Ethylene-based polymers and compositions, methods of making the same, and articles prepared therefrom

[0001] Geomembranes are thick sheets for use in various applications, such as liquid tanks, tank covers, linings of water transport systems, liners and external coatings of waste landfills. The LLDPE geomembrane for covering external landfills must meet the requirements of the Geosynthetic Research Institute (GRI), such as tensile strength at break (MPa), elongation at break (%) and requirements for multi-axis stretching. In addition, the resin must process well, have high melt strength, preferably without mixing with other resins, and have improved performance at low cost.

[0002] International publication no. WO2006 / 067180 discloses a geomembrane, produced by flat sheet extrusion or sheet extrusion, using a bimodal resin consisting of medium density polyethylene (MDPE), with a density of 0.925 ₃ up to 0.945 g / cm³. In one embodiment, the MDPE resin is produced by chemical blending using a single metallocene catalytic system in a double loop reactor. US Patent 6,355,733 discloses a blend comprising medium density high molecular weight polyethylene (HMW, MDPE) and linear low density polyethylene (LLDPE). The blend contains from 20 wt. up to 80 wt. HMW MDPE. HMW MDPE has a density of 0.92 to 0.944₃ g / cm³, MI2 melt flow index from 0.01 to 0.5 dg / min and MFR melt flow index ratio from 50 to 300. The blend also contains 20 wt. up to 80 wt. LLDPE. LLDPE has₃ density in the range of 0.90 to 0.925 g / cm³ and MI2 in the range of 0.50 to 50 dg / min. It has been disclosed that the blend produces films with significantly increased toughness and tear strength compared to MDPE or HDPE, and with a higher modulus of elasticity compared to LLDPE.

[0004] International publication no. WO 2004/016688 discloses a polyethylene composition₃ 0.945 to 0.960 g / cm³ and a melt flow index of 0.1 to 0.4. The composition is a melt blend of the resin in the form of low density linear polyethylene and / or the resin in the form of medium low density linear polyethylene and the resin in the form of high density polyethylene.

[0005] US 6,187,432 discloses peroxide treated LLPDE material that can be used as a geomembrane liner in land areas for storing toxic waste, municipal landfills, leachate leachate pools or slurry, and other such applications in tanks for on land, as well as in applications requiring a strong non-biodegradable material that is impermeable to air and moisture.

[0006] Irrigation systems have evolved over the past 50 years from flood irrigation to the increased use of sprinklers and micro irrigation systems. The main driving force of such systems is the global focus on water resources management due to drought, increased environmental care and high daily US water demand (billions of gallons each day).

[0007] There is a need for micro irrigation systems based on economical polymers on

It is based on ethylene bases, inexpensive extra-reactor mixtures or reactor mixtures in situ and which have sufficient or improved hydrostatic and mechanical properties. Typical ISO materials used are PE 32 and PE 40, both of which are polyethylene-based materials, or PE 1404 resin according to American Standards Test Methods (ASTM).

[0008] Linear low-density polyethylene (LLDPE) is preferred for micro-tubing compared to high-density polyethylene due to the lower modulus of elasticity. Micro tubing based on LLDPE can be "pierced" for effective manipulation and repairs in the field of operation. In addition, the flexibility of LLDPE-based piping allows rolling of the piping without tangling in the entire irrigated area. However, typical LLDPE resins must be mixed with higher density polyethylenes to improve hydrostatic strength.

[0009] In US Patent US20070273066A1 discloses a multimodal linear low density polyethylene composition for producing a pressure pipe. The composition is prepared in situ and has a density of 910-940 kg / m3, an elastic modulus E in the range below 800 MPa, an abrasion resistance below 20 and a flow rate index (MFR2) below 2 g / 10 min. This product requires many reactors to produce different LMW and HWM fractions for the final multimodal composition.

[0010] US Patent 5,455,303 discloses the following polymer composition: (A) a polyolefin composition consisting essentially of (i) low density linear polyethylene and (ii) a copolymer of ethylene and / or C4-C8 α-olefin, where R is an alkyl radical having 2 to 10 carbon atoms, and (B) low density polyethylene. This composition contains a mixture of two resins, which increases the cost of the product.

[0011] International application W02005 / 097888A1 discloses a blend containing 70 to 98 percent by weight of a polyethylene resin produced using a chromium-based catalyst, based on the total weight of the blend, and from 2 to 30 percent by weight of a bimodal poly resin₃ ethylene with a density of 0.940 to 0.965 g / cm³, and with an ESCR that is at least greater than that of a resin produced using an equivalent density chromium catalyst produced using a Ziegler-Natta or metallocene catalyst system. It has been disclosed that the mix exhibits increased stress corrosion resistance and good processing characteristics, without loss of rigidity. Again, mixing increases the overall cost of the final resin.

[0012] Additional polymers, blends and / or compositions based on ethylene, and articles made therefrom, are disclosed in international publications No. WO 01/98409, WO 04/016688, WO 08/051824, WO 08/153586; US publications no. 2006/0122362, 2007/0078225, 2005/0245689, 2010/0003439; and in US Patent Nos. 5,221,570, 6,187 423 and 6,355,733.

[0013] There is a need for cheap ethylene-based polymers that are not expensive free radical treated polymers or expensive bimodal mixtures, but also with sufficient or better alloy properties and mechanical properties for applications as geomembranes. There is also a need for irrigation tubing made from cheap ethylene-based polymers, not from expensive treated polymers or expensive non-reactor mixtures or in situ mixtures with sufficient or better hydrostatic properties2

EP 2 393 852 B1 2 and mechanical for micro-irrigation applications. These needs were met by the following invention.

SUMMARY OF THE INVENTION [0014] The invention provides an ethylene-based interpolymer with the following characteristics:

₃

a) a density of 0.910 to 0.930 g / cm³, measured in accordance with ASTM D-792-98, measuring method B;

b) melt flow index (I2) from 0.1 to 0.5 g / 10 min, measured in accordance with ASTM-1238-04,

2.16 kg at 190 ° C; and

c) High-density fraction on the ATREF curve of the short chain branching distribution (SCBD), eluting above 92 ° C, from more than 10 percent to less than 28 percent of the total area under the ATREF SCBD curve

d) absolute molecular weight distribution, Mw / Mn, over 11.5, determined by GPC.

[0015] The invention also provides a composition comprising an ethylene-based interpolymer with the following characteristics:

₃

a) a density of 0.919 to 0.928 g / cm³, measured in accordance with ASTM D-792-98, measuring method B;

b) melt flow index (I2) from 0.1 to 0.8 g / 10 min, measured in accordance with ASTM-1238-04,

2.16 kg at 190 ° C; and

c. high-density fraction on the ATREF curve of the short chain branching distribution (SCBD), eluting above 92 ° C, from more than 10 percent to less than 28 percent of the total area under the ATREF SCBD curve; and

d) absolute molecular weight distribution, Mw / Mn, over 11.5, determined by GPC.

[0016] The invention also provides a hollow tube containing at least one component made of a composition comprising an ethylene-based interpolymer with the following characteristics:

₃

a) a density of 0.919 to 0.928 g / cm³, measured in accordance with ASTM D-792-98, measuring method B;

b) melt flow index (I2) from 0.1 to 0.8 g / 10 min, measured in accordance with ASTM-1238-04,

2.16 kg at 190 ° C; and

c. high-density fraction on the ATREF curve of the short chain branching distribution (SCBD), eluting above 92 ° C, from more than 10 percent to less than 28 percent of the total area under the ATREF SCBD curve; and d) absolute molecular weight distribution, Mw / Mn, over 11.5, determined by GPC and₂ where the hydrostatic design base (HDB) is at least 7 MPa (1000 pounds / inch)²) at 23 ° C according to ASTM D-2837, regression method.

BRIEF DESCRIPTION OF THE DRAWINGS [0017]

Each of Figures 1-8 shows an ATREF profile of a comparative resin.

Each of Figures 9-12 shows the ATREF profile of the resin of the invention.

EP 2 393 852 B1

Each of Figures 13-14 shows an ATREF profile of a competitive resin.

Figure 15 shows the ATREF profile of a comparative resin.

Figure 16 shows the ATREF profile of a resin according to the invention.

Figure 17 shows data for "peripheral stress as a function of time to failure" of the comparison resin.

Figure 18 shows data for "peripheral stress as a function of time to failure" of the resin of the invention.

DETAILED DESCRIPTION OF THE INVENTION [0018] As discussed above, in a first aspect, the invention provides an ethylene-based interpolymer with the following characteristics:

₃

a) a density of 0.910 to 0.930 g / cm³, measured in accordance with ASTM D-792-98, measuring method B;

b) melt flow index (I2) from 0.1 to 0.5 g / 10 min, measured in accordance with ASTM-1238-04,

2.16 kg, at 190 ° C; and

c. high-density fraction on the ATREF curve of the short chain branching distribution (SCBD), eluting above 92 ° C, from more than 10 percent to less than 28 percent of the total area under the ATREF SCBD curve; and

d) absolute molecular weight distribution, Mw / Mn, over 11.5, determined by GPC.

[0019] In a second aspect, the invention also provides a composition comprising an ethylene-based interpolymer with the following characteristics:

₃

a) a density of 0.910 to 0.928 g / cm³, measured in accordance with ASTM D-792-98, measuring method B;

b) melt flow index (I2) from 0.1 to 0.8 g / 10 min, measured in accordance with ASTM-1238-04,

2.16 kg, at 190 ° C; and

c. high-density fraction on the ATREF curve of the short chain branching distribution (SCBD), eluting above 92 ° C, from more than 10 percent to less than 28 percent of the total area under the ATREF SCBD curve; and

d) absolute molecular weight distribution, Mw / Mn, over 11.5, determined by GPC.

[0020] In a third aspect, the invention provides a hollow tube containing at least one component made of a composition comprising an ethylene-based interpolymer with the following characteristics:

₃

a) a density of 0.919 to 0.928 g / cm³, measured in accordance with ASTM D-792-98, measuring method B;

b) melt flow index (I2) from 0.1 to 0.8 g / 10 min, measured in accordance with ASTM-1238-04,

2.16 kg, at 190 ° C; and

c. high-density fraction on the ATREF curve of the short chain branching distribution (SCBD), eluting above 92 ° C, from more than 10 percent to less than 28 percent of the total area under the ATREF SCBD curve; and d) absolute molecular weight distribution, Mw / Mn, over 11.5, determined by GPC, where the hydrostatic design base (HDB) for the tube is at least 7 MPa (1000 lb / in)²) at 23 ° C according to ASTM D-2837, regression method.

[0021] The total area under the ATREF SCBD curve includes the non-crystalline fraction (

The purge fraction), SCBD fraction and high density fraction.

[0022] The following embodiments apply to all aspects of the invention.

[0023] In one embodiment, the ethylene-based interpolymer is polymerized using a chromium catalyst, preferably a CrO catalyst, and more preferably a titanium and fluorine modified CrO catalyst.

[0024] In one embodiment, the high-density fraction is eluted above 92 ° C and below 150 ° C.

[0025] In one embodiment, the high-density fraction makes up over 12 percent, and preferably over 15 percent of the total area under the ATREF SCBD curve.

[0026] In one embodiment, the high-density fraction is less than or equal to 26 percent of the total area under the ATREF SCBD curve.

[0027] In one embodiment, the high-density fraction comprises from over 12 percent to less than 26 percent of the total area under the ATREF SCBD curve, and preferably from over 15 percent to less than 23 percent of the total area under the ATREF SCBD curve.

[0028] In one embodiment, the interpolymer exhibits such an SCBD profile (with respect to the high density fraction and the SCBD fraction) that it contains a high density fraction with a peak height greater than or equal (and preferably larger) than the peak height (maximum peak height) or the height of the peak at maximum intensity) of the SCBD fraction, and the profile shows clear bimodality at temperatures higher than the peak temperature of the non-crystalline fraction (eluted from about 35 ° C-30 ° C and below), and where the SCBD fraction is eluted (at lower temperatures) before the high density fraction. In this case, pronounced bimodality means that the peak height at maximum intensity of the SCBD fraction is greater than or equal to 85 percent, preferably greater than or equal to 90 percent of the peak height at maximum intensity of the high density fraction. In a further embodiment, the elution of the SCBD fraction begins at a temperature below 40 ° C, preferably below 35 ° C.

[0029] In one embodiment, the interpolymer exhibits such an SCBD profile (with respect to the high density fraction and the SCBD fraction) that it contains a high density fraction with a peak height greater than or equal (and preferably larger) than the peak height (maximum peak height) ) of the SCBD fraction, and the profile shows clear bimodality at temperatures higher than the peak temperature of the non-crystalline fraction ( purge fraction) (eluted from about 35 ° C-30 ° C and below), and where the SCBD fraction is eluted (at lower temperatures) before the high density fraction. In this case, pronounced bimodality means that the peak height at the maximum intensity of the SCBD fraction is greater than or equal to 75 percent, preferably greater than or equal to 80 percent of the peak height at the maximum intensity of the high density fraction. In a further embodiment, the elution of the SCBD fraction begins at a temperature below 40 ° C, preferably below 35 ° C.

[0030] In one embodiment, the interpolymer is characterized by an SCBD curve in which the high-density fraction has a higher peak height than the height of the SCBD fraction, and the SCBD curve shows pronounced bimodality at temperatures higher than the peak temperature of the non-crystalline fraction (from 35 ° C to 105 ° C), wherein the high-density fraction is eluting in the range of 92 ° C to 105 ° C and the SCBD fraction is eluting in the range of 80 ° C to 91 ° C. In this case, pronounced bimodality means that the relative minimum value between the high density fraction peak and the SCBD peak is greater than or equal to 90 percent of the high density fraction peak height.

[0031] In one embodiment, the interpolymer is characterized by a SCBD curve on which a large density fraction

It has a higher peak height than the peak height of the SCBD fraction, and the SCBD curve exhibits pronounced bimodality at temperatures higher than the peak temperature of the non-crystalline fraction (from 35 ° C to 105 ° C), the high-density fraction being eluted in between 92 ° C and 105 ° C, and the SCBD fraction is eluted between 80 ° C and 91 ° C. In this case, pronounced bimodality means that the relative minimum value between the high density fraction peak and the SCBD peak is greater than or equal to 80 percent of the high density fraction peak.

[0032] In one embodiment, the ethylene-based interpolymer is a linear interpolymer.

[0033] In one embodiment, the ethylene-based interpolymer is a heterogeneously branched linear interpolymer.

[0034] In one embodiment, the ethylene-based interpolymer is an ethylene / α-olefin interpolymer. In a further embodiment, the α-olefin is selected from the group consisting of C6 to C10 α-olefins. In further embodiments, the aolefin is selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, preferably 1-hexene and 1-octene, and more preferably 1-hexene.

[0035] The absolute molecular weight distribution Mw / Mn of the interpolymer is over 11.5, determined by GPC.

[0036] In one embodiment, the absolute molecular weight distribution Mw / Mn of the interpolymer is less than or equal to 20, preferably less than or equal to 15, determined by GPC.

[0037] In one embodiment, the molecular weight distribution (Mw / Mn) of the interpolymer is preferably from 12 to 15, determined by conventional GPC.

[0038] In one embodiment, the interpolymer Mw / Mn, determined by conventional GPC, is from "over 11" to 14.5.

[0039] In one embodiment, the absolute average molecular weight of Z, Mz, the interpolymer is over 640,000, and the absolute average molecular weight of Z + 1, Mz + 1 is over 3,000,000 g / mol, as determined by GPC.

[0040] In one embodiment, the absolute average molecular weight of Z, Mz, the interpolymer is over 680,000 g / mol, preferably over 720,000 g / mol, and the absolute average molecular weight Z + 1, Mz + 1, over 3,500,000 g / mol, preferably over 4,000,000 g / mol, determined by GPC.

[0041] In one embodiment, the interpolymer has an absolute Mz / Mw ratio of greater than 5.9, and an absolute Mz + 1 / Mw ratio of greater than 30, as determined by GPC.

[0042] In one embodiment, the interpolymer has an absolute Mz / Mw ratio of greater than 5.9, and an absolute Mz + 1 / Mw ratio of greater than 33, preferably greater than 35, determined by GPC.

[0043] In one embodiment, the interpolymer I21 / I2 ratio is greater than or equal to 50, preferably greater than or equal to 55, more preferably greater than or equal to 60.

[0044] In one embodiment, the interpolymer I21 / I2 ratio is greater than or equal to 70, preferably greater than or equal to 75, more preferably greater than or equal to 80.

[0045] In one embodiment, the interpolymer I21 / I2 ratio is greater than or equal to 80, preferably greater than or equal to 90, more preferably greater than or equal to 95.

[0046] In one embodiment, the interpolymer I21 / I2 ratio is less than or equal to 150, preferably less than or equal to 130, more preferably less than or equal to 120.

[0047] In one embodiment, the interpolymer I21 / I2 ratio is less than or equal to 120, preferably less than

Or equal to 110, and more preferably less than or equal to 100.

[0048] In one embodiment, the interpolymer I21 / I2 ratio is from 50 to 120, preferably from 55 to 110, and more preferably from 60 to 100.

[0049] In one embodiment, the interpolymer I21 / I2 ratio is from 80 to 150, preferably from 90 to 130, and more preferably from 95 to 120.

[0050] In one embodiment, the interpolymer I10 / I2 ratio is greater than or equal to 10, preferably greater than or equal to 15.

[0051] In one embodiment, the interpolymer I10 / I2 ratio is less than or equal to 30, preferably less than or equal to 25.

[0052] In one embodiment, the interpolymer I10 / I2 ratio is from 10 to 30, preferably from 15 to 25.

[0053] In one embodiment, the interpolymer I5 / I2 ratio is greater than or equal to 3, preferably greater than or equal to 4.

[0054] In one embodiment, the interpolymer I5 / I2 ratio is less than or equal to 10, preferably less than or equal to 7.

[0055] In one embodiment, the interpolymer I5 / I2 ratio is from 3 to 10, preferably from 4 to 7, and more preferably from 4 to 6.

[0056] In one embodiment, the interpolymer viscosity ratio (η0.01 / η100) is greater than or equal to 44, preferably greater than or equal to 50, more preferably greater than or equal to 55, and even more preferably greater than or equal to 60.

