td>F50 = 247.1</td>

<td> 50^aboutC; Igepal 100%, shallow 75 mils, cutting 12 mils (F50 hours)</td><td>F0&gt; 2000</td><td>F0&gt; 1188</td><td>F50 = 1071</td><td>F0&gt; 1188</td><td>F0&gt; 1188</td><td>F0&gt; 1188</td>

<td>extrudable</td><td>Okay</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td>Ironing</td><td>Yes</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

EP 2 016 127 B1

<td>imposed close at speeds production</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Part dimensions</td><td>passes</td><td></td><td></td><td></td><td></td><td></td>

<td>High temperature welding test</td><td>passes</td><td></td><td></td><td></td><td></td><td></td>

<td>Test for the moment of removal</td><td>passes</td><td></td><td></td><td></td><td></td><td></td>

<td>Test for removal</td><td>passes</td><td></td><td></td><td></td><td></td><td></td>

<td>IVn</td><td> 0,364</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td>IVw</td><td> 1,347</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td>IVz</td><td> 4,708</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

Table III

<td></td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 4</td><td>Example 5</td><td>Example 6</td>

<td>Irganox 1076 (ppm)</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>

<td>Irganox 1010 (ppm)</td><td> 420</td><td> 536</td><td> 465</td><td> 486</td><td> 481</td><td> 412</td>

<td>Active Irgafos 168 (ppm)</td><td> 353</td><td> 366</td><td> 303</td><td> 360</td><td> 363</td><td> 268</td>

<td>Oxidized Irgafos 168 (ppm)</td><td> 120</td><td> 174</td><td> 114</td><td> 159</td><td> 158</td><td> 195</td>

<td>Irgafos 168 total (ppm)</td><td> 473</td><td> 540</td><td> 507</td><td> 519</td><td> 521</td><td>x463</td>

Table IV

<td></td><td>Comparative AND</td><td>Comparative B</td><td>Comparative C</td><td>Comparative D</td><td>Comparative E</td>

<td>Melt flow rate (I2) (2.16 g / 10 minutes)</td><td> 1,60</td><td> 2,74</td><td> 1,918</td><td> 1,72</td><td> 2,60</td>

<td>Melt flow rate (I5) (5.0 g / 10 minutes)</td><td> 5,65</td><td> 8,07</td><td> 6,838</td><td> 6,65</td><td> 9,28</td>

EP 2 016 127 B1

<td>Melt flow rate (I10) (10.0 g / 10 minutes)</td><td> 19,5</td><td> 19,9</td><td> 21,3</td><td> 23,8</td><td> 27,6</td>

<td>Melt flow rate (I21.6) (21.6 g / 10 minutes)</td><td> 114,2</td><td> 69,2</td><td> 91,6</td><td> 124,2</td><td> 120,8</td>

<td>Melt flow ratio (MI21 / MI2)</td><td> 71,5</td><td> 25,3</td><td> 47,8</td><td> 72,1</td><td> 46,4</td>

<td>Melt flow ratio (MI21 / MI5)</td><td> 20,2</td><td> 8,6</td><td> 13,4</td><td> 18,7</td><td> 13,0</td>

<td>Melt flow ratio (MI10 / MI2)</td><td> 12,2</td><td> 7,3</td><td> 11,1</td><td> 13,8</td><td> 10,6</td>

<td>Density (g / m2³)</td><td> 0,9547</td><td> 0,9525</td><td> 0,9538</td><td> 0,9518</td><td> 0,9547</td>

<td>Hexene content according to 13 C NMR (weight percent)</td><td></td><td> 0,7</td><td></td><td></td><td></td>

<td>Butene content according to 13 C NMR (weight percent)</td><td> 1,1</td><td></td><td> 0,7</td><td> 1,4</td><td> 1,2</td>

<td>Mn</td><td> 7140</td><td> 23240</td><td> 17000</td><td> 9900</td><td> 15200</td>

<td>^Min</td><td> 110610</td><td> 84300</td><td> 136200</td><td> 106000</td><td> 111500</td>

<td>M_in/ M0</td><td> 15,5</td><td> 3,6</td><td></td><td> 8,0 10,7</td><td> 7,3</td>

<td>g '</td><td> 0,951</td><td> 0,975</td><td> 0,841</td><td> 0,961</td><td> 0,88</td>

<td>HD fraction in ATREF (%)</td><td> 77,2</td><td> 82,1</td><td> 79,7</td><td> 67,9</td><td> 85,4</td>

<td>Elution fraction in ATREF (%)</td><td> 6,6</td><td> 12,2</td><td> 12,7</td><td> 9,2</td><td> 4,3</td>

<td>SCBD fraction in ATREF (%) (27 to 86^aboutC)</td><td> 16,2</td><td> 5,7</td><td> 7,6</td><td> 22,9</td><td> 10,3</td>

<td>Average MW according to ATREF</td><td> 57700</td><td> 61560</td><td> 64100</td><td> 55700</td><td> 53100</td>

