Polyethylene recycled blend product

Abstract

A composition is provided that includes a blend of a first HDPE component having a relatively high density and low molecular weight and a second HDPE component having a relatively low density and high molecular weight, which blend exhibits improved ESCR performance compared to currently available HDPE products at a particular density.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 395,255, filed August 4, 2022, which is incorporated herein by reference in its entirety.

[0002] The present disclosure relates to blends of recycled high density polyethylene and virgin high density polyethylene. [Background technology]

[0003] Polyolefins, especially polyethylene, are increasingly consumed in large quantities for many applications, including food and other commodity packaging, electronics, automotive parts, and various manufactured goods. Currently, large amounts of waste plastic material are generated from the differentiated collection of municipal plastic waste, consisting primarily of flexible packaging (cast film, blown film, and BOPP film), rigid packaging, blown bottles, and injection-molded containers. Typically, polyethylene fractions, especially high-density polyethylene (HDPE) recyclables, can be recovered through a separation step from other polymers, such as PVC, PET, and PS.

[0004] Common uses for HDPE resin include, but are not limited to, small blow molding, caps and closures, jerry cans, high molecular weight films, injection molding, tubing, and industrial bulk containers. Direct reuse of such HDPE recyclates is limited in that they typically exhibit reduced crack resistance, melt strength, and / or impact strength compared to virgin HDPE of similar density and high-load melt index. Thermal and / or catalytic degradation of polymer recyclates allows the recovery of the polymer's monomer components, which can then be used as feedstock for the production of new polymers with desirable properties. However, this requires additional, energy-intensive processing steps and, in some cases, generates undesirable by-products that require further processing steps for disposal in a desirable manner.

[0005] It is desirable to return HDPE recycled material more directly to the stream of commerce and minimize the additional processing steps required to do so. A process should be provided for producing HDPE compositions containing HDPE. Such HDPE compositions have a useful combination of properties that are equivalent to or superior to similar virgin HDPE compositions. Ideally, such a process should be highly flexible and can be implemented using commonly used equipment and familiar techniques to produce a variety of products. Summary of the Invention

[0006] Generally, the present disclosure relates to compositions comprising a blend of a first HDPE component and a second HDPE component. The first HDPE component has a relatively lower molecular weight and higher density than the second HDPE component. In some embodiments, the blend has a higher environmental stress crack resistance (ESCR) than virgin HDPE of similar density.

[0007] In some embodiments, the first HDPE component is present in the blend in an amount ranging from 40% to 95% by weight and the second HDPE component is present in the blend in an amount ranging from 5% to 60% by weight, the weight percentages being based on the combined weight of the first HDPE component and the second HDPE component.

[0008] In some embodiments, the first HDPE component has a viscosity of 0.955 g / cm 3 ~0.965g / cm 3 It has a density in the range, a melt index (I5) in the range of 1.50 g / 10 min to 3.50 g / 10 min, and an environmental stress crack resistance ("ESCR") F50 in the range of less than 10 hours to 20 hours at 10% Igepal.

[0009] In some embodiments, the second HDPE component has a viscosity of 0.947 g / cm 3 ~0.954g / cm 3 ~0.954g / cm 3), with a melt index (I5) ranging from 0.10 g / 10 min to 1.50 g / 10 min and an environmental stress crack resistance ("ESCR") F50 of greater than 1,000 hours at 10% Igepal.

[0010] In some embodiments, the blend has a viscosity of 0.951 g / cm 3 ~0.962g / cm 3 , a melt index (I5) ranging from 0.60 g / 10 min to 2.50 g / 10 min, and an environmental stress crack resistance ("ESCR") F50 ranging from 24 hours to 1,000 hours at 100% Igepal and / or 24 hours to 84 hours at 10% Igepal.

[0011] In some embodiments, the composition is made by melt blending the first and second HDPE components, and optionally a primary and / or secondary antioxidant, to form a pelletized product.

[0012] The foregoing has outlined, rather broadly, the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. Those skilled in the art should realize that the conception and specific embodiments disclosed may be readily utilized as a basis for modifying or designing other film structures and / or processes for carrying out the same purposes of the present invention. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features believed characteristic of the present invention, both as to its structure and method of manufacture, together with further objects and advantages, will be better understood from the following description. [Brief explanation of the drawings]

[0013] The claimed subject matter can be understood by reference to the following description in conjunction with the accompanying drawings, in which like reference numerals indicate like elements and in which: [Figure 1] FIG. 1 shows an overlaid graph comparing the ESCR performance of HDPE blends according to embodiments of the invention with other similar HDPE blends. [Figure 2] FIG. 2 compares the ESCR performance of blends using the virgin first HDPE component disclosed herein with other HDPEs. [Figure 3] FIG. 3 compares the ESCR performance of blends disclosed herein using a recycled first HDPE component with other HDPEs. [Figure 4] Figure 4 shows the diameter swell performance of HDPE blends for benchmark diameter swell ranges according to an embodiment of the invention. While the disclosed processes and compositions are susceptible to various modifications and alternative forms, the drawings show specific embodiments described in detail by way of example. It should be understood, however, that the description of specific embodiments herein is not intended to limit the invention to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. DETAILED DESCRIPTION OF THE INVENTION

[0014] Disclosed below are exemplary embodiments of the claimed subject matter. For clarity, some features of an actual implementation may not be described in this specification. It is understood that developing such an actual embodiment will require making numerous implementation-specific decisions that will vary from implementation to implementation in order to achieve a developer's particular goals, including compliance with system-related and business-related constraints. It is further understood that such a development effort, even if complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.

[0015] The words and phrases used herein should be understood and interpreted to have a meaning consistent with the understanding of those words and phrases by those skilled in the relevant art. No special definition of a term or phrase, i.e., a definition that is different from the ordinary and customary meaning understood by those of ordinary skill in the art, is intended to be implied by consistent use of a term or phrase herein. To the extent that a term or phrase is intended to have a special meaning, i.e., a meaning other than the broadest meaning understood by a skilled artisan, such special or clear definition will be expressly set forth in the specification in a defining manner that provides a special or clear definition of that term or phrase. It should also be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless otherwise specified.