[0057] In one embodiment, the interpolymer viscosity ratio (η0.01 / η100) is from 40 to 80, preferably from 45 to 75.

[0058] In one embodiment, the flexural modulus of the interpolymer is from 420 MPa to 700 MPa (60,000 lb / in)² up to 100,000 pounds / inch²).

[0059] In one embodiment, the interpolymer viscosity ratio (η0.01 / η100) is more than 44, preferably greater than or equal to 50, more preferably greater than or equal to 55, and even more preferably 60; and its flexural modulus is from 420 MPa to 700 MPa (60,000 pounds / inch)² up to 100,000 pounds / inch²).

[0060] In one embodiment, the interpolymer tg delta (tg delta 0.01 rad / tg delta100 rad) ratio is from 2.5 to 3.2.

[0061] In one embodiment, the melting point, Tm, of the interpolymer is from 115 ° C to 130 ° C, preferably from 120 ° C to 125 ° C, determined by DSC.

[0062] In one embodiment, the crystallization temperature, Tc, interpolymer is from 105 ° C to 120 ° C, preferably from 108 ° C to 115 ° C, determined by DSC.

[0063] In one embodiment, the interpolymer has a melting heat of 140 J / g to 165 J / g, preferably 144 J / g to 165 J / g, determined by DSC.

[0064] In one embodiment, the heat of crystallization of the interpolymer is from 148 J / g to 162 J / g, preferably from 150 J / g to 162 J / g, determined by DSC.

[0065] The ethylene-based interpolymer is not produced by a modified free radical method, such as, for example, a modified peroxide method.

[0066] The ethylene-based interpolymer is not produced by in-situ mixing during the reaction of two or more polymers, and is not produced by mixing after the reactor two

Or more polymers.

[0067] The ethylene-based interpolymer is not 1) produced by a modified free radical method such as, for example, a modified peroxide method and / or is not 2) produced by in-situ mixing during the reaction of two or more polymers, and is not produced by mixing after the reactor, two or more polymers.

[0068] The interpolymer of the invention may be a combination of two or more of the forms described herein.

[0069] The invention also provides a composition comprising the interpolymer of the invention.

[0070] The composition of the invention may further comprise one or more additives. In one embodiment, the one or more additives are selected from the group consisting of photostabilizers, sterically hindered amines, hindered phenols, metal deactivators, UV absorbers, phosphites, antacids, processing aids, lubricants, anti-blocking additives, lubricating additives, antistatic additives, antimicrobial additives, chemical blowing agents, coloring agents, fillers and combinations thereof.

[0071] In one embodiment, the composition of the invention contains more than 80 percent by weight, preferably more than 90 percent by weight, and more preferably more than 95 percent by weight of an ethylene-based interpolymer, based on the total weight of the composition.

[0072] The composition of the invention may be a combination of two or more of the forms described herein.

[0073] The invention also relates to an article comprising at least one component made of the interpolymer of the invention.

[0074] The invention also relates to an article made from the interpolymer of the invention.

[0075] The invention also relates to an article made from the composition of the invention.

[0076] The invention also relates to an article comprising at least one component made of the composition of the invention.

[0077] In one embodiment, the article has a percent elongation greater than or equal to 700 percent, preferably greater than or equal to 720 percent, more preferably above 745 percent and most preferably above 770 percent, determined in accordance with ASTM D-638-03 at 23 ° C, using Type IV samples from a compression molded plate made in accordance with ASTM D-4703-00 Annexes A1-A7 and procedure C for the appropriate type of resin, based on its density according to section A1.5.6.3 of the Annex. The stretching speed was 5.08 cm (two inches) per minute.

[0078] In one embodiment, the article is a sheet. In a further embodiment, the sheet thickness is from 254 μm to 5080 μm (10 mils to 200 mils), preferably from 508 μm to 3810 μm (20 mils to 150 mils). In another embodiment, the sheet thickness is greater than or equal to 1016 μm (40 mils).

[0079] In one embodiment, the sheet exhibits a percent elongation greater than or equal to 800 percent, preferably greater than or equal to 820 percent, more preferably more than 845 percent, and most preferably more than 870 percent, both in MD and TD direction of the sheet, determined in an ASTM tensile test D6693 using sample type IV according to ASTM D-638. MD is defined as the direction of the sheet machine, a

TD is the transverse direction of the sheet, sometimes referred to as the perpendicular direction.

[0080] In one embodiment, the article is a geomembrane. In another embodiment, the geomembrane thickness is 8

EP 2 393 852 B1 bears from 508 μm to 3048 μm (20 mils to 120 mils). In another embodiment, the geomembrane thickness is greater than or equal to 1016 μm (40 mils).

[0081] In one embodiment, the geomembrane percent elongation is greater than or equal to 800 percent, preferably greater than or equal to 820 percent, more preferably more than 845 percent, and most preferably more than 870 percent, both in the MD and TD direction of the geomembrane, determined in a tensile test according to ASTM D-6693 using sample type IV according to ASTM D-638. MD is defined as the geomembrane machine direction, and TD is the transverse direction of the geomembrane, sometimes referred to as the perpendicular direction.

[0082] In one embodiment, the article is a blow molded article.

[0083] In one embodiment, the article is an injection molded article.

[0084] In one embodiment, the article is a pipe.

[0085] The article of the invention may be a combination of two or more of the forms described herein.

[0086] It has been found that linear low-density ethylene-based interpolymers, preferably made with a chromium catalyst, and with some ATREF characteristics and a certain flow rate (I2) and density, show better processability and surprisingly excellent melt strength. Such properties are achieved without having to mix such interpolymers by chemical or physical means or by crosslinking or chemical modification of such interpolymers. Such interpolymers are particularly suitable for use as geomembranes (e.g. external coatings for landfills, lining swimming pools). In addition, sheets made of the interpolymer of the present invention have excellent tensile properties, these properties being observed for interpolymers with a lower content of comonomer incorporated.

[0087] In one embodiment of the third aspect of the invention, the tube has a HDB value of 7 MPa (1000 ₂ lbs / inch²) at 23 ° C for long term hydrostatic stress (Long Term Hydrostatic Stress, LTHS) after 100,000 hours (11.42 years).

[0088] In one embodiment of the third aspect of the invention, the tube exhibits LTHS greater than or equal to 6.72 MPa (960 lb / in)²).

[0089] In one embodiment of the third aspect of the invention, the tube exhibits LTHS less than or equal to 8.4 MPa (200 lb / in)²).

[0090] In one embodiment of the third aspect of the invention, the hollow tube is selected from the group consisting of flexible tubing, pipes, hoses, inner tubes, drip irrigation tubing and micro irrigation tubing.

[0091] In one embodiment of the third aspect of the invention, the tube is a tube.

[0092] In one embodiment of the third aspect of the invention, the tube is a micro irrigation tube.

[0093] In one embodiment of the third aspect of the invention, the tube is a drip irrigation tube. [0094] In one embodiment of the third aspect of the invention, the thickness of the tubing is preferably from 76 2 μm to 1778 μm (3 mils to 70 mils), more preferably from 127 μm to 1651 μm (5 mils to 65 mils), and most preferably from 254 μm to 1524 μm (10 mils to 60 mils). In another embodiment, the tubing thickness is greater than or equal to 76.2 μm (3 mils), preferably greater than or equal to 127 μm (5 mils). [0095] The hollow pipe according to the invention may be a combination of two or more described

EP 2 393 852 B1 herein.

[0096] It has been found that tubes made of low-density linear ethylene-based interpolymers, exhibiting some ATREF characteristics, and a selected combination of melt index (I2) and density, show improved hydrostatic performance, without the need to mix these interpolymers with other polymers. Such interpolymers are preferably prepared using a chromium catalyst. Such tubes are particularly suitable for use as micro irrigation tubing.

Ethylene-based interpolymer ₃ [0097] The ethylene-based interpolymer has a density greater than or equal to 0.910 g / cm3³, preferably greater than or equal to 0.915 g / cm3³and more preferably greater than or equal to 0.918 g / cm3³ (1 cm³ = 1 cubic centimeter₃ ny). In another embodiment, the ethylene-based interpolymer has a density less than or equal to 0.930 g / cm³, preferably less than or equal to 0.928 g / cm³and more preferably less than or equal to 0.927 g / cm³. In another after₃ The ethylene-based interpolymer density is in the range from 0.910 to 0.930 g / cm³, preferably in the range from 0.915 to 0.925 g / cm³and most preferably in the range of from 0.919 to 0.923 g / cm³.

₃ [0098] In one embodiment, the ethylene-based interpolymer has a density greater than or equal to 0.919 g / cm³, Preferably greater than or equal to 0.9195 g / cm³, more preferably greater than or equal to 0.920 g / cm3³. In another after₃ ethylene-based interpolymer having a density less than or equal to 0.928 g / cm³, preferably less than or equal to 0.9275 g / cm³, more preferably less than or equal to 0.927 g / cm³.

[0099] The melt flow index I2, (190 ° C, load 2.16 kg, ASTM 1238-04), an ethylene-based interpolymer is greater than or equal to 0.10, preferably greater than or equal to 0.15, more preferably greater than or equal to 0, 17 (units - we play for 10 minutes). In another embodiment, the melt flow index I2 of the ethylene-based interpolymer is less than or equal to 0.5, preferably less than or equal to 0.45, more preferably less than or equal to 0.4. In yet another embodiment, I2 is from 0.10 to 0.5 grams per 10 minutes, preferably from 0.15 to 0.45 grams per 10 minutes, most preferably from 0.2 to 0.4 grams per 10 minutes.

[0100] In one embodiment, the melt flow index I2, (190 ° C, load 2.16 kg, ASTM 123804), an ethylene-based interpolymer is greater than or equal to 0.10, preferably greater than or equal to 0.15, more preferably greater than or equal to 0.17 (units - we play for 10 minutes). In another embodiment, the melt flow index I2 of the ethylene-based interpolymer is less than or equal to 0.80, preferably less than or equal to 0.70, more preferably less than or equal to 0.6. In yet another embodiment, I2 is from 0.10 to 0.80 grams per 10 minutes, preferably from 0.15 to 0.70 grams per 10 minutes, and most preferably from 0.17 to 0.60 grams per 10 minutes.

[0101] In one embodiment, the ethylene-based interpolymer has a density of 0.915 g / cm³ up to 0.928 g / cm³, and the melt flow index, I2, from 0.2 g / 10 min to 0.4 g / 10 min, preferably from 0.22 g / 10 min to 0.38 g / 10 min.

[0102] In one embodiment, the ethylene-based interpolymer is an ethylene / α-olefin interpolymer, and preferably an ethylene / α-olefin copolymer. In a further embodiment, the α-olefin is C6-C20 α-olefin, preferably C6-C10 α-olefin, and more preferably C6-C8 α-olefin. Preferred α-olefins include 1-hexene. 1-heptene, 1-octene, 1-nene and 1-decene. Particularly preferred α-olefins include 1-hexene and 1-octene, and most preferably 1-hexene. Preferred copolymers include ethylene / hexene-1 (EH) copolymers and ethylene / octene-1 (EO) copolymers.

[0103] In a preferred embodiment, the ethylene-based interpolymer is an ethylene / 1-hexene interpolymer, and preferably an ethylene / 1-hexene copolymer. In a further embodiment, the molar percentage of 1-hexene in the ethylene / 1-hexene copolymer is from 2.0 to 3.5, preferably from 2.1 to 3.4 and most preferably from 2.2 to 3.3 based on the amount of polymerized monomers.

[0104] In a preferred embodiment, the ethylene-based interpolymer is a linear ethylene-based interpolymer, preferably a heterogeneously branched linear ethylene-based interpolymer. As used herein, the term "linear ethylene-based interpolymer," refers to an interpolymer that does not contain long chain branches or does not contain significant amounts of long chain branches, as determined by techniques known in the art, such as NMR spectroscopy (for example 1C NMR as described by Randall , Rev. Macromal. Chem. Phys., C29 (2 & 3), 1989, pp. 285-293). Some examples of long chain branched interpolymers are described in US Patent Nos. 5,272,236 and 5,278,272. As is known in the art, heterogeneously branched linear and homogeneously branched linear interpolymers contain short chain branches caused by the introduction of the comonomer into the growing polymer chain.

[0105] Heterogeneously branched interpolymers have a branching distribution in which the ratio of comonomer to ethylene in the polymer molecules is not the same. For example, heterogeneously branched LLDPE polymers typically have a branching distribution, including a highly branched portion (similar to very low density polyethylene), a medium branched portion (similar to medium branched polyethylene), and a substantially linear portion (similar to a linear polyethylene homopolymer) . Such linear interpolymers contain no long chain branching or measurable amounts of long chain branching as discussed above.

[0106] As used herein, the terms "homogeneous" and "homogeneously branched" are used to refer to an ethylene / α-olefin polymer (or interpolymer) in which the α-olefin comonomer is randomly / randomly distributed in a given polymer molecule, and all polymer particles have the same or substantially the same comonomer to ethylene ratio.

[0107] In one embodiment, the flexural modulus of the interpolymer is greater than or equal to 420

MPa (60,000 pounds / inch²) preferably greater than or equal to 441 MPa (63,000 pounds / inch²) more preferably ₂ greater than or equal to 455 MPa (65,000 pounds / inch²).

[0108] In one embodiment, the flexural modulus of the interpolymer is less than or equal to 700

MPa (100,000 pounds / inch)²), preferably less than or equal to 655 MPa (95,000 pounds / inch²) more preferably less than or equal to 630 MPa (90,000 lb / in²).

[0109] In one embodiment, the flexural modulus of the interpolymer is from 420 MPa to 700 MPa (60,000 pounds / inch² up to 100,000 pounds / inch²), preferably from 441 MP to 665 MPa (63,000 pounds / inch² up to 95,000 pounds / inch²), more preferably from 455 MPa to 630 MPa (65,000 pounds / inch.)² up to 90,000 ₂ lbs / inch²).

[0110] The ethylene-based interpolymer may comprise a combination of two or more of the forms described herein.

Catalysts [0111] In a preferred embodiment, the ethylene-based interpolymer is polymerized using a chromium catalyst. The chromium catalyst is preferably a chromium oxide catalyst, and ko11

More preferably, a fluoride-modified chromium oxide catalyst. The chromium oxide catalyst can be CrO3 or any compound that converts to CrO3 under the activation conditions employed. Compounds converting to CrO3 are disclosed in US Patent Nos. 2,822,721, 3,023,203, 3,622,251 and 4,011,382, and include chromium acetylacetonate, chromium chloride, chromium nitrate, chromium acetate, chromium sulfate, ammonium chromate, ammonium dichromate or other soluble salts containing chromium. Chromium (III) acetate is the preferred chromium compound. [0112] The chromium-based catalysts of the present invention are supported on conventional catalyst supports or supports, for example on inorganic oxide materials. Inorganic oxide materials that can be used as a carrier in catalytic compositions are porous materials with a large specific surface area, for example in the range of 50 to 1000 square meters per gram, and a typical particle size of 20 to 200 microns. Inorganic oxides include silica, alumina, thorium oxide, zirconia, aluminum phosphate and other comparable inorganic oxides, as well as mixtures of such oxides. Preferred carriers are both granulated and spray dried silica gels, especially those containing more than 70% of their pore volume in pores over 10 nm (100 angstroms). The support must have sufficient thermal stability so that the surface does not sinter at activation temperatures from 500 ° C up to 1000 ° C. Particularly preferred silica gels are manufactured by Ineos / Philadelphia Quartz and WR Grace and commercially available under various generic names. These include Davison Grade 948, 955 or 957 silica gels and Ineos EP 30X, 30XA, ES70, EP 352 and ES 370 silica gels.

[0113] Methods for depositing a chromium compound, oxidizable to Cr + 6, on a support are known in the art and can be found in previously disclosed publications. The chromium compound is usually deposited on the support from its solution and in an amount to achieve the desired levels of chromium in the catalyst after the activation step. After deposition of the compounds on the carriers and activation, a powder, loose material is obtained in the form of particles.

[0114] Activation of the supported chromium oxide catalyst can be carried out at almost any temperature up to the sintering temperature. Passing a stream of dry air or oxide through the supported catalyst during activation facilitates displacing any water from the carrier and converting, at least partially, the forms of chromium into Cr + 6. Activation temperatures from 300 ° C to 900 ° C are allowed for over one hour and up to 48 hours. Thoroughly dried air or oxygen is used and the temperature is kept below the sintering temperature of the carrier.

[0115] Fluoride sources can be added during the activation process. For example, HF or HF and SiF4 degrading compounds are used. It is known that these compounds will act by causing partial sintering of the surface of the support, especially when silica gel is used as the support. Such fluoridation causes selective contraction of the smallest pores in the gel, which leads to a narrower distribution of molecular weight and composition of the resulting polymer. This is especially important when making linear low density polymer.

[0116] Other compounds may be added to the chromium containing catalyst support. In particular, halogen-free titanium compounds are added to improve reaction conditions

EP 2 393 852 B1 on the effect of the catalyst on molecular weight. Particularly preferred compounds are hydrocarbon-soluble titanium esters, i.e. Ti (OR) 4, where R is a saturated hydrocarbon radical with 2 to 8 carbon atoms. Ethyl, isopropyl and butyl groups are particularly preferred. The titanium compound can be added directly to the fluid bed catalyst activator or, in a separate step, by mixing in a suspension the chromium catalyst support and the titanium ester in a hydrocarbon solvent followed by recovery of the reaction mixture from the solvent. When the latter method of adding titanium is used, the chromium catalyst support is preferably pre-dried to remove adsorbed water from the support. If the fluoride source is added later, the latter method of adding titanium is highly preferred.