<td>SCBD - Mv in ATREF</td><td> 58700</td><td> 62600</td><td> 65500</td><td> 54700</td><td> 53300</td>

<td>Mv washed out ATREF</td><td> 43000</td><td> 54300</td><td> 54300</td><td> 64800</td><td> 47300</td>

<td>Viscosity at a shear rate of 10-2 sec^-1 (Crimson)</td><td> 11580</td><td> 13700</td><td> 12900</td><td> 11200</td><td> 17000</td>

<td>Viscosity at fast</td><td> 805</td><td> 834</td><td> 903</td><td> 918</td><td> 828</td>

EP 2 016 127 B1

<td>10 + 2-1 shear bones sec^-1 (Crimson)</td><td></td><td></td><td></td><td></td><td></td>

<td>The ratio of 10-2 / 10 + 2</td><td> 14,4</td><td> 16,4</td><td> 14,3</td><td> 12,2</td><td> 20,5</td>

<td>Tg delta @ 10-2</td><td> 7,6</td><td> 6,98</td><td> 7,61</td><td> 8,1</td><td> 5,67</td>

<td>Tg delta @ 10 + 2</td><td> 0,828</td><td> 0,19</td><td> 0,81</td><td> 0,94</td><td> 0,76</td>

<td>Alloy strength according to Rheotens (cN)</td><td> 2,3</td><td> 1,6</td><td> 3</td><td> 2,3</td><td></td>

<td>Strength of alloy according to Rheotens (speed in mm / s)</td><td> 245</td><td> 345</td><td> 165</td><td> 153</td><td></td>

<td>Flexural modulus (0.5 inch / min) (psi)</td><td> 212700</td><td> 226600</td><td> 215900</td><td> 194500</td><td> 196900</td>

<td>Standard deviation (+/-)</td><td> 7260</td><td> 9500</td><td> 13400</td><td> 5840</td><td> 14300</td>

<td>Secant module 2% (Psi)</td><td> 158000</td><td> 159800</td><td> 158500</td><td> 150000</td><td> 150000</td>

<td>Standard deviation (+/-)</td><td> 2200</td><td> 3920</td><td> 5080</td><td> 4200</td><td> 1650</td>

<td>Secant module 1% (Psi)</td><td> 188500</td><td> 192500</td><td> 188500</td><td> 176000</td><td> 177800</td>

<td>Standard deviation (+/-)</td><td> 2470</td><td> 6000</td><td> 4280</td><td> 4200</td><td> 3700</td>

<td>Tensile properties (average thickness, mils)</td><td></td><td></td><td></td><td></td><td></td>

<td>Tensile Strength (psi)</td><td> 2380</td><td> 3525</td><td> 2730</td><td> 2590</td><td> 2450</td>

<td>Standard deviation (+/-)</td><td> 121</td><td> 770</td><td> 110</td><td> 265</td><td> 60</td>

<td>Elongation at breaking (%)</td><td> 490</td><td> 1000</td><td> 950</td><td> 840</td><td> 950</td>

<td>Standard deviation (+/-)</td><td> 200</td><td> 110</td><td> 22</td><td> 18</td><td> 20</td>

<td>Strength at the flow limit (psi)</td><td> 3410</td><td> 3550</td><td> 3590</td><td> 3243</td><td> 3350</td>

<td>Standard deviation (+/-)</td><td> 140</td><td> 40</td><td> 65</td><td> 220</td><td> 155</td>

EP 2 016 127 B1

<td>Elongation at melt flow (%)</td><td> 4,21</td><td> 3,8</td><td> 4</td><td> 3,9</td><td> 4,1</td>

<td>Standard deviation (+/-)</td><td> 0,53</td><td> 0,2</td><td> 0,28</td><td> 0,3</td><td> 0,27</td>

<td>ESCR test data</td><td></td><td></td><td></td><td></td><td></td>

<td> 50^aboutC; Igepal 10%, 75 mils tile, 12 mil cuts (F50 hours)</td><td>F50 = 394.1</td><td>F50 = 67.8</td><td>F50 = 36.3</td><td>F50 = 109.2</td><td>F50 = 42.4</td>

<td> 50^aboutC; Igepal 100%, 75 mils tile, 12 mil cuts (F50 hours)</td><td>F0 = 1007; F50 = ~ 2560</td><td>F50 = 63.5</td><td>F50 = 24.8</td><td>F50 = 836.8</td><td>F50 = 29.4</td>

<td>IVn</td><td> 0,358</td><td> 0,72</td><td> 0,585</td><td> 0,412</td><td> 0,557</td>

<td>IVw</td><td> 1,475</td><td> 1,523</td><td> 1,386</td><td> 1,473</td><td> 1,403</td>

<td>IVz</td><td> 3,557</td><td> 2,912</td><td> 2,517</td><td> 3,708</td><td> 2,607</td>