[0016] For example, the following description includes a non-exhaustive list of definitions of some specific terms used in this disclosure (other terms may be definitionally defined or clarified elsewhere in this document). These definitions are intended to clarify the meaning of the terms as used herein. It is believed that the terms are used in a manner consistent with their ordinary meaning, but definitions are nevertheless provided here for clarity. definition

[0017] As used herein, "antioxidant" means a compound that inhibits oxidation, a chemical reaction that produces free radicals and chain reactions. Antioxidants are distinguished based on their mechanism of action and include: (1) primary antioxidants, and (2) secondary antioxidants.

[0018] As used herein, "compounding conditions" means the conditions of temperature, pressure, and shear effected in an extruder to intimately mix two or more polymers and optional additives to produce a substantially homogeneous polymer product.

[0019] In this specification, "HDPE recycled material" refers to a material with a density of 0.940 g / cm 3~0.970g / cm 3 This refers to a portion of polyolefin recycled material in the range of

[0020] As used herein, "HDPE" refers to a polyethylene terephthalate (HDPE) produced by gas phase polymerization and / or slurry phase polymerization and having a density of 0.940 g / cm 3 ~0.970g / cm 3 This refers to ethylene homopolymers and ethylene copolymers in the range

[0021] As used herein, "polyolefin recycle" refers to post-consumer recycled ("PCR") polyolefins and / or post-industrial recycled ("PIR") polyolefins. Polyolefin recycle is derived from end-of-life pre-consumer products (e.g., polyethylene water bottles) and plastic scrap generated as waste from industrial processes. Post-consumer polyolefins include polyolefins collected through commercial and residential recycling programs, such as flexible packaging (cast film, blown film, and BOPP film), rigid packaging, blown bottles, and injection-molded containers. Typically, two major polyolefin fractions are obtained through a separation step from other polymers, such as nylon, polyamide, PVC, PET, and PS: polyethylene recycle (including HDPE, MDPE, LDPE, and LLDPE) and polypropylene recycle (including homopolymers, random copolymers, and heterophase copolymers). Polyethylene recycle can be further separated to recover the polyolefin-based fraction. In addition to contamination by foreign polymers, polyolefin recycled materials often contain impurities such as PMMA, PC, wood, paper, textiles, cellulose, food, and other organic waste, many of which cause unpleasant odors in polyolefin recycled materials before and after normal processing.

[0022] As used herein, "primary antioxidant" refers to a compound that essentially functions as a terminator or scavenger of free radicals. Primary antioxidants react rapidly with peroxy and alkoxy radicals. The majority of primary antioxidants in polymers are sterically hindered phenols.

[0023] As used herein, "processability" refers to whether a polymer composition can be cast into commercial quality blown film or formed into commercial quality molded articles by injection or compression molding at commercially acceptable rates using equipment and conditions.

[0024] As used herein, "secondary antioxidant" means a compound that is a preventative antioxidant that functions by delaying chain initiation. Secondary antioxidants are often called hydroperoxide decomposers because they react with hydroperoxides to form non-radical products.

[0025] As used herein, "virgin HDPE" refers to HDPE that has not been used by a consumer. Pre-consumer HDPE is a product derived directly or indirectly from petrochemical feedstocks fed to a polymerization unit. Pre-consumer polyolefins may undergo post-polymerization processing, such as, but not limited to, extrusion, pelletizing, peroxidation, visbreaking, and / or other processes, before the product reaches the end user. In some embodiments, virgin polyolefins have a single heat history. In some embodiments, virgin polyolefins have multiple heat histories. In some embodiments, virgin polyolefins do not contain additives. In some embodiments, virgin polyolefins contain additives. HDPE Blend Composition

[0026] Disclosed herein are compositions comprising a blend of a first HDPE blend component and a second HDPE blend component, the first HDPE component having a relatively higher density and lower molecular weight than the second HDPE component.

[0027] In some embodiments, the first HDPE component is present in a blend amount ranging from 40% to 95%, 50% to 90%, 60% to 85%, or 70% to 80% by weight. Similarly, the second HDPE component is present in a blend amount ranging from 5% to 60%, 10% to 50%, 15% to 40%, or 20% to 30% by weight. All weight percentages are based on the combined weight of the first and second HDPE components.

[0028] In some embodiments, the blend composition comprises: a) 0.951 g / cm 3 to 0.962 g / cm 3 or 0.956 g / cm 3 to 0.960 g / cm 3 Density in the range b) a melt index (I5) in the range of 0.60 g / 10 min to 2.50 g / 10 min, or 0.80 g / 10 min to 1.80 g / 10 min, and c) having one or more of the following: Environmental Stress Cracking Resistance ("ESCR") F50 in the range of 24 hours to 1,000 hours for 100% Igepal, and / or 24 hours to 84 hours for 10% Igepal.

[0029] In some embodiments, the blend composition comprises: a) Number average molecular weight (M) in the range of 10,000 g / mol to 20,000 g / mol n ), b) a weight average molecular weight (M) in the range of 130,000 g / mol to 230,000 g / mol or 156,000 g / mol to 194,000 g / mol w ), c) molecular weight distribution (MWD) in the range of 8-20 or 10-15; d) a high load melt index (HLMI) in the range of 15 g / 10 min to 45 g / 10 min or 20 g / 10 min to 40 g / 10 min, and e) having one or more of a 2% flexural modulus in the range of 165,000 psi (1,138 MPa) to 215,000 psi (1,482 MPa) or 175,000 psi (1,207 MPa) to 205,000 psi (1,413 MPa).

[0030] In some embodiments, the blend composition comprises: a) Overall polydispersity ratio (PDR) in the range of 15 to 60; b) 1.0 × 10 6 ~3.0×10 7 Zero shear viscosity (η0) in the range c) a bulk intrinsic viscosity ([η]) in the range of 1.5 to 2.5, and d) having one or more of the following long chain branching indices (LCBI) in the range of 0.3 to 1.3.

[0031] In some embodiments, the first HDPE component and the second HDPE component are melt blended at a temperature in the range of 150° C. to 250° C. to form the composition.

[0032] In some embodiments, the blend further comprises a primary antioxidant, a secondary antioxidant, or a combination thereof, hi further embodiments, the primary antioxidant is present in the blend in an amount of 1500 ppm or less and the secondary antioxidant is present in the blend in an amount of 1500 ppm or less, the ppm values being based on the combined weight of the first HDPE component and the second HDPE component.