Manufacturing chemistry - titanium treatment of chromium on silica and fluoride treatment [0117] Preferred catalysts are prepared using commercially available silica meeting the abovementioned requirements, to which chromium (III) acetate has been added as a chromium source. The silica / chromium substrate is then treated with a titanium ester. This treatment occurs on chromium on silica, pre-dried at a temperature of about 150 ° C to 200 ° C, to remove physically adsorbed water. The titanate is added as a solution to a suspension of silica in isopentane as a solvent. The suspension is dried and then activated in air at a temperature up to 1000 ° C. During activation, titanium transforms on the surface to oxide. Chromium acetate (3) is also converted to Cr + 6 oxide. When a fluorinating agent is used as the surface modifier, (NH4) 2SiF6 is particularly preferred because of its ease of handling and thermostability. Such compounds are a safe alternative to very dangerous HF, which can also be used as a catalyst modifier. Compound (NH4) 2SiF6 decomposes to form HF, which reacts both with the silica surface and optionally with Cr and Ti compounds.

Activation [0118] Activation occurs by calcining the titanized support in an atmosphere of air at a temperature above 800 ° C in a fluidized bed. The system is usually maintained under nitrogen until it reaches a temperature of 300 ° C to remove most of the organic components from the carrier before switching to air. The system is then heated in an air atmosphere, cooled in an air atmosphere, and finally placed in a nitrogen atmosphere. The catalyst is then ready for use.

Catalyst Residues [0119] A common methodology for determining the type of catalyst is the determination of residual metals in polymers. Those polymers that are based on Cr catalysts will contain support metals such as Si in the case of a silica support, and catalyst metals as in the present invention, simply Cr and Ti, and F. Polymers containing other residual metals or other combinations of residual metals are from other catalytic systems. For example, it is well known that residual metals from ZN catalyst systems include Ti and Mg and Al, as well as a silica support. Typical molar ratios in the ZN system include Mg / Ti molar ratios from 1 to 10 and Al / Ti ratios from 5 to 100. When Cr is absent, and when these or other metals are present in such molar ratios, such polymers are not Cr catalyzed polymers. Cza13

Alone, it is necessary to determine residual Cr forms in the range below 1 ppm.

Polymerization [0120] Various polymerization methods can be used to prepare the ethylene-based interpolymer. Preferably, gas phase polymerization is used at a pressure above atmospheric in the range of 7 kPa to 7 MPa (1 to 1000 pounds / inch)²), preferably from 340 kPa to 3.4 MPa (50 to 500 pounds / inch)²), most preferably from 700 kPa to 3.1 MPa (100 to 450 pounds / inch²) and a temperature in the range of 30 ° C to 130 ° C, preferably from 65 ° C to 115 ° C. Particularly suitable are gas phase, mixed or fluidized bed reaction systems. In olefin polymerization in a fluidized bed, polymerization is carried out in a fluidized bed reactor in which the bed of polymer particles is maintained in a fluidized state by a floating gas stream containing the reacting gas monomer.

[0121] Polymerization of olefins in a mixed bed reactor differs from gas polymerization in a fluidized bed reactor by the action of a mechanical stirrer inside the reaction zone that contributes to fluidization of the bed. When starting such a polymerization process, a bed of pre-formed polymer-like polymer particles, the production of which is desirable, is usually used. During polymerization, fresh polymer is formed as a result of catalyzed monomer polymerization and the polymer product is discharged to maintain a more or less constant bed volume. In a preferred industrial process, a fluidization grid is used to distribute the fluidizing gas to the bed, and also acts as the basis for the bed when the gas supply is shut off. The stream containing unreacted monomer is discharged continuously from the reactor, compressed, cooled, optionally partially or completely condensed as disclosed in US Patent Nos. 4,528,790 and 5,462,999 and recycled to the reactor. The product is withdrawn from the reactor and the make-up monomer is added to the recycled stream. When desired to control the system temperature, any gas inert to the catalyst and reagent compositions may also be present in the gas stream. Additionally, fluidization auxiliary material such as carbon black, silica, clay or talc may be used as disclosed in US Patent No. 4,994,534. The polymerization can be carried out in a single reactor or in two or more reactors connected in series, and is preferably carried out in a single reactor.

[0122] A gas phase polymerization reaction system, essentially as described in US Patent No. 4,376,191 and US Patent No. 5,317,036, is used to prepare ethylene / 1-hexene copolymers. The reactor used was a simple fluid bed reactor for gas phase polymerization with a nominal diameter of 35.6 cm (14 inches), 3.05 meters (10 feet), and with a cone and expanding portion to free itself from fine particles. The deposit level was usually high

2.44 to 2.74 meters (8 to 9 feet), which corresponded approximately to a bed volume of 0.23 m³ (8 feet³). The reactor operated at a production capacity large enough to reproduce / mimic the residence time observed in industrial reactors (about 2 to 2½ hours). A small amount of triethylaluminum is introduced, preferably continuously, into the reactor to prevent coatings and lumps. The triethylaluminum compound is preferably introduced as a solution in isopentane, directly into the fluidized bed. The rate of introduction of the compound was adjusted so that the weight fraction of the TEAL stream in the ethylene stream was kept above 0.1 and below 1 ppm.

[0123] The catalyst stream in the form of a dry powder is fed into the reactor using nitrogen as the carrier. The catalyst is dosed into the reactor by admission into the holes in a rotating disk that passes over the "intercepting block" (through which the catalyst falls into the carrier nitrogen stream) and into the reactor. Therefore, a "portion" is one hole in the feeder or "portions / minute." Alternative methods of dosing the catalyst may also be used, such as those described in US Patent No. 7202313.

[0124] Oxygen can also be introduced into the reactor as a polymer molecular weight regulating agent; for example, increased amounts of oxygen introduced into the reactor will result in a reduction in molecular weight. The oxygen stream is usually in the range of zero to over 500 ppb (molar), relative to the ethylene fed into the reactor. The gas composition is measured using direct gas chromatography.

Additives [0125] The composition may contain one or more additives. Suitable additional ingredients include, but are not limited to, fillers, processing aids, antacids, UV stabilizers, antioxidants, process stabilizers, metal deactivators, lubricants, anti-blocking agents, anti-static agents, antimicrobials, chemical blowing agents, coupling agents, agents nucleating agents, additives increasing the resistance to oxidation or chlorine, pigments or coloring agents and combinations thereof. A typical selected additive package may contain a phenolic or phosphite type antioxidant mixture.

Manufactured Articles [0126] The interpolymers and compositions of the present invention can be used to make a shaped article or one or more components of a shaped article. Such products can be single-layer or multi-layer products, which are usually produced by suitable known processing techniques, by applying heat, pressure or a combination thereof to obtain the desired product. Suitable processing techniques include, for example, blow molding, coextrusion blow molding, injection molding, stretch blow molding, compression molding, extrusion, pultrusion, calendering and thermoforming. The shaped articles provided by the invention include, for example, films, geomembranes, blown products, injection molded products, compression molded products, drip irrigation tapes, coatings, fibers, pipes, piping, profiles and moldings.

[0127] The compositions of the invention can be used to prepare geomembranes, which are essentially impermeable synthetic sheets used to accumulate liquids, gases and / or solid components. Geomembranes are used to transport water, hold water, cover water and protect water from hazardous materials. Geomembranes are also used as a hydraulic barrier in purification processes and as a gas barrier. In particular, geomembranes are used to collect water for agricultural use, and / or to separate contaminants from a source of clean water. A geomembrane can be made by sealing, by heat or other means, films or sheets (for example, made of compositions containing olefin-based polymers) along one or more overlapping seams to form a long, wide sheet with joined overlaps. A geomembrane can also be 15

It can also be made of polymer sheets welded to each other at the place of final use, for example on a piece of arable field. Geomembranes can be used to cover landfills to isolate pollution. Films and sheets, smooth or textured, may contain multiple layers of coextruded polymer compositions. Olefin-based polymers can be coextruded with polar polymers such as polyamides, ethylene / vinyl alcohol and polyesters. The geomembrane according to the invention can be combined with other films, sheets, fabrics or nonwovens in lamination and / or coextrusion processes.

Piping [0128] Examples of hollow tubes include, but are not limited to, flexible piping, pipes, hoses, internal tubes, drip irrigation piping, and micro irrigation piping. The invention is particularly suitable for the production of pressure tubes, such as irrigation tubes, in particular drip irrigation tubes and micro irrigation tubes. Hollow tubes may take a variety of shapes and sizes and are typically used as means of holding and / or transmitting and / or releasing fluids and / or gases.

[0129] Micro irrigation and irrigation piping is used for water management in greenhouses, landscaping, other lawn applications or in resistant row crops such as nut trees or even vineyards. Piping is the main element of the device, which is mainly used in 'branches' in distribution systems. Piping also referred to as 'thick-walled hose' is usually made of black LLDPE, with a thickness of 889 μm - 1016 μm (35 - 40 mils), however it may vary depending on the user's requirements. Piping diameter is usually from 0.635 cm to 1.59 cm (1/4 inch to 5/8 inch), but may be larger or smaller depending on the irrigation mode,

DEFINITIONS [0130] The term "polymer" as used herein means, for example, a homopolymer, copolymer or terpolymer. The term "polymer" as used herein also includes interpolymers, such as those made by copolymerization of ethylene with α-olefin.

[0131] The term "interpolymer" as used herein refers to polymers prepared by polymerization of at least two different types of monomers. Accordingly, the generic term interpolymer includes a copolymer (referring to polymers made from two different types of monomers) and polymers made from more than two different types of monomers.

[0132] As used herein, the term "ethylene-based interpolymer" refers to an interpolymer containing at least a predominant weight percentage of polymerized ethylene (based on the weight of the interpolymer) and one or more additional comonomers.

[0133] The term "ethylene / α-olefin interpolymer," as used herein, refers to an interpolymer containing at least a predominant weight percentage of polymerized ethylene (based on the weight of the interpolymer), α-olefin, and optionally one or more additional comonomers.

[0134] The term "ethylene / α-olefin copolymer" as used herein refers to a copolymer containing at least a predominant weight percentage of polymerized ethylene (based on the weight of interpolymer) and α-olefin as the only two types of monomers.

[0135] The term "in-situ reaction mixing" as used herein refers to mixing two or more

And the number of polymers by polymerizing at least one polymer in the presence of at least one other polymer.

[0136] As used herein, "post-reactor mixing" refers to the mixing of two or more polymers, each of which has been polymerized in a separate reactor.

[0137] The terms "comprising", "including", "having" and derivatives thereof are not intended to exclude the presence of any other component, step or procedure, regardless of how specifically disclosed. For the avoidance of doubt, all compositions claimed using the term "comprising" may include an additional additive, excipient or component, both polymeric and other, unless otherwise stated. In contrast, the term "comprising essentially" excludes from the scope of any subsequent term any other ingredient, step or procedure except those that are not critical to the action. The term "consisting of" excludes any ingredient, step or procedure that is not specifically designated or listed.

TEST METHODS

Plate production [0138] The plates were made in accordance with ASTM D-4703-00, Annexes A1 - A7 and procedure C for the appropriate type of resin, based on its density according to section A1.5.6.3 of the Annex.

Density [0139] Density was measured according to ASTM D-792-98, test method B. Plates were made according to ASTM D-4703-00, Annexes A1 - A7 and procedure C.

Melt flow rate [0140] ASTM - 1238-04 was used to measure the flow rates of MI2 (2.16 kg), MI10 (10.0 kg), MI21 (21.6 kg) at 190 ° C.

Bending properties [0141] ASTM D790-03, Procedure B, was used to measure the modulus of elasticity when bending the resin at a rate of 0.127 cm (0.05 inch) per minute. "Compressed press samples were made in accordance with ASTM D-4703 -00 as described above.

Sheets [0142] The resin of the invention can be extruded into sheets using standard sheet fabrication, pouring and blowing techniques. As with any production method, the resin is fed in the form of solid pellets at the feed end of the extruder. The resin is then melted, compressed and finally dosed through the screw and then introduced as the molten polymer through the nozzle head. Different temperature profiles can be used to facilitate this process.

[0143] The resins of the invention can be extruded into poured and blown sheets on production lines on an experimental scale, at typical boring temperatures used in industry. Typical screw diameters are 6.35 to 8.89 cm (2.5 to 3.5 inches) for blown sheet and 2.54 cm to 6.35 cm (1 to 2.5 inches) for cast sheet. Typical ratios of "screw length" to "screw diameter" range from 24: 1 to 30: 1. The appropriate nozzle gap is selected to achieve a sheet thickness of 1.016 cm (40 mils) or above. Ana17

DSC lysis of the resins according to the invention shows that the melting point (Tm) range is about 121122 ° C. This is in line with expectations for the Tm range for LLDPE. In addition, all resins of the invention showed sufficient melt strength for the experimental lines to produce both cast and blown sheets. There are two main industrial methods for producing sheets by extrusion: through a round die (blown films) and by extrusion with pouring. The production line capacity is usually over 317.5 kg / h (700 lb / h) and the sheet thickness is from 254 μm to 5080 μm (10 mils to 200 mils).

[0144] An example of extrusion through a round nozzle includes an industrial packaging line with a Battenfeld Gloucester extruder in which the screw diameter is, for example, from 10.16 to 25.4 cm (4 to 10 inches) and the ratio of "screw length" to "screw diameter, "or L / D, can be 24/1, 36: 1 or 30: 1. The nozzle is usually a round, non-rotating head with a diameter in the range of 1.8 meters to 4.6 meters (6 feet to 15 feet), with a flattening element up to 7 meters (23 feet). The device should also include an air ring, bladder housing, primary gripping roller and winder.

[0145] A pouring extrusion line, such as Killion, should include a flat head (as opposed to a round nozzle), extruding a flat sheet up to 7 meters (23 feet) wide, cooling rollers downstream of the nozzle, and no air ring. Snails with dimensions similar to those above may be used.

Tensile properties of the sheets [0146] ASTM D-6693 was used to measure the tensile properties of the sheets. Each sheet was tested at 23 ° C and 50% relative humidity (RH), without any additional conditioning. The stretching speed required by ASTM D-6693 was 5.08 cm (two inches) per minute.

Tensile Molded Plate Properties [0147] ASTM D-638-03 was used to measure tensile molded plate properties. Type IV "dog bone" bars were cut from molded plates in accordance with ASTM D-63803. The required stretching speed was 5.08 cm (two inches) per minute (2-inches / min). Plates were made in accordance with ASTM D-4703-00, annexes A1 - A7 and procedure C.

Sheet thickness [0148] ASTM D-5199 was used to measure sheet thickness.

Sheet's puncture resistance [0149] ASTM D-4833 was used to measure sheet's puncture resistance.

Sheet tear strength [0150] ASTM D-1004 was used to measure the sheet tear strength in MD (machine direction) and CD (transverse direction) or TD (perpendicular direction).

Soot Percent [0151] The modified ASTM D-1603 standard was used to measure the percentage of soot in samples. The study was modified to include the use of a muffle furnace according to ASTM D-4218.

Differential Scanning Calorimetry (DSC) - DSC calibration and sample analysis

[0152] Calibration of the DSC Q1000 baseline / baseline (TA Instruments) was performed using the calibration guide with the software supplied with this instrument. The baseline was first determined by heating the cell from -80 ° C to 280 ° C, without any sample in the aluminum DSC pan. Then sapphire patterns were used according to the instructions in the guide. A fresh sample of about 1-2 mg indium was then analyzed by heating the sample to 180 ° C, cooling the sample to 120 ° C at a cooling rate of 10 ° C / min, then maintaining the sample under isothermal conditions at 120 ° C for one minute, followed by the sample was heated from 120 ° C to 180 ° C with a heating rate of 10 ° C / min. The heat of fusion and the onset of melting of the indium sample were determined and it was checked whether the result differs by no more than "0.5 ° C" from "156.6 ° C" in relation to the onset of melting and not more than "0.5 J / g "from" 28.71 J / g "in relation to the heat of melting. Then deionized water was analyzed by cooling a small drop of deionized water in a DSC pan from 25 ° C to 30 ° C, with a cooling rate of 10 ° C / min. The sample was kept isothermal at -30 ° C for two minutes and heated to 30 ° C at a heating rate of 10 ° C / min. The onset of melting was determined and checked if it differs by no more than "0.5 ° C" from "0 ° C."

[0153] Polymer samples (pellets) were pressed into a thin film at 177 ° C (350 ° F) (approximately ₂

10.5 MPa (1500 lb / in²) for 10 seconds, ambient atmosphere) and allowed to cool to room temperature. About 5 to 8 mg of foil was weighed and placed in a DSC cup. The lid was crimped on the pan to ensure a closed atmosphere. The sample pan was placed in the DSC cell and then heated at a high rate of about 100 ° C / min to a temperature about 30 ° C higher than the melting point of the polymer. The sample was held at this temperature for about three minutes. The sample was then cooled at 10 ° C / min to -40 ° C and kept isothermal at this temperature for three minutes (first cooling). The sample was consistently heated at a rate of 10 ° C / min until complete melting (second heating). The enthalpy curves obtained were analyzed. The crystallization temperature and melting point and the corresponding melting heat were determined from the first cooling profile and the second heating profile, respectively.

Gel Chromatography (GPC) [0154] The molecular weight of the polymer was characterized using high temperature three-dimensional gel permeation chromatography (3D-GPC). The chromatographic system included a high-temperature (150 ° C) Waters chromatograph (Milford, MA), equipped with a dual-angle laser light scattering detector Precision Detectors (Amherst, MA), Model 2040 and a 4-capillary detector in the form of a differential viscometer, Model 150R, from Viscotek ( Houston, TX). The "15 ° angle" scattered light detector was used for calculation purposes. The concentration was measured with an infrared detector (IR4) from PolymerChar (Valencia, Spain).

[0155] Data collection was performed using Viscotek TriSEC software version 3 and 4-channel Viscotek Data Manager DM400. 1,2,4-trichlorobenzene (TCB) was used as the carrier solvent. The system was equipped with an in-line solvent degassing device from Polymer Laboratories. The carousel compartment and column compartment operated at 150 ° C. Four columns "Polymer Laboratories Mixed-A 30 cm, 20 μm (microns)" were used as columns. Polymer solutions of reference samples and samples of the invention were prepared in TCB. Sample solutions were prepared at a concentration of "0.1 gram polymer in 50 ml solvent." Solvent

The chromatographic (TCB) and sample preparation solvent (TCB) contained 200 ppm of butylated hydroxytoluene (BHT). Both solvent sources were sparged with nitrogen. Polyethylene samples were mixed gently at 160 ° C for four hours. The injection volume was 200 μl and the flow rate was 1.0 ml / minute.