[0033] Figure 1 shows the general trend for the FHC / SHC blends disclosed herein, which show improved ESCR compared to blends of HDPE recycle with a typical unimodal Cr-HDPE (made using a chromium catalyst) or a typical multimodal HDPE. -First HDPE blend composition

[0034] The first HDPE component is 0.955 g / cm 3 ~0.966g / cm 3It has a density in the range of 1.50g / 10min to 3.50g / 10min, a melt index (I5) in the range of 1.50g / 10min to 3.50g / 10min, and an ESCR F50 of less than 24 hours at 100% Igepal.

[0035] In some embodiments, the first HDPE component is a) Number average molecular weight (M) in the range of 8,000 g / mol to 20,000 g / mol or 12,000 g / mol to 16,000 g / mol n ), b) a weight average molecular weight (M) in the range of 100,000 g / mol to 170,000 g / mol or 115,000 g / mol to 145,000 g / mol w ), c) molecular weight distribution (MWD) in the range of 5-14 or 6-9; d) a high load melt index (HLMI) in the range of 35 g / 10 min to 70 g / 10 min or 40 g / 10 min to 65 g / 10 min; e) Average molecular weight (M) in the range of 500,000 g / mol to 2,000,000 g / mol z ), f) z+1 average molecular weight (M) in the range of 1,000,000 g / mol to 3,500,000 g / mol z +1), and g) having one or more of a 2% flexural modulus in the range of 170,000 psi (1,172 MPa) to 230,000 psi (1,586 MPa) or 180,000 psi (1,241 MPa) to 210,000 psi (1,778 MPa).

[0036] In some embodiments, the first HDPE component is 1.1×10 7 ~1.6×10 7 a zero shear viscosity (η0) in the range of 0.40 to 1.75, a bulk intrinsic viscosity ([η]) in the range of 1.40 to 1.75, a viscosity ratio in the range of 0.800 to 1.100, and a long chain branching index (LCBI) in the range of 0.6 to 2.0.

[0037] In some embodiments, the first HDPE component comprises one or more HDPE homopolymers, one or more HDPE copolymers, or a combination thereof.

[0038] In some embodiments, the first HDPE component comprises one or more HDPE recycles, one or more virgin HDPE, or a combination thereof.

[0039] In some embodiments, the first HDPE component comprises one or more HDPE homopolymer recycles, one or more HDPE copolymer recycles, or a combination thereof. -Second HDPE blend composition

[0040] The second HDPE component is 0.947 g / cm 3 ~0.954g / cm 3 It has a density in the range of 0.10 g / 10 min to 1.50 g / 10 min, a melt index (I5) in the range of 0.10 g / 10 min to 1.50 g / 10 min, and an ESCR F50 at 100% Igepal in the range of 1,000 hours or more.

[0041] In some embodiments, the second HDPE component has a density at least 0.003 g / cm 3 lower than the density of the first HDPE component. 3 It has one or more of a low density, an I5 that is at least 0.02 g / 10 min lower than the I5 of the first HDPE component, and an ESCR F50 at 100% Igepal that is at least 100 hours higher than the ESCR of the first HDPE component.

[0042] In some embodiments, the second HDPE component is a) Number average molecular weight (M) in the range of 9,000 g / mol to 25,000 g / mol or 12,000 g / mol to 22,000 g / mol n ), b) a weight-average molecular weight (M) in the range of 150,000 g / mol to 350,000 g / mol or 200,000 g / mol to 300,000 g / mol w ), c) molecular weight distribution (MWD) in the range of 5-40 or 7-30; d) a high load melt index (HLMI) in the range of 5 g / 10 min to 40 g / 10 min or 7 g / 10 min to 30 g / 10 min; Average molecular weight (M) in the range of 500,000 g / mol to 2,000,000 g / mol z ), and f) z+1 average molecular weight (M) in the range of 1,000,000 g / mol to 3,500,000 g / mol z +1), and g) having one or more of a 2% flexural modulus in the range of 120,000 psi (827 MPa) to 170,000 psi (1,172 MPa) or 136,000 psi (938 MPa) to 146,000 psi (1,007 MPa).

[0043] In some embodiments, the second HDPE component is 1.0×10 5 ~1.0×10 8 a zero shear viscosity (η0) in the range of 0.80 to 1.100, a bulk intrinsic viscosity ([η]) in the range of 1.80 to 3.00, a viscosity ratio in the range of 0.800 to 1.100, and a long chain branching index (LCBI) in the range of 0.1 to 2.0.

[0044] In some embodiments, the second HDPE component comprises one or more HDPE homopolymers, one or more HDPE copolymers, or a combination thereof. -High density polyethylene

[0045] In some embodiments, the HDPE described herein comprises units derived from ethylene and units derived from C3-C 12 These include homopolymers and / or copolymers with units derived from one or more of the alpha olefins. 12 The α-olefins include substituted or unsubstituted C3 to C6 olefins such as propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and their isomers. 12When comonomers are present, the amount can be up to 20%, 15%, 10%, or 5% by weight.

[0046] Such ethylene homopolymers and / or copolymers can be produced in suspension, solution, slurry, or gas phase processes using known equipment and reaction conditions. In some embodiments, the polymerization temperature ranges from about 0° C. to about 300° C. at pressures of from about 1 psig (6.9 kPa) to 1,000 psig (6.9 MPag).

[0047] Slurry or solution polymerization systems can utilize subatmospheric pressure (less than 1 atm or about 14.7 psig, or between 1 and 14.7 psig), atmospheric pressure (about 1 atm or about 14.7 psig), or superatmospheric pressure (greater than 1 atm or about 14.7 psig, or between 1 and 1,000 psig), and temperatures ranging from about 40°C to about 300°C. Exemplary liquid-phase polymerization systems are described in U.S. Pat. No. 6,323,523 and U.S. Pat. No. 3,324,095, the disclosures of which are incorporated herein by reference in their entirety. Liquid-phase polymerization systems generally consist of a reactor to which olefin monomers and a catalyst composition are added, containing a liquid reaction medium for dissolving or suspending the polyolefin. The liquid reaction medium can consist of bulk liquid monomer or an inert liquid hydrocarbon that is unreactive under the polymerization conditions employed. Such an inert liquid hydrocarbon does not necessarily function as a solvent for the catalyst composition or the polymer obtained by the process, but typically functions as a solvent for the monomers used in the polymerization. Suitable inert liquid hydrocarbons for this purpose include isopentane, hexane, cyclohexane, heptane, benzene, toluene, etc. Reactive contact between the olefin monomer and the catalyst composition should be maintained by constant stirring or agitation. The reaction medium containing the olefin polymer product and unreacted olefin monomer is continuously removed from the reactor. The olefin polymer product is separated, and the unreacted olefin monomer and liquid reaction medium are recycled to the reactor.

[0048] Gas-phase polymerization systems can utilize pressures ranging from 1 psig (6.9 kPag) to 1,000 psig (6.9 MPa), 50 psig (344 kPag) to 400 psig (2.8 MPa), or 100 psig (689 kPag) to 300 psig (2.1 MPa), and temperatures ranging from 30°C to 130°C or 65°C to 110°C. Gas-phase polymerization systems can be stirred or fluidized bed. In some embodiments, a gas-phase fluidized bed process is carried out by continuously passing a stream containing one or more olefin monomers through a fluidized bed reactor under reactive conditions and in the presence of a catalyst composition at a velocity sufficient to maintain a bed of solid particles in suspension. A stream containing unreacted monomer is continuously removed from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled to the reactor. Product is removed from the reactor, and make-up monomer is added to the recycle stream. Gases inert to the catalyst composition and reactants may also be present in the gas stream as required for temperature control of the polymerization system.

[0049] In some embodiments, a Group VIB metal-based catalyst is used. In some embodiments, the catalyst is a chromium-based catalyst. Such HDPE homopolymers and / or copolymers have some long chain branching and a viscosity of 0.940 g / cm 3 ~0.970g / cm 3 The density is in the range of

[0050] In some embodiments, Ziegler-Natta (ZN) catalysts are used. Such catalysts are based on a Group IVB transition metal compound and an organoaluminum compound (cocatalyst). Such transition metals include, but are not limited to, Ti, Zr, Hf, and the like. Non-limiting examples of ZN catalyst systems include TiCl4 + Et3Al and TiCl3 + AlEt2Cl. Such HDPE homopolymers and / or copolymers have some long chain branching and a densitometric value of 0.940 g / cm 3 ~0.970g / cm 3The density is in the range of

[0051] In some embodiments, the HDPE described herein is produced according to the processes and conditions described in U.S. Patent Nos. 9,249,286 and 10,501,613, the disclosures of each of which are incorporated herein by reference in their entireties. In other embodiments, the HDPE described herein is produced according to the processes and conditions described in PCT Publication Nos. WO20140134193, WO20160206959, WO20160206958, WO20160206957, and WO20190121234, the disclosures of each of which are incorporated herein by reference in their entireties. In yet other embodiments, the HDPE described herein is produced according to the processes and conditions described in "Introduction to Industrial Polyethylene" by Dennis B. Malpass (2010), the disclosures of which are incorporated herein by reference in their entireties. For example, HDPE having the ESCR, zero shear viscosity, bulk intrinsic viscosity, and / or LCBI properties described herein can be produced using a chromium catalyst under system conditions such as an operating pressure of about 590-620 PSI, an operating temperature of about 205-230°F, and a residence time of about 0.7-0.9 hours. -Compound extruder

[0052] In some embodiments, the first and second HDPE components are fed into an extruder or mixer, where the blend is subjected to compounding conditions. The compounding conditions are performed in the extruder or mixer and are tailored to the specific polyolefin and, optionally, additives (such as one or more primary antioxidants, one or more secondary antioxidants, and / or peroxides) blend. The second extruder or mixer performs temperature, pressure, and shear conditions sufficient to intimately mix the first and second HDPE components, and optionally, additives, to produce a substantially homogeneous polymer blend of the first and second HDPE components. In some embodiments, the compounding conditions include a temperature in the compounding zone of 300°C or less, 250°C or less, or 200°C or less. In some embodiments, the temperature in the compounding zone can range from 130°C to 280°C, 140°C to 265°C, or 150°C to 250°C. -Antioxidants

[0053] In some embodiments, primary and / or secondary antioxidants are added to stabilize the reaction when exposed to oxygen during compounding.

[0054] Primary antioxidants react rapidly with peroxy and alkoxy radicals. Examples of primary antioxidants, sometimes referred to as "long-term antioxidants," include phenolic antioxidants and hindered amine antioxidants, as disclosed in U.S. Pat. No. 5,623,523. The disclosure of U.S. Pat. No. 6,392,056 is incorporated herein in its entirety. Suitable primary antioxidants include, but are not limited to, Irganox® antioxidants available from BASF, such as Irganox® 1010, Irganox® 1076, Irganox® 1098, Irganox® 1330, Irganox® 1425WL, Irganox® 3114, Irganox® 245, and Irganox® 1135. Examples of suitable antioxidants, including phenolic antioxidants and hindered amine antioxidants, are described in U.S. Patent No. 6,363,953 and U.S. Patent No. 7,285,617, the disclosures of which are incorporated herein in their entirety.

[0055] Non-limiting examples of primary antioxidants include 2,6-di-tertbutyl-4-methylphenol, pentaerythrityl-tetrakis(3-(3',5'-di-tertbutyl-4-hydroxyphenyl)-propionate, octadecyl 3-(3',5'-di-tertbutyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tertbutyl-4-hydroxyphenyl)benzene, 1,3,5-tris(3',5 '-Di-tertbutyl-4'-hydroxybenzyl)isocyanurate, bis-(3,3-bis-(4-'-hydroxy-3'-tertbutylphenyl)butanoic acid)-glycol ester, N,N'-hexamethylenebis(3,5-di-tertbutyl-4-hydroxy-hydrocinnamide, 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol, 2,2'-ethylidenebis(4,6-di-tertbutylphenoxy) ol), 1,1,3-tris(2-methyl-4-hydroxy-5-tertbutylphenyl)butane, 1,3,5-tris(4-tertbutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,-6-(1H,3H,5H)-trione, 3,9-bis(1,1-dimethyl-2-(beta-(3-tertbutyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl)-2,4,8,10-tetraoxaspiro(5,5 ) undecane, 1,6-hexanediylbis(3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoate), 2,6-di-tertbutyl-4-nonylphenol, 4,4'-butylidenebis(6-tertbutyl-3-methylphenol), 2,2'-methylenebis(4-methyl-6-tertbutylphenol), and triethylene glycol bis(3-tertbutyl-4-hydroxy-5-methylphenyl)propionate.