[0156] A preferred set of columns included a "20 μm (micron)" and "mixed" porosity gel to accurately separate the highest molecular weight fractions as required. The GPC column set calibration was performed using 21 polystyrene standards with a narrow molecular weight distribution. The molecular weight range was from 580 to 8,400,000 g / mol and the standards were prepared as six mixtures, "cocktails", with at least a decade of separation between the individual molecular weights.

[0157] Peaks of the molecular weight of the polystyrene standard were converted to the molecular weights of polyethylene using the following equation (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

_B

Mpolythene = A x (polystyrene)^B (1), where M is the molecular weight, A has a quoted value of 0.4316 and B is 1.0.

[0158] Instead of the quoted value "A", the value "q" (or "factor q") was used, where it was experimentally determined that this value "q" is about 0.39 (Equation 1 above). The best estimate of "q" was determined using a predetermined weight average molecular weight of a linear spread polyethylene homopolymer (Mw ~ 115,000 g / mol, Mw / Mn ~ 3.0). This weight average molecular weight obtained in a manner consistent with Zimma (Zimm, BH, J.Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, pp. 113-136, Oxford, NY (1987)). The response factor, KLS, of the laser detector was determined using the certified value of weight average molecular weight NIST 1475 (52,000 g / mol). The method of determining "factor q" is described in more detail below.

[0159] First order polynomials were used to match the corresponding equivalent polyethylene calibration points obtained from Equation 1 to the elution volumes observed for them. Real polynomial matching was achieved to relate the logarithm of the equivalent molecular weight of polyethylene to the observed elution volumes (and associated exponents) for each polystyrene standard.

[0160] The total number of GPC column shelves was determined using EICOSANE (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). The number of shelves and symmetry were measured for the injected volume of 200 microliters, according to the following equations:

₂

Number of shelves = 5.54 * (RY at maximum peak / (peak width in ½ height))² (2) where RV is the retention volume in milliliters and the peak width is in milliliters.

Symmetry = (back peak width at 1/10 height - RV at maximum peak) / (RV at peak maximum - front width at 1/10 height (3) where RV is the retention volume in milliliters and the peak width is in milliliters.

[0161] The number of shelves for the chromatographic system (based on EICOSANE as outlined above) should be over 22,000 and the symmetry should be between 1.00 and 1.12.

[0162] The systematic approach to determining the offset of each detector was determined in a manner consistent with the publication of Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chap. 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chap. 13, (1992)), using data obtained for three detectors during linear analysis polyethylene homopolymer with a wide spread (115,000 g / mol) and narrow polystyrene standards. A systematic approach was used to optimize the offset of each detector in order to obtain molecular weight results as close as possible to those observed using a conventional GPC method. The total concentration of the injected portion used to determine the molecular weight and intrinsic viscosity was obtained from the sample surface in the infrared spectrum and calibration of the infrared detector (or mass constant) for a 115,000 g / mol linear polyethylene homopolymer. Chromatographic concentrations were assumed low enough to eliminate addressing of the effects of the second virial coefficient (concentration effects on molecular weight).

[0163] Calculations of Mn, Mw, Mz and Mz + 1 based on GPC results using an IR4 detector and calibration with narrow standards were performed using the following equations:

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(4), (5), (6), (7).

Μ W = -: Σ '* _ Σ ^ *^Μπ.ι)

Μζ = -, _ and (^iR7Mr_EJ)

Mz + 1 = -Σ (^ * Μ '·_Ε/ [0164] Where IR and MPE, i are the IR baseline corrected baseline and conventionally calibrated polyethylene molecular weight for the i-th IR response segment, a set of paired elution volume data. Equations 4, 5, 6 and 7 are used for calculations for polymers prepared in solutions in TCB.

[0165] The "factor q" described above was determined by matching "q" or A in Equation 1, until Mw, the weight average molecular weight calculated using Equation 5 and the corresponding retention volume polynomial, matched the independently determined Mw value obtained according to the Zimm method for a broad polyethylene linear homopolymer (115,000 g / mol). [0166] The weight percentage of polymer fraction with a molecular weight&gt; 10⁶ g / mol was calculated by adding the IR response with the corrected baseline, IRi, for the elution volumes of the segments for which the calibrated molecular weights, MPE, and, were above 10⁶ g / mol and expressing this partial sum as a fraction of the sum of all IR responses with the corrected baseline for the volume

EP 2 393 852 B1 elutes all segments. A similar method was used to calculate the weight percent of the polymer fraction with an absolute molecular weight&gt; 10⁶ and 10⁷ g / mol. The absolute molecular weight was calculated using a 15 ° laser light scatter signal and a concentration IR detector, MPE, I, abs = KLS * (LSi) / (IRi), using the same KLS calibration constant as in Equation 8. Set of paired data The i-th segment, IR response and LS response were set using a fixed offset, as discussed in the Systematic Approach.

[0167] In addition to the above calculations, a set of variant values ​​of Mw, Mz and Mz + 1 [Mn (abs), Mw (abs), Mz (abs) and Mz + 1 (abs)] was also calculated by the method proposed by Yau and Gillespie (Yau and Giliespie, Polymer, 42, 8947-8958 (2001)) and were determined from the following equation:

I _ Σ (^) £ (// ¾ / ^,) (8), _ Żfo)

Mw {abs) = K, J-where KLS = LS-MW calibration constant. As explained previously, the response factor, KLS, laser detector was determined using a certified weight average molecular weight value of NIST 1475 (52,000 g / mol).

And _ ^ [IR ^ LSJIRfl

Mz (abs) -Ku * -. // ^,)] (10).

and _ £ [//?; * (/ Ą // V]

Mz +1 (α / w) = K._at * -η, · ^ [IR.ĄLSJIRf}. (. 1.1), where LSi is an LS signal at an angle of 15 degrees, and the LS detector aligns as described previously.

[0168] To monitor deviations over time that may include the elution related component (caused by chromatographic changes) and the flow related component (caused by changes in the pump), the late narrow elution peak is typically used as the "flow rate marker peak . " Therefore, the flow rate marker was determined based on the flow marker in the form of decane dissolved in the eluted sample prepared in TCB. This flow rate marker was used to linearly correct the flow rate of all samples by equating to decane peaks.

Dynamic mechanical spectroscopy (DMS) [0169] Resins were compression molded into discs "thickness 3 mm x diameter 25 mm" at 117 ° C (350 ° F) for 5 minutes at 10.5 MPa (1500 lb / in)²) outdoors. The sample was then removed from the press and placed on the counter to cool.

[0170] Melt rheology, with frequency sweeping at a constant temperature, was performed with use

EP 2 393 852 B1 of the "Advanced Rheometric Expansion System (ARES)" system from TA Instruments, equipped with parallel circular plates "25 mm thick", with nitrogen purge. The sample was placed on the plate and allowed to melt for five minutes at 190 ° C. The plates were then closed with a "2 mm gap" and the sample diameter was cut to roughly match the diameter of the plates, after which the test was started. The method includes a built-in additional five minutes delay to allow temperature equalization. The experiment was conducted at 190 ° C in the frequency range 0.01 to 100 rad / s. The strain amplitude was constant at 10%. The response in the form of stress was analyzed in terms of amplitude and phase, and the module's real component (G '), the imaginary component of the module (G "), dynamic viscosity η * and tangent (δ) were calculated.

Melt strength [0171] Melt strength was determined using a Gottfert Rheotens 71.97 instrument (an independent alloy taking the alloy from a rheometer located in front of this unit). A sample (usually pellets in the amount of about 20-25 grams) was introduced into a rheometer (Gottfert Rheotester 2000) in which the sample melted (190 ° C) and the melt was introduced into a Gottfert Rheotens 71.97 apparatus, as discussed above. The rheometer operated at 190 ° C, unless otherwise stated, and was equipped with a 12 mm cylinder and a flat inlet nozzle (L = 30 mm and ID = 2 mm) and a piston moving at a speed of 0.265 mm / s. The Gottfert Rheotens 71.97 apparatus had an air gap - the distance from the nozzle outlet to the take-up wheels, which was set to 100 mm, and the wheel acceleration was 2.4₂ mm / s².

[0172] Rheotens values ​​of the alloy strength, given in centinewtons (cN), correspond to the force exerted by the wheels at the maximum speed, that is, immediately before the sample break.

Analytical temperature elution fractionation (ATREF) [0173] Each of the granulated comparative samples (C4 V1-9) and the samples according to the invention (C6 XGMB A, CE) and pelletized competitive samples (MARLEX resins) were characterized by ATREF. Samples of the invention and comparative samples were mixed without conventional additives, in typical amounts, to meet the stabilization requirements when used as geomembranes, while competitive resins contained typical amounts of antioxidants. Typical amounts of additives in competitive resins do not affect the appropriate ATREF profiles. Each of the pelletized comparative sample (NT resin) and the inventive sample (0.3 LLDPE resin) was characterized by the ATREF method. ATREF meaning "Analytical elution fraction with increasing temperature" is described, for example, in Hazlitt, J. Appl. Polym. Sci .: Appl. Poly. Symp., 45, 25-37 (1990), a publication which is entirely incorporated herein by reference. See also Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982). See also US Patent 4,798,811 (Hazlitt et al.) And US Patent 5,089,321 (Chum et al.).

[0174] The heating rate was 1 ° C / min. An IR detector from PolymerChar (Spain) was used as a concentration detector. The oven temperature was calibrated using NIST 1475a linear polyethylene. The NIST 1475a linear polyethylene used for calibration has an ATREF peak temperature of 102.0 ° C. [0175] The process controlling analyzer in the form of a gas chromatograph (GC) was used as the basis for design and operation, as a computer-controlled as a phenomena sequencer and a multiple GC furnace programmer. The basic components of the GC analyzer included two large, isothermal

EP 2 393 852 B1 (135 ° C) forced air ovens and four smaller programmable GC ovens with forced air circulation. A "5-ml" sample loop consisting of stainless steel tubing with a large internal diameter (ID) of 0.16 cm (1/16 ") was used as a transient collector of freshly injected polymer solution. The syringe pump kit (5 ml syringe barrel and air cylinder to drive the piston) provided the vacuum necessary to move the polymer solution into the sample loop. Polymer solutions were introduced into the system through a carousel sample assembly. In each GC programmable furnace there was a small ATREF column made of 0.32 cm (1/8 ") thin-walled stainless steel tubing filled with stainless steel shot (for example, 0.058 cm χ 0.058 cm (0.023" 0 0.023 cm stainless steel shot) ") from Pellets Inc. The total intergranular volume of the column was 1.5 ml. The LC pump was used to move the solvent, 1,2,4-trichlorobenzene (TCB) through the system. The polymer was dissolved in TCB at a concentration of about 0.1 to 0.4% by weight; the concentration is adjusted to match the sharpness and intensity of the eluted peaks. The polymer solutions were placed in 15 ml vials with caps with openings fitted with TEFLON partitions and then placed on the carousel. The polymer solution (5 ml) was injected into the column (excess solution washed away from the system) and the polymer crystallized on steel grit in an ATREF column (for example, by lowering the column temperature from 122 ° C to 106 ° C at a rate of ~ 10C / min, and then from 106 ° C to 20 ° C at a rate of ~ 0.1 ° C / min). Fresh solvent was then injected into the column, increasing the temperature from 20 ° C to 120 ° C at a rate of 1 ° C / minute. After leaving the column, the solvent was passed through an IR detector for mass determination. See Hazlitt, J. Appl. Polym. Sci .: Appl. Poly. Symp., 45, 25-37 (1990).

[0176] The ATREF curve is also often referred to as the short chain branching (SCBD) curve because it indicates how the comonomer (for example, 1-hexene) is distributed in the sample because as the elution temperature decreases, the comonomer content increases. The IR detector provides data on polymer concentration as a function of temperature, which can be used to generate a short chain branching distribution curve. The generated curve representing data obtained from the IR detector is known as the ATREF overlay profile.

[0177] The ATREF profile has three distinct features: the non-crystalline fraction, the SCBD fraction and the high-density (HD) fraction. The non-crystalline fraction is usually eluted at a temperature (at which the maximum peak intensity is observed) 35 ° C or lower, the HD fraction is eluted in a temperature range above the elution temperature range of the SCBD fraction, and the SCBD fraction is eluted in a temperature range between the other two fractions.

SCBD fraction calculation:

[0178] As discussed, the ATREF SCBD curve contains three fractions: high density fraction, non-crystalline fraction and SCBD fraction. The ATREF report provides calculated values ​​for% high density fraction and% non-crystalline fraction. The percentage of SCBD fraction (SCBDf%) is calculated as "100% minus the sum of% HD fraction (HDf%) and% non-crystalline fraction Fniekr%)." See Equation (i) below.

SCBDf% = 100 - (HDf% + Fniekr%) (i) [0179] For example, for the comparative example "C4 V1," the content of the non-crystalline fraction is

20.6% (relative to the total ATREF profile peak area), and the high density fraction content is 4.1% (relative to the total ATREF peak area). From the above equation

(I) SCBDf% = 100 - (20.6+ 4.1) = 75.3%. See LG Hazlitt, J. Appl. Polym. Sci .: Appl. Poly. Symp., 45, 25-37 (1990).

[0180] Another example of calculation is as follows. For the comparative example "NT resin" the content of the non-crystalline fraction is 17.5% (relative to the total peak area of ​​the ATREF profile) and the high density fraction is 8.9% (relative to the total peak area of ​​the ATREF profile). From the above equation (i) SCBDf% = 100 - (8.9 + 17.5) = 73.6%.

IR based structure [0181] Following ASTM D-6264-98 was used to determine vinyl groups and trans-unsaturation per 1000 carbon atoms.

[0182] The ASTM D-2238-92 was followed to determine methyl groups per 1000 carbon atoms.

[0183] The ASTM D-3124-93 was followed to determine vinylidene unsaturation per 1000 carbon atoms.

2.54 cm (single inch) DR 11 extrusion [0184] 2.54 cm (one inch) tube samples were manufactured using a Sterling Pipe extruder which consisted of a 6.35 cm (2½ inch) screw, L / D 24: 1, vacuum chamber, cooling tank, pipe drawing machine, cutting device and winder. Extrusion conditions are given in Table 33 below. The pipe was extruded in accordance with the requirements given in Table 3 (Wall Thickness and Tolerances for DR-PR PE Plastic Piper) in ASTM D-3035-08, and the dimensions of the pipe were measured in accordance with ASTM D-2122-98.

Test of 2.54 cm hydrostatic pressure (1 inch) DR 11 pipe [0185] Time to failure at constant internal pressure of the extruded black sample pipe DR 11 was tested according to ASTM D-1598-02 on the IPT Airless System (available from the Airless System). This system consists of a 23 ° C water tank containing pipe samples, water circulation pumps and a separate system that maintains a constant water pressure at a fixed point for each pipe sample at each station. The micro-regulators automatically set individual pressures for each station. The system design automatically records the test start time and end time when the pipe breaks.

Hydrostatic Strength Regression Analysis [0186] The "time to failure" data for each pipe set was subjected to a regression analysis according to ASTM D-2837-04 (Obtaining Hydrostatic Design Basis for Thermoplastic Pipe Materials or Pressure Design Basis for Thermoplastic Pipe Products). This ASTM procedure details the regression method used to determine the hydrostatic strength of the pipe. The method is based on "stress cracking data as a function of time" and is used to determine the average long-term hydrostatic resin strength (LTHS, measured in accordance with ASTM D 2837-04), with a required intersection of 100,000 hours (11.4 years). This LTHS intersection is identified by linear regression "stress log as a function of time log."

[0187] The term "stress" refers to banding stress, which is calculated based on the internal pressure in the pipe, wall thickness and the external diameter of the pipe. The following equation describes the relationship between these parameters,

S = P (Dt) / (2 * t) (Equation ii)

EP 2 393 852 B1 where:

S = shear stress P = internal pressure in the pipe.

D = average outer diameter t = minimum wall thickness

EXPERIMENTAL PART [0188] The following examples are given to illustrate the present invention and not to limit it. Ratios, parts and percentages are by weight unless otherwise stated.

Preparation of the catalyst [0189] The catalyst was prepared according to the following multi-step procedure (see EP 0640625A2. [0190] Step 1: (Drying) - Silica containing chromium acetate (~ 0.2 weight percent Cr) with a pore volume of 70, pore size over 100 angstrom (silica grade Davison® 957, available from Grace-Davison Corporation), was fed into a fluid bed drying tank, kept under nitrogen, at ambient temperature and pressure. The tank temperature was raised to 150 ° C at a rate of 50 ° C / hour. The silica was held at 150 ° C for 4 hours, after which it was cooled to below 100 ° C for 2 to 3 hours.

[0191] Stage 2: (Titanation) —The product of Stage 1 (190 kg) was loaded into a jacketed mixing tank. For each kg of product from Stage 1, "5.4 liters" of isopentane was added to the tank while stirring and increasing the jacket temperature to 55 ° C. After reaching 55 ° C, 0.55 liters of "50 percent by weight tetraisopropyl titanate in hexane" was added for each kilogram of product from Step 1. The pressure in the tank was increased from atmospheric to 4.1 atmospheres and the contents were stirred for two hours. The jacket temperature was increased to 90-100 ° C and the pressure was reduced to 1.15 atmosphere, allowing the solvents, isopentane and hexane to evaporate. Two hours after the pressure was released, the mixture was purged from the bottom of the tank with nitrogen at 18 kg / hour for up to 24 hours.

[0192] Step 3. (Activation) - The product of step 2 was placed in an activation tank. Ammonium hexafluorosilicate (0.25 wt.% Relative to the titanized chromium-containing silica) was added, and, under good fluidization, the mixture was warmed from ambient temperature to 150 ° C at 50 ° C / hour, under nitrogen. It was then heated at 150 ° C for two hours, after which the temperature was raised from 150 ° C to 325 ° C at a rate of 50 ° C / hour under a nitrogen atmosphere. The product was held at 325 ° C for two hours under nitrogen and then for one hour under air. The temperature was raised from 325 ° C to 825 ° C at a rate of 100 ° C / h in an air atmosphere and held at 825 ° C for four hours in an air atmosphere. Then the temperature was lowered as soon as possible (which usually took 3-5 hours) to 300 ° C in an air atmosphere. At 300 ° C the air was exchanged for nitrogen and the temperature was lowered to ambient temperature as soon as possible (which usually took about 2 hours).