[0056] Secondary antioxidants, also known as "short-term antioxidants," can be added at any convenient location in the mixer / extruder. Secondary antioxidants are commercially available, such as Irgafos® antioxidants available from BASF (Irgafos® 168, Irgafos® 126, Irganox® PS800, Irganox® PS802, etc.).

[0057] Examples of secondary antioxidants include, for example, aliphatic thiols, phosphites, phosphonites, etc. Specific examples of secondary antioxidants include distearyl pentaerythritol diphosphite, isodecyl diphenyl phosphite, diisodecyl phenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, dilauryl-β,β-thiodipropionate, β-naphthyl disulfide, thiol-β-naphthol, 2-mercaptobenzothiazole, benzothiazyl disulfide, phenothiazine, tris(p-nonylphenyl) phosphite, and zinc dimethyldithiocarbamate. -Peroxide

[0058] In some embodiments, a peroxide-modified resin can be used in the blend. The peroxide treatment conditions are carried out in an extruder. In some embodiments, the peroxide treatment conditions refer to subjecting the HDPE and peroxide blend to conditions of pressure, temperature, and shear sufficient for the peroxide to react with the HDPE, causing polymer chain scission and / or attachment of some polymer chains along the backbone of other polymer chains, resulting in long chain branching.

[0059] In some embodiments, the amount of peroxide radical initiator added to the polyethylene composition ranges from 0.1 to 100 ppm, alternatively 0.5 to 100 ppm, by weight of peroxide relative to the polyethylene composition. In some embodiments, the amount of peroxide radical initiator added to the polyethylene composition is determined by rheology or film testing. In some embodiments, the amount of radical initiator added to the polyethylene composition is determined by the desired change in rheological polydispersity (ER). In some embodiments, the amount of radical initiator added to the polyethylene composition is determined by foam stability testing.

[0060] In some embodiments, the first HDPE component, the second HDPE component, and / or the composition are treated with peroxide in an extruder under temperature, pressure, and shear conditions sufficient to increase long-chain branching and thereby enhance the processability of the first polyethylene component, the second polyethylene component, and / or the composition, as the case may be. The blended composition can also be treated with peroxide during the process of blending the first and second HDPE components under compounding conditions in an extruder or mixer. Improving the processability of the first HDPE component and / or the second HDPE component prior to blending improves the processability of the composition after the components are blended.

[0061] In some embodiments, the first HDPE component, the second HDPE component, and / or the composition are processed under the compounding conditions disclosed herein. In some embodiments, without wishing to be bound by theory, it is believed that temperatures in the range of 150°C to 250°C promote long-chain branching over chain scission, resulting in processed polymers with higher long-chain branching and improved processability due to higher melt strength. It is believed that as the temperature is reduced from 250°C to 150°C, more long-chain branching occurs.

[0062] Non-limiting examples of suitable radical initiators include 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, 2-hydroxy-1,1-dimethylbutyl peroxyneoheptanoate, α-cumyl peroxyneoheptanoate, t-amyl peroxyneodecanoate, t-butyl peroxyneodecanoate, di(2-ethylhexyl) peroxydicarbonate, di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, t-butyl peroxydicarbonate, Cineoheptanoate, t-amyl peroxypivalate, t-butyl peroxypivalate, diisononanoyl peroxide, didecanoyl peroxide, 3-hydroxy-1,1-dimethylbutylperoxy-2-ethylhexanoate, didecanoyl peroxide, 2,T-azobis(isobutyronitrile), di(3-carboxypropionyl) peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, dibenzoyl peroxide, t-amyl peroxy 2-ethylhexanoate, t-butyl peroxide peroxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxy-(cis-3-carboxy)propenoate, 1,1-di(t-amylperoxy)cyclohexane, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, OO-t-amyl O-(2-ethylhexyl) monoperoxycarbonate, OO-t-butyl O-isopropyl monoperoxycarbonate, OO-t-butyl O-(2-ethylhexyl) monoperoxycarbonate Carbonate, polyether tetrakis(t-butylperoxycarbonate), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-amyl peroxyacetate, t-amyl peroxybenzoate, t-butyl peroxyisononanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, di-t-butyl diperoxyphthalate, 2,2-di(t-butylperoxy)butane, 2,2-di(t-amylperoxy)propane, n-butyl 4,4-di(t-butylperoxy)valerate, ethyl 3,3-Di(t-amylperoxy)butyrate, ethyl 3,3-di(t-butylperoxy)butyrate, dicumyl peroxide, a,a'-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di(t-amyl)peroxide, t-butyl α-cumyl peroxide, di(t-butyl)peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, dicetyl peroxydicarbonate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7 -triperoxonane, tert-butylperoxy 2-ethylhexyl carbonate, tert-butylperoxide n-butyl fumarate (benzoate), dimyristoyl peroxydicarbonate, 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, tert-butyl hydroperoxide, bis(4-t-butylcyclohexyl) peroxydicarbonate, and 1,2,4,5,7,8-hexoxonane, 3,6,9-trimethyl-3,6,9-tris(ethyl and propyl derivatives). - Compression molding / Blow molding

[0063] Compression molding is a high-speed plastics conversion process for caps and closures, offering efficient processing in terms of short cycle times and low energy consumption. This results in excellent performance in terms of throughput and dimensional consistency of the final product. Low conversion temperatures make the material less susceptible to degradation.

[0064] Polyolefins useful in injection molding processes are also typically useful in compression molding processes, including, but not limited to, the production of caps and closures. In some embodiments, polyolefins used in compression molding have significant shear thinning properties and proportionally low resistance to flow. These properties help maintain high throughput and excellent properties of the final products (e.g., ESCR) produced.

[0065] Die swell is a common phenomenon in polyolefin extrusion processes, where a stream of molten polymer material is forced through a die. Related processes include, but are not limited to, compression molding, injection molding, and blow molding. Die swell is a phenomenon directly related to entropy and relaxation of the polymer within the flowstream. The polymer melt flowstream has a constant velocity before entering the die, and the polymer chains within the stream assume a roughly spherical structure, maximizing entropy. Upon extrusion through the die, the cross-sectional area within the die decreases, thereby increasing the polymer flow rate. The polymer chains within the polymer melt flowing through the die begin to lose their spherical shape due to the increased flow rate. The polymer chains become longer, and the physical entanglements between them decrease to some extent depending on the length of time the polymer remains in the die. As the polymer stream leaves the die, the remaining physical entanglements allow the polymer chains within the die stream to regain some of their previous shape and spherical volume, returning to a roughly spherical structure that maximizes entropy.

[0066] Because polymer chain disentanglement is a kinetic process, the longer the die or the lower the flow rate, the longer the disentanglement process. Commercial incentives impose a lower limit on the polymer flow rate through the die and an upper limit on the time the polymer can remain in the die. Therefore, there is a demand for polymers that are less susceptible to polymer chain entanglement.

[0067] One of the challenges of using polymer recyclates in compression molded caps and closures is excessive die swell. Die swell causes problems during the slicing stage of the extrudate and transfer to the die. The polymer swells to a "mushroom" shape at the top, making transfer difficult. This swell can be a problem in polymer recyclate streams, especially in the case of I2 and / or I 21 is a material property inherent to the low recycle stream.

[0068] Die swell is related to polymer elasticity, as polymer systems can shrink and swell. When a random-coil system of entangled polymer chains enters a capillary die in the molten state, it contracts, partially relaxes within the capillary, and then partially recovers at the exit when it is no longer confined by the capillary. Swelling upon capillary discharge can be very severe for polyolefins such as polyethylene and polypropylene. The effects of swelling are not limited to compression molding, but are important in some polymer processes. Excessive swelling can cause processing problems and defects in molded parts. ISO 11443 specifies a method for measuring die swell through an attachment to a capillary rheometer.

[0069] Because polymer chain disentanglement is a kinetic process, the longer the die or the lower the flow rate, the longer the disentanglement. Commercial incentives impose a lower limit on the polymer flow rate through the die and also an upper limit on the time the polymer can remain in the die. Thus, there is a demand for polymers that are less susceptible to polymer chain entanglement.

[0070] Typically, die swell can also be reduced by using polymers that are less susceptible to such chain entanglements, such as, but not limited to, polymers with shorter average chain lengths, resulting in lower I and / or I 21 Since recycled polymers inherently contain a large amount of long chain polymers, the I2 and / or I 21 I2 and / or I 21 Dry blending and / or compounding high virgin polymers with polymer recycles (low flow polyethylene) can improve the overall I2 and / or I 21 However, this approach provides limited improvement in overall die swell due to the continued presence of long molecular weight chains in the polymer recycle component of the blend.

[0071] Visbroken polymer recycles have high enough I2 and / or I to reduce die swell during compression molding to acceptable levels. 21 Such treated polymer recycles can be used in compression molding operations, either alone or in combination with one or more virgin polymers and / or one or more other treated polymer recycles.

[0072] In some embodiments, processed polyolefin recycle materials useful for compression molding have a die swell (as measured by ASTM D3835 or ISO 11443) of 150% or less, 140% or less, 130% or less, 120% or less, 110% or less, or 100% or less.

[0073] In some embodiments, processed polyolefin recycle materials useful for compression molding have a die swell (as measured by ASTM D3835 or ISO 11443) of 200% or less, 190% or less, or 180% or less. Specific Embodiments

[0074] In some embodiments, the composition comprises a blend of a first HDPE component and a second HDPE component. The first HDPE component has a viscosity of 0.955 g / cm 3 ~0.966g / cm 3 , a melt index (I5) in the range of 1.50 g / 10 min to 3.50 g / 10 min, and an environmental stress crack resistance ("ESCR") F50 of less than 24 hours on 100% Igepal. The second HDPE component has: i) a viscosity of 0.947 g / cm 3 ~0.954g / cm 3 It has a density in the range of 0.10g / 10min to 1.50g / 10min, an I5 in the range of 0.10g / 10min to 1.50g / 10min, and an ESCR F50 in the range of over 1,000 hours at 100% Igepal.

[0075] In some embodiments, the first HDPE component is present in the blend in an amount ranging from 40% to 95%, 50% to 90%, 60% to 85%, or 70% to 80% by weight, respectively, and the second HDPE component is present in the blend in an amount ranging from 5% to 60%, 10% to 50%, 15% to 40%, or 20% to 30% by weight, respectively. The weight percentages are based on the combined weight of the first and second HDPE components.

[0076] In some embodiments of the composition, in addition to any one or more of the foregoing limitations, the composition may further comprise a composition in which the second HDPE component has a density at least 0.003 g / cm 3 greater than the density of the first HDPE component. 3 It is further characterized by having one or more of a low density, an I5 at least 0.02 g / 10 min lower than the I5 of the first HDPE component, and / or an ESCR F50 at 100% Igepal at least 100 hours greater than the ESCR F50 at 100% Igepal at least 100 hours of the first HDPE component.

[0077] In some embodiments of the composition, in addition to any one or more of the limitations above, the composition is characterized in that the first HDPE component has one or more of the following: a) M in the range of 8,000 g / mol to 20,000 g / mol or 12,000 g / mol to 16,000 g / mol n , b) M in the range of 100,000 g / mol to 170,000 g / mol or 115,000 g / mol to 145,000 g / mol w , c) MWD in the range of 5–14 or 6–9; d) HLMI in the range of 35g / 10min to 70g / 10min or 40g / 10min to 65g / 10min, and e) A 2% flexural modulus in the range of 170,000 psi (1,172 MPa) to 230,000 psi (1,586 MPa) or 180,000 psi (1,241 MPa) to 210,000 psi (1,778 MPa).