Polymers, compositions and sheets of the invention [0193] The polymers of the invention were polymerized in a gas phase reactor, in the presence of a fluorinated and titanized CrO catalyst, activated at 825 ° C, with a gas of suitable composition (C6 / C2 ratios and the like). For the preparation of the samples according to the invention as a comonomer

1-hexene was used, and 1-butene was used as a comonomer in the comparative samples. The granulated polymer was removed from the reactor, cooled and freed from residual hydrocarbons by blowing, so that no degradation occurred. The granulated samples were then mixed, under mild mixing conditions, with appropriate additives (primary and secondary type), taking all precautions not to introduce any long chain branching at this stage.

[0194] Cast sheets according to the invention were then extruded on cast sheets using an experimental scale production line. DSC analysis of the resins of the invention showed that the melting point (Tm) range from about 121 ° C to 122 ° C. This value matches the expected Tm range for LLDPE. In addition, the resins of the invention showed sufficient melt strength necessary for extrusion.

[0195] The tests were carried out in accordance with the above test methods using compression molded plates or extruded sheets of granular resin or pelletized resin with appropriate additives. The properties of the samples are presented in Tables 4-26.

Representative Polymerizations [0196] The fluidized bed reactor described above was used for gas phase polymerization. Reaction conditions and some properties are summarized in Tables 1, 2 and 3.

Table 1: Samples of the invention with 1-hexene

<td></td><td>C6 XGMB-A</td><td>C6 XGMB-C</td><td>C6 XGMB-D</td><td>C6 XGMB-E</td>

<td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td>wt% Cr on a carrier</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td>

<td>Reaction conditions</td><td></td><td></td><td></td><td></td>

<td>Temp. reactor ° C</td><td> 88</td><td> 87</td><td> 88,4</td><td> 86</td>

<td>Temp. at the inlet</td><td> 81,3</td><td> 79,1</td><td> 80,3</td><td> 77,3</td>

<td>₂Overpressure, MPa (pounds / inch)</td><td> 2,44 (348)</td><td> 2,44 (348)</td><td> 2,44 (348)</td><td> 2,44 (348)</td>

<td>Part of the C2. Pressure, MPa (lb / in²)</td><td> 1,748 (249,7)</td><td> 1,746 (249,4)</td><td> 1,747 (249,6)</td><td> 1,745 (249,3)</td>

<td>H2 / C2 molar ratio</td><td> 0,05</td><td> 0,05</td><td> 0,0499</td><td> 0,05</td>

<td>C6 / C2 molar ratio</td><td> 0,0295</td><td> 0,038</td><td> 0,0295</td><td> 0,035</td>

<td>Ethylene stream, pph</td><td> 62,564</td><td> 64,311</td><td> 65,433</td><td> 65,857</td>

<td>Nitrogen, mol%</td><td> 26,549</td><td> 26,239</td><td> 26,413</td><td> 26,567</td>

<td>Isopentane, mol%</td><td> 0,164</td><td> 0,183</td><td> 0,161</td><td> 0,167</td>

<td>O2 / C2</td><td> 0</td><td> 40,143</td><td> 0</td><td> 54,984</td>

<td>Production capacity, kg / h (lbs / h)</td><td> 16,2 (35,714)</td><td> 18,9 (41,758)</td><td> 19,1 (42,117)</td><td> 20,4 (45,066)</td>

EP 2 393 852 B1

<td></td><td>C6 XGMB-A</td><td>C6 XGMB-C</td><td>C6 XGMB-D</td><td>C6 XGMB-E</td>

<td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td>Bed weight, kg (pounds)</td><td> 57,0 (125,7)</td><td> 49,9 (110,1)</td><td> 56,9 (125,5)</td><td> 56,3 (124)</td>

<td>FBD (kg / m2³) ((pounds / foot³))</td><td> 281,9 (17,6)</td><td> 233,9 (14,6)</td><td> 285,1 (17,8)</td><td> 275,5 (17,2)</td>

<td>Bed height</td><td> 7,5</td><td> 7,9</td><td> 7,4</td><td> 7,5</td>

<td>₃Al flux cm / h</td><td> 135,9</td><td> 133,6</td><td> 133,5</td><td> 124,8</td>

<td>Alkyl type</td><td>0.01% TEAL</td><td>0.01% TEAL</td><td>0.01% TEAL</td><td>0.01% TEAL</td>

<td>Residence time, h</td><td> 3,52</td><td> 2,64</td><td> 2,98</td><td> 2,75</td>

<td>SGV (m / s) ((feet / s))</td><td> 0,52 (1,7)</td><td> 0,55 (1,8)</td><td> 0,52 (1,7)</td><td> 0,52 (1,7)</td>

<td>Resin properties</td><td></td><td></td><td></td><td></td>

<td>Chromium, ppmw</td><td> 0,39</td><td> 0,44</td><td> 0,52</td><td> 0,44</td>

<td>Al ppm - calculated</td><td> 0,13</td><td> 0,11</td><td> 0,11</td><td> 0,09</td>

<td>Al / Cr</td><td> 0,6246</td><td> 0,4675</td><td> 0,392</td><td> 0,4018</td>

<td>Catalyst efficiency, (kg / kg) ((lb / lb))</td><td> 2334,6 (5147)</td><td> 2078,8 (4583)</td><td> 1759,0 (3878)</td><td> 2064,3 (4551)</td>

<td>₃Bulk density (kg / m³) ((pounds / foot³))</td><td> 427,7 (26,7)</td><td> 389,3 (24,3)</td><td> 434,1 (27,1)</td><td> 435,7 (27,2)</td>

<td>APS, cm (inches)</td><td> 0,084 (0,033)</td><td> 0,089 (0,035)</td><td> 0,086 (0,034)</td><td> 0,084 (0,033)</td>

<td>Fine particles, wt. LT 120 Mesh</td><td> 0,4</td><td> 0,8</td><td> 0,3</td><td> 1,3</td>

<td>ppm TEAL in the stream</td><td> 0,55</td><td> 0,46</td><td> 0,45</td><td> 0,4</td>

Table 2: Comparative samples with 1-butene

<td></td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td></td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td>

<td>Cr, wt% on the carrier</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td>

<td>Reaction conditions</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Temp. ° C</td><td> 90,0</td><td> 90,0</td><td> 90,0</td><td> 90,0</td><td> 91 ,3</td><td> 91 ,4</td><td> 88,8</td><td> 84,6</td><td> 84,5</td>

<td>Temp. at the inlet</td><td> 85,0</td><td> 84,6</td><td> 84,1</td><td> 83,7</td><td> 84,1</td><td> 83,1</td><td> 79,3</td><td> 76,6</td><td> 76,5</td>

<td>Hypertension,</td><td> 2,44</td><td> 2,44</td><td> 2,43</td><td> 2,43</td><td> 2,43</td><td> 2,43</td><td> 2,44</td><td> 2,44</td><td> 2,44</td>

EP 2 393 852 B1

<td></td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td></td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td>

<td>MPa (pounds / inch²)</td><td> (348)</td><td> (348)</td><td> (347)</td><td> (347)</td><td> (347)</td><td> (347)</td><td> (348)</td><td> (348)</td><td> (348)</td>

<td>C2 MPa partial pressure (fun</td><td> 1,747</td><td> 1,745</td><td> 1,746</td><td> 1,745</td><td> 1,742</td><td> 1,744</td><td> 1,745</td><td> 1,746</td><td> 1,747</td>

<td>you / inch²)</td><td> (249,6)</td><td> (249,3)</td><td> (249,4)</td><td> (249,3)</td><td> (248,9)</td><td> (249,2)</td><td> (249,3)</td><td> (249,4)</td><td> (249,6)</td>

<td>H2 / C2 molar ratio Molar ratio</td><td> 0,0510</td><td> 0,0510</td><td> 0,0510</td><td> 0,0510</td><td> 0,0512</td><td> 0,0510</td><td> 0,0509</td><td> 0,0509</td><td> 0,0510</td>

<td>C4 / C2 molar ratio</td><td> 0,0824</td><td> 0,0811</td><td> 0,0810</td><td> 0,0810</td><td> 0,0770</td><td> 0,0758</td><td> 0,0737</td><td> 0,0816</td><td> 0,0852</td>

<td>Ethylene stream pph</td><td> 52,115</td><td> 51,676</td><td> 53,678</td><td> 54,669</td><td> 57,340</td><td> 57,766</td><td> 64,193</td><td> 59,093</td><td> 57,907</td>

<td>Nitrogen, mol%</td><td> 22,914</td><td> 23,323</td><td> 23,044</td><td> 22,846</td><td> 23,559</td><td> 23,567</td><td> 23,278</td><td> 22,122</td><td> 22,293</td>

<td>Isopentane, mol%</td><td> 0,036</td><td> 0,033</td><td> 0,043</td><td> 0,043</td><td> 0,066</td><td> 0,047</td><td> 0,073</td><td> 0,049</td><td> 0,055</td>

<td>O2 / C2</td><td> 19,609</td><td> 23,352</td><td> 81,808</td><td> 49,514</td><td> 23,346</td><td> 19,500</td><td> 18,757</td><td> 19,068</td><td> 11,717</td>

<td>EB production efficiency,</td><td> 13,293</td><td> 14,174</td><td> 14,624</td><td> 15,322</td><td> 17,138</td><td> 19,411</td><td> 21,508</td><td> 19,036</td><td> 19,203</td>

<td>kg / h (lbs / h)</td><td> (29,307)</td><td> (31,249)</td><td> (32,240)</td><td> (33,779)</td><td> (37,783)</td><td> (42,793)</td><td> (97,416)</td><td> (41,967)</td><td> (42,335)</td>

<td>Bed weight, kg</td><td> 65,8</td><td> 66,0</td><td> 47,6</td><td> 47,8</td><td> 52,7</td><td> 55,0</td><td> 67,1</td><td> 66,5</td><td> 66,7</td>

<td>(pounds)</td><td> (145,1)</td><td> (145,5)</td><td> (105,0)</td><td> (105,3)</td><td> (116,1)</td><td> (121,2)</td><td> (148,0)</td><td> (146,7)</td><td> (147,0)</td>

<td>FBD (kg / m2³)</td><td> 209,8</td><td> 222,7</td><td> 177,8</td><td> 184,2</td><td> 193,8</td><td> 213,1</td><td> 281,9</td><td> 283,5</td><td> 286</td>

<td>((pounds / foot))</td><td> (13,1)</td><td> (13,9)</td><td> (11,1)</td><td> (11,5)</td><td> (12,1)</td><td> (13,3)</td><td> (17,6)</td><td> (17,7)</td><td> (17,9)</td>

<td>Bed height</td><td> 11,6</td><td> 10,9</td><td> 10,0</td><td> 9,6</td><td> 10,1</td><td> 9,6</td><td> 8,8</td><td> 8,7</td><td> 8,6</td>

<td>Alky stream</td><td> 100,0</td><td> 100,0</td><td> 100,0</td><td> 100,0</td><td> 105,0</td><td> 99,0</td><td> 110,0</td><td> 100,0</td><td> 100,0</td>

<td></td><td> 0,01%</td><td> 0,01%</td><td> 0,01%</td><td> 0,01%</td><td> 0,01%</td><td> 0,01%</td><td> 0,01%</td><td> 0,01%</td><td> 0,01%</td>

<td>Alkyl type</td><td>TEAL</td><td>TEAL</td><td>TEAL</td><td>TEAL</td><td>TEAL</td><td>TEAL</td><td>TEAL</td><td>TEAL</td><td>TEAL</td>

<td>Residence time, h</td><td> 4,95</td><td> 4,66</td><td> 3,26</td><td> 3,12</td><td> 3,07</td><td> 2,83</td><td> 3,12</td><td> 3,50</td><td> 3,47</td>

<td></td><td> 0,46</td><td> 0,46</td><td> 0,49</td><td> 0,49</td><td> 0,49</td><td> 0,49</td><td> 0,49</td><td> 0,49</td><td> 0,49</td>

<td>SGV (feet / s)</td><td> (1,5)</td><td> (1,5)</td><td> (1,6)</td><td> (1,6)</td><td> (1,6)</td><td> (1,6)</td><td> (1,6)</td><td> (1,6)</td><td> (1,6)</td>

Table 3: Comparative samples with 1-Butene (continued)

<td></td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td>Sample Type</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td>

<td colspan="10">Resin properties</td>

EP 2 393 852 B1

<td></td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td>Sample Type</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td><td>Comp.</td>

<td colspan="10">Resin properties</td>

<td>Chrome ppmw</td><td> 0,29</td><td> 0,25</td><td> 0,53</td><td> 0,45</td><td> 0,32</td><td> 0,36</td><td> 0,22</td><td> 0,22</td><td> 0,27</td>

<td>Al ppm</td><td> 0,12</td><td> 0,11</td><td> 0,10</td><td> 0,10</td><td> 0,09</td><td> 0,08</td><td> 0,08</td><td> 0,08</td><td> 0,08</td>

<td>Al / Cr or Zn / Cr</td><td> 0,7505</td><td> 0,8056</td><td> 0,3725</td><td> 0,4237</td><td> 0,5584</td><td> 0,4153</td><td> 0,6733</td><td> 0,6964</td><td> 0,5484</td>

<td>Productivity, kg / kg (fun</td><td> 3129</td><td> 3582</td><td> 1708</td><td> 2036</td><td> 2858</td><td> 2554</td><td> 4129</td><td> 4158</td><td> 3303</td>

<td>you / pound)</td><td> (6898)</td><td> (7896)</td><td> (3766)</td><td> (4489)</td><td> (6301)</td><td> (5630)</td><td> (9102)</td><td> (9166)</td><td> (7282)</td>

<td rowspan="2">Bulk density, (kg / m³)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 435,7</td><td> 445,3</td><td> 378,0</td><td> 378,0</td><td> 410,1</td><td> 429,3</td><td> 467,7</td><td> 467,7</td><td> 474,2</td>

<td>((Pounds / foot³))</td><td> (27,2)</td><td> (27,8)</td><td> (23,6)</td><td> (23,61</td><td> (25,6)</td><td> (26,8)</td><td> (29,2)</td><td> (29,2)</td><td> (29,6)</td>

<td></td><td> 0,114</td><td> 0,114</td><td> 0,079</td><td> 0,089</td><td> 0,112</td><td> 0,099</td><td> 0,091</td><td> 0,099</td><td> 0,102</td>

<td>APS, cm (inches)</td><td> (0,045)</td><td> (0,045)</td><td> (0,031)</td><td> (0,035)</td><td> (0,044)</td><td> (0,039)</td><td> (0,036)</td><td> (0,039)</td><td> (0,040)</td>

<td>Fine particles, wt. LT</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>120 Mesh</td><td> 0,3</td><td> 0,3</td><td> 0,3</td><td> 0,4</td><td> 0,5</td><td> 0,3</td><td> 0,6</td><td> 0,3</td><td> 0,2</td>

<td>Power supply ppm TEAL / C 2</td><td> 0,27</td><td> 0,28</td><td> 0,27</td><td> 0,26</td><td> 0,26</td><td> 0,25</td><td> 0,25</td><td> 0,24</td><td> 0,25</td>

Table 4: Data on physical / mechanical properties

<td>Method research</td><td>Product</td><td>Requirements industrial</td><td>C6 XGMB A</td><td>C6 XGMB C</td><td>C6 XGMB D</td><td>C6 XGMB E</td>

<td></td><td></td><td></td><td>According to the invention</td><td>According to the invention</td><td>According to the invention</td><td>According to the invention</td>

<td>ASTM D792</td><td>Density (g / cm3)</td><td>0.939 max</td><td> 0,926</td><td> 0,924</td><td> 0,921</td><td> 0,919</td>

<td>ASTM D1238</td><td>I2 g / 10 min</td><td></td><td> 0,29</td><td> 0,36</td><td> 0,31</td><td> 0,25</td>

<td rowspan="4">ASTM D1238</td><td>I2 after mixing g / 10 min</td><td></td><td> 0,3</td><td> 0,340</td><td> 0,320</td><td> 0,272</td>

<td>15 g / 10 min</td><td></td><td> 1,49</td><td> 1,64</td><td> 1,47</td><td> 1,33</td>

<td>I10 g / 10 min</td><td></td><td> 5,30</td><td> 6,33</td><td> 6,00</td><td> 5,13</td>

<td>I21 g / 10 min</td><td></td><td> 30,19</td><td> 35,06</td><td> 34,25</td><td> 27,66</td>

<td></td><td>MFR (110 / I2)</td><td></td><td> 18,2</td><td> 17,4</td><td> 19,3</td><td> 20,7</td>

<td></td><td>MFR (121 / I2)</td><td> 100</td><td> 104</td><td> 97</td><td> 110</td><td> 111</td>

<td></td><td>MFR (I5 / I2)</td><td></td><td> 5,1</td><td> 4,5</td><td> 4,7</td><td> 5,4</td>

EP 2 393 852 B1

<td>Method research</td><td>Product</td><td>Requirements industrial</td><td>C6 XGMB A</td><td>C6 XGMB C</td><td>C6 XGMB D</td><td>C6 XGMB E</td>

<td></td><td></td><td></td><td>According to the invention</td><td>According to the invention</td><td>According to the invention</td><td>According to the invention</td>

<td></td><td>MFR (I21 / I5)</td><td></td><td> 20,3</td><td> 21,3</td><td> 23,3</td><td> 20,8</td>

Table 5: Rheological properties &amp; IR structure

<td>Research Method</td><td></td><td>C6 XGMB-A</td><td>C6XGMB - C</td><td>C6XGMB - D</td><td>C6 XGMB-E</td>

<td></td><td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td></td><td>Rheological properties</td><td></td><td></td><td></td><td></td>

<td></td><td>Viscosity ratio [102/10 + 2] (rad / rad)</td><td> 53</td><td> 48</td><td> 57</td><td> 65</td>

<td></td><td>Tg Delta ratio [102/10 + 2] (rad / rad)</td><td> 3,02</td><td> 3,15</td><td> 2,99</td><td> 2,86</td>

<td></td><td>IR structure</td><td></td><td></td><td></td><td></td>

<td>ASTM D6248-98</td><td>Trans / 1000 carbon atoms</td><td> 0,165</td><td> 0,174</td><td> 0,199</td><td> 0,167</td>

<td>ASTM D6248-98</td><td>Vinyls / 1000 carbon atoms</td><td> 0,883</td><td> 0,928</td><td> 0,914</td><td> 0,834</td>

<td>ASTM2238-92</td><td>Methyl / 1000 carbon atoms</td><td> 10,9</td><td> 11,4</td><td> 12,8</td><td> 14,5</td>

Table 6: DSC data

<td></td><td>C6 XGMB -A</td><td>C6 XGMB -C</td><td>C6 XGMB -D</td><td>C6 XGMB -E</td>

<td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td>Melting point (° C)</td><td> 122,4</td><td> 122,18</td><td> 121,74</td><td> 121,57</td>

<td>Heat of melting (J / g)</td><td> 155,9</td><td> 156,8</td><td> 149</td><td> 144,8</td>

<td>Crystallization temperature (° C)</td><td> 111,9</td><td> 111,95</td><td> 111,4</td><td> 111,3</td>

<td>Heat of crystallization (J / g)</td><td> 156,8</td><td> 157,9</td><td> 151,2</td><td> 151,2</td>

Table 7: ATREF &amp; GPC data

<td></td><td>XGMB-C6 A</td><td>XGMB-C6 C</td><td>XGMB-C6 D</td><td>XGMB-C6 E</td>

<td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td>ATREF results *</td><td></td><td></td><td></td><td></td>

EP 2 393 852 B1

<td></td><td>XGMB-C6 A</td><td>XGMB-C6 C</td><td>XGMB-C6 D</td><td>XGMB-C6 E</td>

<td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td>High density fraction (%)</td><td> 21,1</td><td> 18,1</td><td> 20,1</td><td> 18,1</td>

<td>Minimum Temp. (° C)</td><td> 92,6</td><td> 93,5</td><td> 94,4</td><td> 92,4</td>

<td>Non-crystalline fraction (%)</td><td> 11,3</td><td> 11,9</td><td> 0,9</td><td> 15,9</td>

<td>SCB% (calculated)</td><td> 67,6</td><td> 70</td><td> 79</td><td> 66</td>

<td>Medium Mv</td><td> 75 435</td><td> 80 408</td><td> 92 958</td><td> 70 902</td>

<td>MV SCB</td><td> 73 712</td><td> 80 311</td><td> 93 801</td><td> 76 054</td>

<td>Mv non-crystalline fraction</td><td> 88 953</td><td> 81 128</td><td> 89</td><td> 43 650</td>

<td>GPC data</td><td></td><td></td><td></td><td></td>

<td>Conventional GPC</td><td></td><td></td><td></td><td></td>

<td>Mn</td><td> 9 170</td><td> 8 890</td><td> 9 730</td><td> 9 890</td>

<td>mw</td><td> 124 430</td><td> 117 240</td><td> 127 720</td><td> 132 910</td>

<td>Mz</td><td> 865 400</td><td> 733 700</td><td> 838 800</td><td> 1 066 100</td>

<td>Mw / Mn</td><td> 13,6</td><td> 13,2</td><td> 13,1</td><td> 13,4</td>

<td>Absolute GPC</td><td></td><td></td><td></td><td></td>

<td>Mn</td><td> 9 315</td><td> 9 460</td><td> 10 784</td><td> 10 790</td>

<td>mw</td><td> 122 180</td><td> 120 300</td><td> 136 530</td><td> 135 970</td>

<td>Mw / Mn</td><td> 13,1</td><td> 12,7</td><td> 12,7</td><td> 12,6</td>

<td>Mz (BB)</td><td> 900 700</td><td> 1 053100</td><td> 1 613 400</td><td> 1 584 800</td>

<td>Mz (abs)</td><td> 760 800</td><td> 751 500</td><td> 1 180,300</td><td> 881 500</td>

<td>Mz + 1 (BB)</td><td> 4 568 100</td><td> 14 453,500</td><td> 24 555,200</td><td> 23 146 600</td>

<td>Mz (abs) / Mw (abs)</td><td> 6,2</td><td> 6,2</td><td> 8,6</td><td> 6,5</td>

<td>Mz + 1 (BB) / Mw (abs)</td><td> 37,4</td><td> 120,1</td><td> 179,9</td><td> 170,2</td>

<td>Comparative Mz / Mw</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td> 0,9</td>

<td colspan="5">* Graphic feature for each sample of the invention: pronounced bimodality on the SCBD curve, with the HD peak height greater than the SCBD peak height. Peak HD&gt; 92 ° C, &lt;105 ° C; SCBD peak&gt; 80 ° C, &lt;91 ° C.</td>

EP 2 393 852 B1

Table 8: Tensile properties of the plates

<td>Method research</td><td>Product</td><td>Industrial requirements</td><td>C6 XGMB-A</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMB-E</td>

<td></td><td>Type IV @ 5.08 cm / min (2 inches / min), sample thickness 1905 μm (75 mils)</td><td>Type IV, 5.08 cm / min (2 inches / min), sample thickness 1905 μm (75 mils)</td><td></td><td></td><td></td><td></td>

<td rowspan="4">ASTM D638</td><td>Tensile strength at break (MPa) ((lb / in²))</td><td> &gt; 26,6 (3800)</td><td> 27,4 (3911)</td><td> 28,3 (4038)</td><td> 26,5 (3789)</td><td> 26,7 (3807)</td>

<td>% elongation at break</td><td> &gt; (800%)</td><td> 780</td><td> 829</td><td> 803</td><td> 797</td>

<td>Stress at yield point (MPa) ((Lb / inch²))</td><td></td><td> 13,8 (1975)</td><td> 12,8 (1828)</td><td> 11,6 (1662)</td><td> 11,1 (1585)</td>

<td>% elongation at the yield point</td><td></td><td> 11,0</td><td> 12,0</td><td> 12,0</td><td> 13,0</td>

<td></td><td>Secant module 2% (MPa) ((lb / in²))</td><td></td><td> 297,3 (42465)</td><td> 297,5 (42494)</td><td> 240,6 (34368)</td><td> 259,1 (37007)</td>

Table 9: Tensile strength data

<td>Method research</td><td>Product</td><td>Requirements industrial</td><td>C6 XGMBA</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMBE</td>

<td></td><td></td><td></td><td>According invention</td><td>According invention</td><td>According invention</td><td>According invention</td>

<td></td><td>Stretching (Black)</td><td>Type IV, stretching speed 5.08 cm / min (2 inches / min)</td><td></td><td></td><td></td><td></td>

<td>ASTM D5199</td><td>Thickness ^ m] ((mils))</td><td></td><td> 1600 (63)</td><td> 1549 (61)</td><td> 1727 (68)</td><td> 1676 (66)</td>

<td>ASTM D1505</td><td>₃Density [g / cm³]</td><td></td><td> 0,936</td><td> 0,935</td><td> 0,933</td><td> 0,932</td>

<td>ASTM D1603</td><td>% Soot</td><td></td><td> 2,59</td><td> 2</td><td> 2,33</td><td> 2,18</td>

<td>ASTM D1238</td><td>I2 at 190 ° C / 2.16 kg (g / 10 min)</td><td></td><td> 0,32</td><td> 0,38</td><td> 0,35</td><td> 0,31</td>

<td rowspan="2">ASTM D6693</td><td>Tension at yield point, MD (ppi)</td><td></td><td> 125</td><td> 109</td><td> 121</td><td> 108</td>

<td>Tension at yield stress, MD (MPa) ((fun</td><td></td><td> 13,9 (1984)</td><td> 12,5 (1787)</td><td> 12,45 (1779)</td><td> 11,5 (1636)</td>

EP 2 393 852 B1

<td>Method research</td><td>Product</td><td>Requirements industrial</td><td>C6 XGMBA</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMBE</td>

<td></td><td></td><td></td><td>According invention</td><td>According invention</td><td>According invention</td><td>According invention</td>

<td></td><td>you / inch²))</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Tension at yield point, TD (ppi)</td><td></td><td> 117</td><td> 118</td><td> 115</td><td> 108</td>

<td></td><td>Tension at yield stress, TD (MPa) ((pounds / inch²))</td><td></td><td> 13,0 (1857)</td><td> 13,5 (1934)</td><td> 11,8 (1691)</td><td> 11,5 (1636)</td>

<td></td><td>Tensile strength at break, MD (ppi)</td><td></td><td> 293</td><td> 286</td><td> 316</td><td> 300</td>

<td></td><td>Tensile strength at break, MD (MPa) ((pounds / inch²))</td><td> &gt;3800</td><td> 32,6 (4651)</td><td> 32,8 (4689)</td><td> 32,5 (4647)</td><td> 31,8 (4545)</td>

<td></td><td>Tensile strength at break, TD (ppi)</td><td></td><td> 313</td><td> 293</td><td> 300</td><td> 290</td>

<td></td><td>Tensile strength at break, TD (MPa) ((pounds / inch²))</td><td> &gt;3800</td><td> 34,8 (4968)</td><td> 33,6 (4803)</td><td> 30,9 (4412)</td><td> 30,8 (4394)</td>

<td></td><td>% elongation at yield, MD</td><td></td><td> 24</td><td> 20</td><td> 22</td><td> 23</td>

<td></td><td>% elongation at yield, TD</td><td></td><td> 21</td><td> 19</td><td> 20</td><td> 19</td>

<td></td><td>% elongation at break, MD</td><td> &gt;800%</td><td> 942</td><td> 966</td><td> 1049</td><td> 1082</td>

<td></td><td>% elongation at break, TD</td><td> &gt;800%</td><td> 994</td><td> 971</td><td> 992</td><td> 994</td>

Table 10: Black sheet perforation and tear data

<td>Method research</td><td></td><td>Industrial requirements</td><td>C6 XGMBA</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMBE</td>

<td></td><td></td><td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td>ASTM D4833</td><td>Resistance to puncture [kg] ((pounds))</td><td>373.7 N (84 lb.) at 1524 μm (60 mils)</td><td> 52,2 (115)</td><td> 56,7 (125)</td><td> 51,3 (113)</td><td> 49,9 (110)</td>

<td>ASTM D1004</td><td>MD tear strength [kg]</td><td>146.8 N (33 pounds of force) at 1524 μm</td><td> 20,0 (44)</td><td> 21,3 (47)</td><td> 20,0 (44)</td><td> 20,0 (44)</td>

EP 2 393 852 B1

<td>Method research</td><td></td><td>Industrial requirements</td><td>C6 XGMBA</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMBE</td>

<td></td><td></td><td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td></td><td>((pounds of strength))</td><td>(60 mils)</td><td></td><td></td><td></td><td></td>

<td>ASTM D1004</td><td>Tear strength TD [kg] ((pounds of strength))</td><td>146.8 N (33 pounds of force) at 1524 μm (60 mils)</td><td> 20,4 (45)</td><td> 20,4 (45)</td><td> 20,4 (45)</td><td> 19,5 (43)</td>

Table 11: Data regarding the stretching of the natural sheet

<td>Method research</td><td>Product</td><td>Des. thought.</td><td>over-</td><td>C6 XGMBA</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMBE</td>

<td></td><td></td><td colspan="2"></td><td>according invention</td><td>according invention</td><td>according invention</td><td>according invention</td>

<td></td><td>Stretching (natural)</td><td colspan="2">Type IV, stretching speed 5.08 cm / min (2 inches / min)</td><td></td><td></td><td></td><td></td>

<td>ASTM D5199</td><td>Thickness ^ m] ((mils))</td><td colspan="2"></td><td> 1626 (64)</td><td> 1651 (65)</td><td> 1702 (67)</td><td> 1676 (66)</td>

<td>ASTM D1505</td><td>₃Density [g / cm³]</td><td colspan="2"></td><td> 0,925</td><td> 0,925</td><td> 0,922</td><td> 0,921</td>

<td>ASTM D1603</td><td>% Soot</td><td colspan="2"></td><td> 0,01</td><td> 0,01</td><td> 0,01</td><td> 0,01</td>

<td>ASTM D1238</td><td>I2 at 190C / 2.16 kg</td><td colspan="2"></td><td> 0,35</td><td> 0,41</td><td> 0,39</td><td> 0,32</td>

<td></td><td>Tension at yield point, MD (ppi)</td><td colspan="2"></td><td> 117</td><td> 123</td><td> 122</td><td> 108</td>

<td></td><td>Tension at yield stress, MD (MPa) ((pounds / inch²))</td><td colspan="2"></td><td> 12,8 (1828)</td><td> 13,2 (1892)</td><td> 12,8 (1821)</td><td> 11,5 (1636)</td>

<td>ASTM D6693</td><td>Tension at yield point, TD (ppi)</td><td colspan="2"></td><td> 124</td><td> 125</td><td> 120</td><td> 113</td>

<td></td><td>Tension at yield stress, TD (MPa) ((pounds / inch²))</td><td colspan="2"></td><td> 13,6 (1938)</td><td> 13,5 (1923)</td><td> 12,5 (1791)</td><td> 12,0 (1712)</td>

<td></td><td>Tensile strength at break, MD (ppi)</td><td colspan="2"></td><td> 276</td><td> 277</td><td> 285</td><td> 294</td>

<td></td><td>Stress at</td><td colspan="2"> &gt;26,6 (3800)</td><td> 30,2 (4313)</td><td> 29,8 (4262)</td><td> 29,8 (4254)</td><td> 31,2 (4455)</td>

EP 2 393 852 B1

<td>Method research</td><td>Product</td><td>Des. industry.</td><td>C6 XGMBA</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMBE</td>

<td></td><td></td><td></td><td>according invention</td><td>according invention</td><td>according invention</td><td>according invention</td>

<td></td><td>tearing, MD (MPa) ((pounds / inch²))</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Tensile strength at break, TD (ppi)</td><td></td><td> 289</td><td> 287</td><td> 303</td><td> 290</td>

<td></td><td>Tensile strength at break, TD (MPa) ((pounds / inch²))</td><td> &gt;26,6 (3800)</td><td> 31,6 (4516)</td><td> 30,9 (4415)</td><td> 31,7 (4522)</td><td> 30,8 (4394)</td>

<td></td><td>% elongation at yield, MD</td><td></td><td> 21</td><td> 23</td><td> 23</td><td> 23</td>

<td></td><td>% elongation at yield, TD</td><td></td><td> 19</td><td> 20</td><td> 22</td><td> 22</td>

<td></td><td>% elongation at break, MD</td><td></td><td> 881</td><td> 894</td><td> 925</td><td> 1041</td>

<td></td><td>% elongation at break, TD</td><td></td><td> 901</td><td> 945</td><td> 979</td><td> 1025</td>

Table 12: Data on the perforation and tearing of the natural sheet

<td>Method research</td><td>Product</td><td>Industrial requirements</td><td>C6 XGMBA</td><td>C6 XGMBC</td><td>C6 XGMBD</td><td>C6 XGMBE</td>

<td></td><td></td><td></td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td><td>according to the invention</td>

<td>ASTM D4833</td><td>Resistance to puncture [kg] (pounds)</td><td>373.7 N (84 lb) at 1524 μm (60 mils)</td><td> 55,8 (123)</td><td> 53,1 (117)</td><td> 50,4 (111)</td><td> 47,6 (105)</td>

<td>ASTM D1004</td><td>Tear resistance, MD [kg] (pounds)</td><td>146.8 N (33 pounds of force) at 1524 μm (60 mils)</td><td> 20,0 (44)</td><td> 20,4 (45)</td><td> 19,5 (43)</td><td> 20,0 (44)</td>

<td></td><td>Tear resistance, TD [kg] (pounds)</td><td>146.8 N (33 pounds of force) at 1524 μm (60 mils)</td><td> 20,9 (46)</td><td> 20,4 (45)</td><td> 20,4 (45)</td><td> 19,5 (43)</td>

Table 13: Physical properties of comparative samples

<td>Research</td><td></td><td>Industry requirement ..</td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td>ASTM D-792</td><td>Density (g / 10 min)</td><td>0.939 max</td><td> 0,920</td><td> 0,919</td><td> 0,920</td><td> 0,919</td><td> 0,919</td><td> 0,919</td><td> 0,922</td><td> 0,921</td><td> 0,921</td>

EP 2 393 852 B1

<td>Research</td><td></td><td>Industry requirement ..</td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td>ASTM D-1238</td><td>I2 g / 10 min</td><td></td><td> 0,54</td><td> 0,52</td><td> 1,07</td><td> 1,08</td><td> 0,82</td><td> 0,64</td><td> 0,26</td><td> 0,14</td><td> 0,15</td>

<td>ASTM D-1238</td><td>12 after mixing, g / 10 min</td><td></td><td> 0,53</td><td> 0,53</td><td> 1,08</td><td> 1,08</td><td> 0,82</td><td> 0,62</td><td> 0,29</td><td> 0,17</td><td> 0,20</td>

<td>ASTM D-1238</td><td>I5 g / 10 min</td><td></td><td> 2,06</td><td> 2,10</td><td> 4,08</td><td> 4,07</td><td> 3,04</td><td> 2,52</td><td> 1,23</td><td> 0,72</td><td> 0,73</td>

<td>ASTM D-1238</td><td>I10 g / 10 min</td><td></td><td> 8,51</td><td> 8,21</td><td> 15,41</td><td> 15,25</td><td> 11,62</td><td> 9,76</td><td> 5,35</td><td> 3,49</td><td> 3,61</td>

<td>ASTM D-1238</td><td>121 g / 10 min</td><td></td><td> 39,61</td><td> 39,97</td><td> 74,70</td><td> 72,59</td><td> 54,93</td><td> 48,09</td><td> 29,13</td><td> 20,91</td><td> 21,12</td>

<td></td><td>MFR I10 / I2</td><td></td><td> 16,0</td><td> 15,4</td><td> 14,3</td><td> 14,1</td><td> 14,2</td><td> 15,8</td><td> 18,4</td><td> 20,5</td><td> 18,0</td>