[0078] In some embodiments of the composition, in addition to any one or more of the limitations above, the composition is characterized in that the first HDPE component has one or more of the following: a) 1.1 x 10 7 ~1.6×10 to 1.6x10 7 The zero shear viscosity (η0) is in the range b) a bulk intrinsic viscosity ([η]) in the range of 1.40 to 1.75, and c) Long-chain branching index (LCBI) in the range of 0.6–2.0.

[0079] In some embodiments of the composition, in addition to any one or more of the limitations above, the composition is characterized in that the second HDPE component has one or more of the following: a) M in the range of 9,000 g / mol to 25,000 g / mol or 12,000 g / mol to 22,000 g / mol n , b) M in the range of 150,000 g / mol to 350,000 g / mol, or 200,000 g / mol to 300,000 g / mol w , c) MWD in the range of 10–40 or 15–30; d) HLMI in the range of 5g / 10min to 40g / 10min or 7g / 10min to 30g / 10min, and e) A 2% flexural modulus in the range of 120,000 psi (827 MPa) to 170,000 psi (1,172 MPa) or 136,000 psi (938 MPa) to 146,000 psi (1,007 MPa).

[0080] In some embodiments of the composition, in addition to any one or more of the limitations above, the composition is characterized in that the second HDPE component has one or more of the following: a) 1.0 × 10 5 ~1.0×10 8 Zero shear viscosity (η0) in the range b) a bulk intrinsic viscosity ([η]) in the range of 1.80 to 3.00, and c) Long-chain branching index (LCBI) in the range of 0.1 to 2.0.

[0081] In some embodiments of the composition, in addition to any one or more of the limitations above, the composition is characterized in that the blend composition has one or more of the following: a) 0.951 g / cm 3 ~0.962g / cm 3 or 0.956 g / cm 3 ~0.960g / cm 3 Density in the range b) a melt index (I5) in the range of 0.60 g / 10 min to 2.50 g / 10 min, or 0.80 g / 10 min to 1.80 g / 10 min, and c) Environmental Stress Cracking Resistance ("ESCR") F50 ranging from 24 hours to 1,000 hours for 100% Igepal and / or 24 hours to 84 hours for 10% Igepal; d) M in the range of 10,000 g / mol to 20,000 g / mol n , e) M in the range of 130,000 g / mol to 230,000 g / mol or 156,000 g / mol to 194,000 g / mol w , f) MWD in the range of 8–20 or 10–15; g) HLMI in the range of 15g / 10min to 45g / 10min or 20g / 10min to 40g / 10min; h) overall polydispersity ratio (PDR) in the range of 15 to 60; i) 1.0 × 10 6 ~3.0×10 7 Zero shear viscosity (η0) in the range j) bulk intrinsic viscosity ([η]) in the range of 1.5 to 2.5; k) a long-chain branching index (LCBI) in the range of 0.3 to 1.3, and l) A 2% flexural modulus in the range of 165,000 psi (1,138 MPa) to 215,000 psi (1,482 MPa), or 175,000 psi (1,207 MPa) to 205,000 psi (1,413 MPa).

[0082] In some embodiments of the composition, in addition to one or more of the limitations set forth above, the first HDPE component is a) one or more HDPE homopolymers, one or more HDPE copolymers, or a combination thereof; b) one or more recycled HDPE materials, one or more virgin HDPE materials, or a combination thereof; or c) Contains one or more HDPE homopolymer recycles, one or more HDPE copolymer recycles, or a combination thereof.

[0083] In some composition embodiments, in addition to one or more of the foregoing limitations, the composition is characterized in that the first HDPE component and / or the second HDPE component are treated with peroxide prior to blending, or the blend composition is treated with peroxide during or after blending, wherein such peroxide treatment of the components or composition is carried out in an extruder at a temperature in the range of 150°C to 270°C under conditions of pressure and shear sufficient to enhance the melt strength of the final blend composition compared to a corresponding blend composition in which the components or composition have not been treated with peroxide.

[0084] In some embodiments of the composition, in addition to one or more of the limitations set forth above, the second HDPE component comprises one or more virgin HDPE homopolymers, one or more virgin HDPE copolymers, or a combination thereof.

[0085] In some embodiments of the composition, in addition to one or more of the foregoing limitations, the first HDPE component and the second HDPE component are melt blended at a temperature ranging from 150°C to 270°C. In further embodiments, the blend further comprises one or more primary antioxidants, one or more secondary antioxidants, or a combination thereof. In further embodiments, the total amount of the primary antioxidants and / or the total amount of the secondary antioxidants can be present in the blend at up to 1,900 ppm, up to 1,500 ppm, or up to 1,000 ppm, respectively, based on the total weight of the first HDPE component and the second HDPE component.

[0086] The following examples are illustrative of the present invention, but those skilled in the art will recognize that many variations are possible within the spirit of the invention and the scope of the claims. In order to better understand the present invention, the following examples of preferred embodiments are provided. The following examples are not intended to limit or define the scope of the present invention in any way. Example

[0087] The following examples are included to demonstrate preferred embodiments of the invention. It should be understood by those of skill in the art that the techniques disclosed in the examples which follow are techniques discovered by the inventors to function well in the practice of the invention, and therefore are believed to constitute preferred modes for the practice of the invention. However, those of skill in the art should, in light of the present disclosure, understand that many changes can be made in the specific embodiments which are disclosed and still obtain like or similar results without departing from the spirit and scope of the invention.

[0088] In the following examples, HDPE recycled and / or commercially available recycled materials are replaced with commercially available low melt index HDPE compositions. Test Method

[0089] Environmental Stress Cracking Resistance (ESCR) - The environmental stress cracking resistance (ESCR) of a resin was measured according to ASTM-D1693-01, Method B, which measures the resin's susceptibility to mechanical failure by cracking under constant strain conditions and in the presence of crack accelerators such as soaps and other wetting agents. Measurements were performed on notched specimens in a 10 percent by volume aqueous solution of Igepal CO-630 (vendor: Rhone-Poulec, NJ) held at 50°C. Ten specimens were evaluated per measurement. The ESCR value of the resin was reported as F50, the 50 percent failure time calculated from a probability graph.

[0090] Density was measured according to ASTM D-4703 and ASTM D-1505 / ISO-1183.