<td></td><td>MFR I21 / I2</td><td> 100</td><td> 74</td><td> 75</td><td> 69</td><td> 67</td><td> 67</td><td> 78</td><td> 100</td><td> 123</td><td> 106</td>

<td></td><td>MFR I5 / I2</td><td></td><td> 3,9</td><td> 3,9</td><td> 3,8</td><td> 3,8</td><td> 3,7</td><td> 4,1</td><td> 4,3</td><td> 4,2</td><td> 3,6</td>

<td></td><td>MFR I21 / I5</td><td></td><td> 19,3</td><td> 19,1</td><td> 18,3</td><td> 17,8</td><td> 18,1</td><td> 19,1</td><td> 23,6</td><td> 29,0</td><td> 29,1</td>

Table 14: Rheological properties data and IR structure of comparative samples

<td></td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td>Viscosity ratio [10-2 / 10 + 2] (rad / rad)</td><td> 36</td><td> 35</td><td> 27</td><td> 26</td><td> 27</td><td> 16</td><td> 59</td><td> 80</td><td> 82</td>

<td>Delta tg ratio [10-2 / 10 + 2] (Rad / rad)</td><td> 3,03</td><td> 3,12</td><td> 3,58</td><td> 3,63</td><td> 3,54</td><td> 2,7</td><td> 2,41</td><td> 2,45</td><td> 2,48</td>

<td>Trans / 1000 carbon atoms</td><td> 0,14</td><td> 0,12</td><td> 0,18</td><td> 0,18</td><td> 0,14</td><td> 0,14</td><td> 0,13</td><td> 0,13</td><td> 0,14</td>

<td>Vinyls / 1000 carbon atoms</td><td> 0,82</td><td> 0,82</td><td> 0,98</td><td> 0,98</td><td> 0,86</td><td> 0,87</td><td> 0,86</td><td> 0,85</td><td> 0,87</td>

<td>Methyl / 1000 carbon atoms</td><td> 20,5</td><td> 21,5</td><td> 22,2</td><td> 21,3</td><td> 20,5</td><td> 20,4</td><td> 17,1</td><td> 17</td><td> 17,7</td>

Table 15: DSC data for comparative samples

<td></td><td>C4 V 1</td><td>C4 V 2</td><td>C4 V 3</td><td>C4 V 4</td><td>C4 V 5</td><td>C4 V 6</td><td>C4 V 7</td><td>C4 V 8</td><td>C4 V 9</td>

<td>Melting point (° C)</td><td> 117,91</td><td> 117,73</td><td> 118,43</td><td> 117,87</td><td> 117,5</td><td> 118,07</td><td> 118,7</td><td> 118,87</td><td> 118,86</td>

<td>Heat of melting (J / g)</td><td> 141,1</td><td> 140,5</td><td> 143,4</td><td> 140,1</td><td> 139,8</td><td> 142,7</td><td> 147,2</td><td> 147,4</td><td> 143,7</td>

<td>Temp. crystallization (° C)</td><td> 105,79</td><td> 105,52</td><td> 106,15</td><td> 106</td><td> 105,12</td><td> 105,7</td><td> 106,76</td><td> 107,15</td><td> 106,62</td>

<td>Heat of crystallization (J / g)</td><td> 139,3</td><td> 138,5</td><td> 140</td><td> 139,4</td><td> 137</td><td> 140,6</td><td> 144</td><td> 144,7</td><td> 142,2</td>

EP 2 393 852 B1

Table 16; Data on AT REF &amp; GPC comparative samples

<img file="PL2393852T3_D0002.tif" />

EP 2 393 852 B1

<img file="PL2393852T3_D0003.tif" />

ASTM D- Elongation at the plastic border 633 6ci,% 14.5 15.1 13.5 13.2 15.5 13.8 13.1 13.23 13.39

EP 2 393 852 B1

Table 18: Physical properties of competing samples

<td>Method research</td><td>Product</td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203 *</td><td>MARLEX K203 * -2 sample</td>

<td></td><td></td><td></td><td>competitive</td><td>competitive</td><td>competitive</td>

<td>ASTM D792</td><td>Density (g / 10 min)</td><td>0.939 max</td><td> 0,918</td><td> 0,926</td><td> 0,925</td>

<td rowspan="4">ASTM D1238</td><td>I2 g / 10 min</td><td></td><td> 0,34</td><td> 0,14</td><td> 0,14</td>

<td>I5 g / 10 min</td><td></td><td> 1,16</td><td> 0,66</td><td> 0,70</td>

<td>I10 g / 10 min</td><td></td><td></td><td> 2,80</td><td> 2,80</td>

<td>I21 g / 10 min</td><td></td><td> 13,53</td><td> 14,76</td><td> 12,40</td>

<td></td><td>MFR (I10 / I2)</td><td></td><td></td><td> 19,4</td><td> 20,7</td>

<td></td><td>MFR (I21 / I2)</td><td> 100</td><td> 40</td><td> 103</td><td> 92</td>

<td></td><td>MFR (I5 / I2)</td><td></td><td> 3,4</td><td> 4,6</td><td> 5,2</td>

<td></td><td>MFR (I21 / I5)</td><td></td><td> 11,7</td><td> 22,3</td><td> 17,6</td>

Table 19: Rheological properties and IR structure of competitive samples

<td>Product</td><td>MARLEX 7104</td><td>MARLEX K203</td><td>MARLEX K203 sample</td><td> 2</td>

<td></td><td>competitive</td><td>competitive</td><td colspan="2">Competitive</td>

<td>Rheological properties</td><td></td><td></td><td colspan="2"></td>

<td>Viscosity ratio [10-2 / 10 + 2] (Rad / rad)</td><td> 22</td><td> 70</td><td colspan="2"> 73</td>

<td>Delta tg ratio [10-2 / 10 + 2) (rad / rad)</td><td> 3,8</td><td> 2,62</td><td colspan="2"> 2,52</td>

<td>IR structure</td><td></td><td></td><td colspan="2"></td>

<td>Trans / 1000 carbon atoms</td><td> 0,024</td><td> 0,055</td><td colspan="2"></td>

<td>Vinyls / 1000 carbon atoms</td><td> 0,151</td><td> 1,117</td><td colspan="2"></td>

<td>Methyl / 1000 carbon atoms</td><td> 12,8</td><td> 4,16</td><td colspan="2"></td>

Table 20: DSC data from competitive samples

<td>Product</td><td>MARLEX 7104</td><td>MARLEX K203</td><td>MARLEX K203 - 2 sample</td>

<td>Patent sample type</td><td>competitive</td><td>competitive</td><td>competitive</td>

<td>Melting point (° C)</td><td> 125,33</td><td> 123,13</td><td> 122,85</td>

<td>Heat of melting (J / g)</td><td> 127,6</td><td> 146,9</td><td> 156,4</td>

<td>Crystallization temperature (° C)</td><td> 112,42</td><td> 111,3</td><td> 111,91</td>

EP 2 393 852 B1

<td>Product</td><td>MARLEX 7104</td><td>MARLEX K203</td><td>MARLEX K203 - 2 sample</td>

<td>Patent sample type</td><td>competitive</td><td>competitive</td><td>competitive</td>

<td>Heat of crystallization (J / g)</td><td> 127,2</td><td> 144,7</td><td> 153,7</td>

Table 21: ATREF &amp; GPC data from competitive samples

<td>Product</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td>competitive</td><td>competitive</td>

<td>ATREF results</td><td></td><td></td>

<td>High density fraction (%)</td><td> 30,6</td><td> 9,8</td>

<td>Temp Min (° C)</td><td> 92,7</td><td> 94,9</td>

<td>Non-crystalline fraction (%)</td><td> 24,1</td><td> 19,1</td>

<td>SCB t (calculated)</td><td> 45,3</td><td> 71,1</td>

<td>Average Mv</td><td> 74 479</td><td> 82 597</td>

<td>Mv SCB</td><td> 76 431</td><td> 84 902</td>

<td>Mv non-crystalline fraction</td><td> 68 332</td><td> 72 835</td>

<td>Conventional GPC</td><td></td><td></td>

<td>Mn</td><td> 31 170</td><td> 8 930</td>

<td>mw</td><td> 135 730</td><td> 135 210</td>

<td>Mz</td><td> 430 400</td><td> 766 100</td>

<td>Mw / Mn</td><td> 4,4</td><td> 15,1</td>

<td>Absolute GPC</td><td></td><td></td>

<td>Mn</td><td> 33 199</td><td> 11 568</td>

<td>mw</td><td> 147 140</td><td> 127 270</td>

<td>Mw / Mn</td><td> 4,4</td><td> 11,0</td>

<td>Mz (BB)</td><td> 542 600</td><td> 514 900</td>

<td>Mz (abs)</td><td> 565 400</td><td> 514 400</td>

<td>Mz + 1 (BB)</td><td> 1 290 300</td><td> 1 173100</td>

<td>Mz (abs) / Mw (abs)</td><td> 3,8</td><td> 4,0</td>

<td>Mz + 1 (BB) / Mw (abs)</td><td> 8,8</td><td> 9,2</td>

<td>Comparative Mz / Mw</td><td> 1,0</td><td> 0,7</td>

EP 2 393 852 B1

Table 22: Tensile data of competing molded plates

<td>Method research</td><td>Product</td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td></td><td></td><td>competitive</td><td>competitive</td>

<td></td><td>Stretching (tiles) Type IV at 5.08 cm / min (2 inches / min). 1905 μm (75 mils)</td><td>Type IV, 5.08 cm / min (2 inch / min)</td><td></td><td></td>

<td rowspan="4">ASTM D638</td><td>Tensile strength at break (MPa) ((lb / in²))</td><td> 26,6 (3800)</td><td> 30,0 (4285)</td><td> 28,2 (4028)</td>

<td>Elongation at break,%</td><td> &gt;800%</td><td> 819</td><td> 799</td>

<td>Stress at yield (MPa) ((lb / in²))</td><td></td><td> 10,8 (1547)</td><td> 12,9 (1842)</td>

<td>Elongation at yield point,%</td><td></td><td> 13,3</td><td> 11,9</td>

Table 23: Stretch data for competing black sheets

<td>Method research</td><td>Product</td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td></td><td></td><td>competitive</td><td>competitive</td>

<td></td><td>Stretching (black)</td><td>Type IV, stretching speed 5.08 cm / min (2 inches / min)</td><td></td><td></td>

<td>ASTM D5199</td><td>Thickness ^ m] ((mils))</td><td></td><td> 1422 (56)</td><td> 1524 (60)</td>

<td rowspan="7">ASTM D6693</td><td>Stress at yield point, MD (ppi)</td><td></td><td> 103</td><td> 127</td>

<td>Stress at yield point, MD (MPa) ((pounds / inch²))</td><td></td><td> 12,9 (1839)</td><td> 14,8 (2117)</td>

<td>Stress at yield point, TD (ppi)</td><td></td><td> 101</td><td> 123</td>

<td>Stress at yield point, TD (MPa) ((pounds / inch²))</td><td></td><td> 12,6 (1804)</td><td> 14,4 (2050)</td>

<td>Tensile strength at break, MD (ppi)</td><td></td><td> 292</td><td> 277</td>

<td>Tensile strength at break, MD (MPa) ((pounds / inch²))</td><td> &gt; 26,6 (3800)</td><td> 36,5 (5214)</td><td> 32,3 (4617)</td>

<td>Tensile strength at break, TD (ppi)</td><td></td><td> 289</td><td> 283</td>

EP 2 393 852 B1

<td>Method research</td><td>Product</td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td></td><td></td><td>competitive</td><td>competitive</td>

<td></td><td>Tensile strength at break, TD (MPa) ((pounds / inch²))</td><td> &gt; 26,6 (3800)</td><td> 36,1 (5161)</td><td> 33,0 (4717)</td>

<td></td><td>Elongation at yield point, MD,%</td><td></td><td> 22</td><td> 19</td>

<td></td><td>Elongation at yield point, TD,%</td><td></td><td> 19</td><td> 16</td>

<td></td><td>Elongation at break, MD,%</td><td> &gt;800%</td><td> 1059</td><td> 905</td>

<td></td><td>Elongation at break, TD,%</td><td> &gt;800%</td><td> 1053</td><td> 892</td>

Table 24: Puncture and tear data of competing black sheets

<td>Method research</td><td>Product</td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td></td><td></td><td>competitive</td><td>competitive</td>

<td>ASTM 4833</td><td>Puncture resistance [kg] ((pounds of strength))</td><td>373.7 N (84 lb.) at 1524 μm (60 mils)</td><td> 48,1 (106)</td><td> 51,3 (113)</td>

<td rowspan="2">ASTM D1004</td><td>Tear resistance, MD [kg] ((pounds of strength))</td><td>146.8 N (33 pounds of force) at 1524 μm (60 mils)</td><td> 17,7 (39)</td><td> 19,1 (42)</td>

<td>Tear resistance, TD [kg] ((pounds of strength))</td><td>Tear resistance, MD [kg] ((pounds of strength))</td><td> 17,2 (38)</td><td> 19,1 (42)</td>

Table 25: Tensile data of a competitive natural sheet

<td>Method research</td><td></td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td>Stretching (natural)</td><td>Type IV, stretching speed 5.08 cm / min (2 inches / min)</td><td></td><td></td>

<td>ASTM D5199</td><td>Thickness ^ m] ((mils))</td><td></td><td> 1499 (59)</td><td> 1499 (59)</td>

<td></td><td>Stress at yield point, MD (ppi)</td><td></td><td> 99</td><td> 119</td>

<td></td><td>Stress at yield point, MD (MPa) ((pounds / inch²))</td><td></td><td> 11,8 (1678)</td><td> 14,1 (2017)</td>

<td></td><td>Stress at yield point, TD (ppi)</td><td></td><td> 94</td><td> 122</td>

<td></td><td>Stress at the plan boundary</td><td></td><td> 11,2 (1593)</td><td> 14,5 (2068)</td>

EP 2 393 852 B1

<td>Method research</td><td></td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td>tangency, TD (MPa) ((pounds / inch²))</td><td></td><td></td><td></td>

<td>ASTM</td><td>Tensile strength at break, MD (ppi)</td><td></td><td> 294</td><td> 276</td>

<td>D6693</td><td>Tensile strength at break, MD (MPa) ((pounds / inch²))</td><td> &gt; 26,6 (3800)</td><td> 34,9 (4983)</td><td> 32,8 (4678)</td>

<td></td><td>Tensile strength at break, TD (ppi)</td><td></td><td> 313</td><td> 276</td>

<td></td><td>Tensile strength at break, TD (MPa) ((pounds / inch²))</td><td> &gt; 26,6 (3800)</td><td> 37,1 (5305)</td><td> 32,8 (4678)</td>

<td></td><td>Elongation at yield point, MD,%</td><td></td><td> 18</td><td> 21</td>

<td></td><td>Elongation at yield point, TD,%</td><td></td><td> 18</td><td> 17</td>

<td></td><td>Elongation at break, MD,%</td><td> &gt;800%</td><td> 1041</td><td> 869</td>

<td></td><td>Elongation at break, TD,%</td><td> &gt;800%</td><td> 1191</td><td> 891</td>

Table 26: Stress data for competing natural sheet samples

<td>Method research</td><td></td><td>Industrial requirements</td><td>MARLEX 7104</td><td>MARLEX K203</td>

<td></td><td></td><td></td><td>competitive</td><td>competitive</td>

<td>ASTM D4833</td><td>Puncture resistance [kg] ((pounds of strength))</td><td>373.7 N (84 lb.) at 1524 μm (60 mils)</td><td> 51,7 (114)</td><td> 50,8 (112)</td>

<td rowspan="2">ASTM D1004</td><td>Tear resistance, MD [kg] ((pounds of strength))</td><td>146.8 N (33 pounds of force) at 1524 μm (60 mils)</td><td> 17,2 (38)</td><td> 19,5 (43)</td>

<td>Tear resistance, TD [kg] ((pounds of strength))</td><td>146.8 N (33 pounds of force) at 1524 μm (60 mils)</td><td> 18,1 (40)</td><td> 18,6 (41)</td>

[0197] Sheets made from the resins according to the invention were tested and shown to meet the physical and mechanical properties of the Geosynthetic Research Institute standard for LLDPE, GM-17 sheets. Axis 22 bent stress at break, approximately 28 to 34.3 MPa (4,000 lb / in² up to 4,900 pounds / inch²) was ₂ well above the requirements for GM-17 26.6 MPa (3,800 pounds / inch²). The elongation at break achieved, about 940% -1000%, was also greater than the requirements for GM-17&gt; 800%. The sheets of the invention also had better tensile properties compared to the comparative examples. The resins of the invention also exhibited excellent melt strength, as evidenced by the melt flow ratios, especially I21 / I2, and / or rheological data, for example a viscosity ratio of (10^-2 rad / 100 rad). In addition, the resins of the invention are not expensive at

Matching (for example, matching with peroxide or oxygen) with resins, and still exhibit excellent melt strength as evidenced by high viscosity ratios (0.10 rad / 100 rad).

Polymers, compositions and piping according to the invention [0198] Samples according to the invention were polymerized in a gas phase reactor, in the presence of a fluorinated and titanized CrO catalyst, activated at 825 ° C, with appropriate gas compositions (C6 / C2 ratios and the like). 1-hexene was used as the comonomer in the samples of the invention. The granulated polymer was removed from the reactor, cooled and freed from residual hydrocarbons by blowing, so that no degradation occurred. The granulated samples were then mixed, under mild mixing conditions, with appropriate additives (primary and secondary type) and granulated. The tests were carried out, in accordance with the above test methods, on granulated resin, compression-molded plates or extruded pipes.

Representative Polymerization [0199] The fluidized bed reactor described above was used for gas phase polymerization. Reaction conditions and some resin properties are summarized in Table 27. Additional resin properties are summarized in Tables 28-32. The resin of the invention had good mechanical and rheological properties. FIG. 15 depicts the ATREF profile of the comparative "NT resin," and FIG. 16 depicts the ATREF profile of the "0.3 LLDPE" resin according to the invention.

[0200] Pipe extrusion conditions for the resin of the invention are summarized in Table 33. The properties of the pipes are summarized in Tables 34 and 35. Figure 17 shows "strand stress versus time for failure" data for "NT resin (12 tubes tested)" and Figure 18 shows "strand stress as time versus failure" data for "0.3 LLDPE resin (35 tubes tested) . " In each figure, certain data points overlap due to similar times to failure (stress cracking) at similar stress levels.

Table 27: Sample of the invention with 1-hexene

<td></td><td></td><td colspan="2">0.3 LLDPE resin</td>

<td></td><td>units</td><td>Medium</td><td>standard deviation. stand.</td>

<td>Reaction</td><td></td><td></td><td></td>

<td>Fluidized bed temperature</td><td>° C</td><td> 88,5</td><td> 0,00</td>

<td>Gas inlet temperature</td><td>° C</td><td> 81,4</td><td> 0,64</td>

<td>Total hypertension</td><td>MPa (pounds / inch²)</td><td> 2,44 (348)</td><td> 0,3</td>

<td>C2H4 partial pressure</td><td>Absolute MPa (pounds / inch²)</td><td> 1,76 (250)</td><td> 0,2</td>

<td>H2 feed rate</td><td>milli-kg / h (milli-pounds / h)</td><td> 27,8 (61,3)</td><td> 0,85</td>

<td>O2 additional feed rate</td><td>milli-kg / h (milli-pounds / h)</td><td> 0,00</td><td> 0,000</td>

<td>Feed rate C₂H4</td><td>kg / h (lbs / h)</td><td> 28,7 (63,3)</td><td> 1,01</td>

EP 2 393 852 B1

<td></td><td></td><td colspan="2">0.3 LLDPE resin</td>

<td></td><td>units</td><td>Medium</td><td>standard deviation. stand.</td>

<td>C6H12 Feed Rate</td><td>kg / h (lbs / h)</td><td> 2,05 (4,53)</td><td> 0,092</td>

<td>Feed rate i-C5H12</td><td>kg / h (lbs / h)</td><td> 0,43 (0,95)</td><td> 0,013</td>

<td>TEAL feed rate</td><td>mg / h</td><td> 8,61</td><td> 0,099</td>

<td>Catalyst Cr load</td><td>wt%</td><td> 0,20</td><td></td>

<td>Catalyst feed rate</td><td>g / h</td><td> 4,02</td><td> 0,254</td>

<td>Degassing rate C2H4</td><td>kg / h (lbs / h)</td><td> 12,3 (27,2)</td><td> 1,77</td>

<td>Degassing rate C6H12</td><td>kg / h (lbs / h)</td><td> 1,06 (2,345)</td><td> 0,2561</td>

<td>Solubility of the resin in C6H12</td><td>(pounds / 100 pounds)</td><td> 1,48</td><td> 0,07</td>

<td>O2 / C2 feed ratio</td><td>ppbv</td><td> 0,0</td><td> 0,00</td>

<td>C6 / C2 administration ratio</td><td>kg / kg (lb / lb)</td><td> 0,0032 (0,0715)</td><td> 0,00237</td>

<td>Non-degassed C6 / C2 ratio</td><td>kg / kg (lb / lb)</td><td> 0,0027 (0,0604)</td><td> 0,00099</td>

<td>TEAL / Cr feed ratio</td><td>mol / mol</td><td> 0,490</td><td> 0,0362</td>

<td>H2 / C2 composition ratio</td><td>mol / mol</td><td> 0,050</td><td> 0,0001</td>

<td>The composition ratio of C6 / C2</td><td>mol / mol</td><td> 0,0287</td><td> 0,00130</td>

<td>Share of i-C5</td><td>mol%</td><td> 0,17</td><td> 0,024</td>

<td>Medium static voltage</td><td>medium voltage</td><td> -43</td><td> 1</td>

<td>Static bandwidth</td><td>60 volts</td><td> 72</td><td> 7</td>

<td>Supercritical Gas Speed</td><td>m / s (feet / s)</td><td> 0,53 (1,73)</td><td> 0,004</td>

<td>Apparent density of the fluidized bed</td><td>₃kg / m '(pounds / foot)</td><td> 286,7 (17,9)</td><td> 0,26</td>

<td>Fluid bed mass</td><td>kg (pounds)</td><td> 57,6 (121)</td><td> 0,8</td>

<td>Fluid bed height (3.05 m Rx) ((10 ft Rx))</td><td>m (feet)</td><td> 2,26 (7,42)</td><td> 0,141</td>

<td>Production efficiency</td><td>kg / h (lbs / h)</td><td> 17,1 (37,8)</td><td> 2,85</td>

<td>Residence time</td><td>h</td><td> 3,37</td><td> 0,242</td>

<td>Space-time efficiency</td><td>kg / h / m³ (Lb / hr / ft³)</td><td> 85,4 (5,33)</td><td> 0,315</td>

<td>Total monomer ratio</td><td>kg / kg (lb / lb)</td><td> 0,82 (1,80)</td><td> 0,116</td>

EP 2 393 852 B1

<td></td><td></td><td colspan="2">0.3 LLDPE resin</td>

<td></td><td>units</td><td>Medium</td><td>standard deviation. stand.</td>

<td>Total ratio of non-degassed monomers</td><td>kg / kg (lb / lb)</td><td> 0,46 (1,025)</td><td> 0,0007</td>

<td>Catalyst efficiency</td><td>Mkg / kg (Mfunty / lb) Cat</td><td> 1,93 (4,26)</td><td> 0,105</td>

<td>Performance relative to chromium</td><td>MMkg / kg (MMfounds / pound) Cr</td><td> 0,97 (2,13)</td><td> 0,053</td>

Table 28: Density and melt flow index

<td></td><td></td><td>NT resin</td><td>Resin 0.3</td>

<td>Research Method</td><td></td><td>comparative</td><td>according to the invention</td>

<td>ASTM D-792-98</td><td>₃Density [g / cm]</td><td> 0,9198</td><td> 0,927</td>

<td rowspan="3">ASTM D-1238-04</td><td>I2 g / 10 min at 190C</td><td> 0,62</td><td> 0,25</td>

<td>I10 g / 10 min at 190C</td><td> 10,1</td><td> 4,7</td>

<td>I21 g / 10 min at 190C</td><td> 48</td><td> 20</td>

<td></td><td>MFR (I10 / I2)</td><td> 16</td><td> 19</td>

<td></td><td>MFR (I21 / I2)</td><td> 78</td><td> 80</td>

Table 29: Rheological properties and IR structure

<td></td><td></td><td>Resin comparative NT *</td><td>Resin 0.3 according to the invention</td>

<td>Research Method</td><td></td><td></td><td></td>

<td>Rheological properties</td><td></td><td></td><td></td>

<td></td><td>Viscosity ratio [10^-2/ 10⁺²] from DMS</td><td> 40</td><td> 69</td>

<td></td><td>Delta tg ratio [10^-2 / 10+²] from DMS</td><td> 3,0</td><td> 2,6</td>

<td></td><td>Alloy strength [cN]</td><td> 7,5-8</td><td> 8-8,5</td>

<td>IR structure</td><td></td><td></td><td></td>

<td>D-6264-98</td><td>Trans / 1000 carbon atoms</td><td> 0,080</td><td> 0,101</td>

<td>D-6264-98</td><td>Vinyls / 1000 carbon atoms</td><td> 0,92</td><td> 0,95</td>

EP 2 393 852 B1

<td></td><td></td><td>Resin comparative NT *</td><td>Resin 0.3 according to the invention</td>

<td>Research Method</td><td></td><td></td><td></td>

<td>Rheological properties</td><td></td><td></td><td></td>

<td>D-2238-92</td><td>Methyl / 1000 carbon atoms</td><td> 16,7</td><td> 10,8</td>

<td colspan="4">* NT resin is an ethylene / butene copolymer (LLDPE) made on a chromium catalyst (this resin is commercially available as FINGERPRINT DFDA-7510 NT Linear Low Density Polyethylene Resin, available from The Dow Chemical Company).</td>

Table 30: ATREF and GPC data

<td></td><td>NT resin</td><td>Resin 0.3</td>

<td>ATREF</td><td></td><td></td>

<td>High density fraction [%]</td><td> 8,9</td><td> 19</td>

<td>Minimum temperature [° C]</td><td> 91,8</td><td> 93,5</td>

<td>Non-crystalline fraction [%]</td><td> 17,5</td><td> 14,5</td>

<td>% SCB [calculated]</td><td> 73,6</td><td> 66,5</td>

<td>Mv average</td><td> 53 504</td><td> 56 283</td>

<td>MV SCB</td><td> 58 358</td><td> 58 140</td>

<td>Mv non-crystalline fraction</td><td> 30 057</td><td> 45 332</td>

<td>GPC</td><td></td><td></td>

<td>Conventional GPC</td><td></td><td></td>

<td>Mn</td><td> 7 620</td><td> 9 430</td>

<td>mw</td><td> 105 540</td><td> 124 160</td>

<td>Mz</td><td> 575 200</td><td> 594 500</td>

<td>Mw / Mn</td><td> 13,9</td><td> 13,2</td>

<td>Absolute GPC</td><td></td><td></td>

<td>Mn</td><td> 7 434</td><td> 9 717</td>

<td>mw</td><td> 103 180</td><td> 128 640</td>

<td>Mw / Mn</td><td> 13,9</td><td> 13,2</td>

<td>Mz (BB)</td><td> 536 400</td><td> 559 200</td>

<td>Mz (abs)</td><td> 529 400</td><td> 547 100</td>

EP 2 393 852 B1

<td></td><td>NT resin</td><td>Resin 0.3</td>

<td>Mz + 1 (BB)</td><td> 1 540 900</td><td> 1 508 600</td>

<td>Mz (abs) / Mw (abs)</td><td> 5,13</td><td> 4,25</td>

<td>Mz + 1 (BB) / Mw (abs)</td><td> 14,93</td><td> 11,73</td>

Table 31: DSC data

<td></td><td></td><td>NT resin</td><td>Resin 0.3</td>

<td rowspan="4">DSC results</td><td>Melting point (° C)</td><td> 118,62</td><td> 122,91</td>

<td>Heat of melting (J / g)</td><td> 143,6</td><td> 158,1</td>

<td>Crystallization temperature (° C)</td><td> 106,43</td><td> 112,02</td>

<td>Heat of crystallization (J / g)</td><td> 144,2</td><td> 157,6</td>

Table 32: Tensile properties and flexural modulus - molded plates

<td></td><td></td><td>NT resin</td><td>Resin 0.3</td>

<td>ASTM D638</td><td>Stretching (shallow) - Type IV @ 5.08 cm / min (2 inches / min), 1905 μm (75 mils)</td><td></td><td></td>

<td></td><td>Average thickness [cm] ([inches])</td><td> 0,1946 (0,0766)</td><td> 0,2012 (0,0792)</td>

<td></td><td>₂Tensile strength at break (MPa) ((pounds / inch))</td><td> 22,8 (3251)</td><td> 30,1 (4300)</td>

<td></td><td>Elongation at break,%</td><td> 713</td><td> 565</td>

<td></td><td>₂Stress at yield point (MPa) ((pounds / inch))</td><td> 11,2 (1605)</td><td> 14,9 (2129)</td>

<td></td><td>Elongation at yield point,%</td><td> 15,8</td><td> 13,5</td>

<td></td><td>Std. stand. - Elongation at break</td><td> 2,0056</td><td> 0,2183</td>

<td></td><td>Std. stand. - Peak load</td><td> 2,61</td><td> 8,33</td>

<td></td><td>Std. stand. - Peak stress</td><td> 136</td><td> 430</td>

<td></td><td>Std. stand. - strain at break</td><td> 201</td><td> 22</td>

<td></td><td>Std. stand. - deformation at the yield point</td><td> 2,024</td><td> 0,3892</td>

<td></td><td>Std. stand. - stress at break</td><td> 136</td><td> 430</td>

<td></td><td>Std. stand. - stress at yield strength</td><td> 65</td><td> 34</td>

<td></td><td>Std. stand. - thickness</td><td> 0,0015</td><td> 0,0013</td>

<td></td><td>Std. stand. - width</td><td> 0</td><td> 0</td>

<td>ASTM D790-03</td><td>₂Flexural modulus [MPa] ((pounds / inch²))</td><td> 402,8 (57543)</td><td> 588,3 (84044)</td>

EP 2 393 852 B1

<td></td><td></td><td>NT resin</td><td>Resin 0.3</td>

<td></td><td>Std. stand. - Flexural modulus</td><td> 3102</td><td> 3964</td>

Table 33: Extrusion parameters "2.54 cm (1-inch)" DR 11 LLDPE 0.3 resin pipe

<td>Nozzle 1 (° C) ((F))</td><td>199 ° C (390F)</td>

<td>Zones 2, 3, 4, 5, 6, 7, 8 (° C) ((F))</td><td>Each 199 ° C (390F)</td>

<td>Cylinder 1 (° C) ((F))</td><td>193 ° C (380F)</td>

<td>2 (° C) ((F))</td><td>196 ° C (385F)</td>

<td>3 (° C) ((F))</td><td>199 ° C (390F)</td>

<td>4 (° C) ((F))</td><td>199 ° C (390F)</td>

<td>Melting (probe) (° C) ((F))</td><td>202 ° C (395F)</td>

<td>Processing parameters</td><td></td>

<td>₂Cylinder pressure (MPa) ((pounds / inch))</td><td> 8,05 (1150)</td>

<td>Snail, rpm</td><td> 81</td>

<td>Motor current load (%)</td><td> 64,5</td>

<td>Push rod speed (m / min) ((feet / min))</td><td> 7,07 (23,2)</td>

<td>Vacuum tank (° C) ((F))</td><td> 32 (90)</td>

<td>Vacuum (cm Hg) ((inch Hg))</td><td> 27,9 (11)</td>

<td>Temp. cooling bath # 1 (° C) ((F))</td><td> 32 (90)</td>

<td>Temp. Cooling bath # 2 (° C) ((F))</td><td>ON</td>

<td>Processing (kg / h) ((pounds / h))</td><td> 108 (238)</td>

<td>Gloss OD (external)</td><td>Approx</td>

<td>ID</td><td>Approx</td>

<td>Nozzle plate outlet</td><td></td>

<td>smoke</td><td>Normal</td>

<td>Smell</td><td>Normal</td>

<td>Dimension of the pipe</td><td></td>

<td>OD (cm) ((inches))</td><td> 3,345 (1,317)</td>

<td>Wall thickness (largest) (cm) ((inches))</td><td> 0,3099 (0,122)</td>

<td>Wall thickness (smallest) (cm) ((inches))</td><td> 0,305 (0,120)</td>

Table 34: ASTM D-2837 Regression for NT basic resin

EP 2 393 852 B1

<td></td><td>NT resin</td>

<td>Average OD of Pipe (cm) ((inches)) (n = 12)</td><td> 3,1 (1,2)</td>

<td>Minimum pipe wall thickness (cm) ((inches))</td><td> 0,185 (0,073)</td>

<td>SDR</td><td> 16,44</td>

<td>Sidra</td><td> 14,44</td>

<td>Test temperature (degrees C)</td><td> 23</td>

<td>Number of data points (# pipes tested)</td><td> 12</td>

<td>Intersection with the Y axis</td><td> 103,0</td>

<td>Slope of the line</td><td> -32,9</td>

<td>Regression equation</td><td>log (t) = (103.0) + (- 32.9) * log (P)</td>

<td>Standard deviation of the prediction</td><td> 0,4600288</td>

<td>note: both "r" and "r2" take account of anticipated damage</td><td></td>

<td>time as a function of actual time to destruction</td><td></td>

<td>Correlation coefficient (r)</td><td> 0,843</td>

<td>r2 value:</td><td> 0,711</td>

<td>Ratio (LCL / LTHS)</td><td> 0,904</td>

<td>Long-term hydrostatic stress (100,000 hours)</td><td> 952</td>

<td>Lower confidence limit (97.5%)</td><td> 860</td>

<td>Basis of hydrostatic design</td><td> 800</td>

Table 35: ASTM D-2837 Regression for LLDPE 0.3 resin

<td></td><td>LLDPE 0.3 (according to the invention)</td>

<td>Average OD of Pipe (cm) ((inches)) (n = 35)</td><td> 3,345 (1,317)</td>

<td>Minimum pipe wall thickness (cm) ((inches))</td><td> 0,305 (0,120)</td>

<td>SDR</td><td> 10,98</td>

<td>Sidra</td><td> 8,98</td>

<td>Test temperature (degrees C)</td><td> 23</td>

<td>Number of data points (# pipes tested)</td><td> 35</td>

<td>Intersection with the Y axis</td><td> 137,8</td>

<td>Slope of the line</td><td> -44,29</td>

EP 2 393 852 B1

<td>Regression equation</td><td>log (t) = (137.8) + (- 44.29) * log (P)</td>

<td>Standard deviation of the prediction</td><td> 0,4233</td>

<td>note: both "r" and "r2" take account of anticipated damage</td><td></td>

<td>time as a function of actual time to destruction</td><td></td>

<td>Correlation coefficient (r)</td><td> 0,494</td>

<td>r2 value:</td><td> 0,244</td>

<td>Ratio (LCL / LTHS)</td><td> 0,978</td>

<td>Long-term hydrostatic stress (100,000 hours)</td><td> 997</td>

<td>Lower confidence limit (97.5%)</td><td> 975</td>

<td>Basis of hydrostatic design</td><td> 1000</td>

[0201] The resin extruded pipe according to the invention was tested in a solid state and was shown to meet the requirements for operating category "HBD 7 MPa (1,000 pounds / inch^{1 2}) at 23 ° C "according to ASTM ₂

D-2837, achieving an LTHS value of 6.98 MPa (997 pounds / inch²). The resin according to the invention provided improvement while maintaining excellent processing properties, as evidenced by the ratio of melt flow indexes I21 / I2, 80, and the viscosity ratio (10^-2 rad / 100 rad) 69, even in the case of high molecular weight, as indicated by I2 0.25 g / 10 min. This increased hydrostatic strength allows a more cost-effective solution for tube / pipe systems, using linear low-density ethylene-based polymers, instead of expensive off-reactor mixes or in-situ reactor mixes, or expensive matched resins.