[0091] Die swell was determined by an in-house developed test using a Goetfert Rheograph 25 capillary rheometer. The polymer melt was extruded through the die at a temperature of 190 °C and a shear rate of 525 s-1. The die swell of the extrudate was measured by a laser positioned 78 mm below the bottom of the die. The die orifice diameter was 1 mm, L / D was 0.25, and the entrance angle was 90°. The extrudate strand was cut 120 mm below the bottom of the die before measurement.

[0092] High Load Melt Index ("I 21 ") was measured according to ASTM D-1238-F (190°C / 21.6 kg).

[0093] Shear rheology measurements were performed according to ASTM 4440-95a to measure dynamic viscoelastic properties (storage modulus G', loss modulus G", and complex viscosity η *, as a function of the oscillation frequency ω) were characterized. A rotational rheometer (TA Instruments) was used for the rheological measurements. A 25 mm parallel-plate fixture was used. Samples were compression molded into disks (approximately 29 mm diameter and 1.3 mm thick) using a hot press at 190 °C. Oscillation frequency sweep experiments (398.1 rad / s to 0.0251 rad / s) were performed at 190 °C. The applied strain amplitude was approximately 10%, and the operating gap was set to 1 mm. Nitrogen was flowed into the sample chamber to minimize thermal oxidation during the measurements.

[0094] Melt elasticity ("ER") was determined as described in R. Shroff and H. Mavridis, "A New Measurement of Polydispersity from Rheological Data of Polymer Melts," J. Applied Polymer Science 57 (1995) 1605. Reference is also made to U.S. Pat. Nos. 7,238,754, 6,171,993, and 5,534,472 (col. 10, lines 20-30), the teachings of which are incorporated herein by reference. Thus, storage modulus (G') and loss modulus (G'') were measured. A linear equation was fitted to the relationship between logG' and logG'' by least squares regression using the lowest nine frequency points (five points per 10 frequencies). ER was calculated as follows: ER = (1.781 × 10 -3 )×G' Here, G' = 5,000 dyn / cm 2 The same ER calculation procedure and formula were used for both linear and long-chain branched polyolefins.

[0095] PDR, or "Total Polydispersity Index", is calculated by the equation 27 of R. Shroff and H. Mavridis, "A New Measure of Polydispersity from Rheological Data of Polymer Melts", Applied Polymer Science 57 (1995) 1605, p. 1619, G* ref,1 =1.95*10 4 dyn / cm 2 and log10 (G* ref,3 / G* ref,1 ) = 2. The same procedure and equations were used for PDR calculations for both linear and long-chain branched polyolefins.

[0096] Complex viscosity η at a frequency of 0.1 rad / s * 0.1 and the complex viscosity η at a frequency of 100 rad / s * 100 The ratio of η * 0.1 / η * 100 is used as an additional measure of the shear sensitivity and hence the rheological breadth, or polydispersity, of the polymer melt.

[0097] Melt index ("I2") was measured according to ASTM D-1238-E (190°C / 2.16 kg).

[0098] Melt index ("I5") was measured according to ASTM D-1238 (190°C / 5kg).

[0099] The molecular weight distribution ("MWD") is z / M w Also known as molecular weight average (number average molecular weight, M n , weight average molecular weight, M w , z average molecular weight, M z , and z+1 average molecular weight, M z+1 ) is determined using high temperature polymer char gel permeation chromatography ("GPC") (also known as size exclusion chromatography ("SEC")) equipped with a filter-based infrared detector, an IR5, 4-capillary differential bridge viscometer, and a Wyatt 18-angle light scattering detector. n , M w , M zThe δ, MWD, and short-chain branching (SCB) profiles are reported using an IR detector, while the long-chain branching parameter g' is determined using a combination of a viscometer and an IR detector at 145°C. Three Agilent PLgel Olexis GPC columns were used at 145°C to fractionate the polymers based on their hydrodynamic size in 1,2,4-trichlorobenzene (TCB) containing 300 ppm of the antioxidant butylated hydroxytoluene (BHT) as the mobile phase. 16 mg of polymer was weighed into a 10 mL vial and sealed for GPC measurement. The dissolution process was carried out automatically at 160°C for 1 h with continuous shaking in an Agilent autosampler (8 mL). in TCB). During the dissolution process, 20 μL of heptane was also injected into the vial as a flow marker. After the dissolution process, 200 μL of the solution was injected into the GPC column. The GPC column was calibrated based on 12 monodisperse polystyrene (PS) standards (provided by PSS) ranging from 578 g / mol to 3,510,000 g / mol. Comonomer compositions (or SCB profiles) were reported based on various calibration profiles obtained using a series of relatively narrow polyethylenes with known values of CH3 / 1000 total carbon (polyethylenes containing 1-hexene and 1-octene comonomers were provided by Polymer Char, while polyethylenes containing 1-butene were synthesized in-house), measured by established solution NMR techniques. GPC One software was used to analyze the data. The long-chain branching parameter g' is determined by the following equation: g'=[η] / [η] lin where [η] is the average intrinsic viscosity of the polymer, which is derived by summing slices on the GPC profile as follows:

number

number

[0100] The zero shear viscosity η is determined using an approximation of the Sabia equation for dynamic complex viscosity and radian frequency, as described in Shroff & Mavridis, (1999) "Long Chain Branching Index of Essentially Linear Polyethylenes," Macromolecules, 32, 8454-8464 (emphasis in Appendix B), the disclosure of which is incorporated herein by reference in its entirety.

[0101] The LCBI is determined using Equation 13.

number

[0102] Long-chain branching frequency is the ratio of long-chain branches per million carbon atoms, or LCB / 10 6 C, determined by the Janzen & Colby method (J. Janzen and R.H. Colby, "Diagnosing Long Chain Branching in Polyethylenes," Journal of Molecular Structure, Vol. 485-486, 10 August 1999, Pages 569-583) using equations (2-3) and the constants in Table 2 of the above reference. Specifically, the zero shear viscosity at 190°C, η * Ois determined by extrapolating complex viscosity data using the Sabia equation, as will be explained later. The weight average molecular weight Mw is determined by GPC. Using these two parameters and the Janzen & Colby methodology, the long chain branching frequency LCB / 10 6 C can be determined numerically and is determined by three parameters (η, M w , LCB / 10 6 C) All of them satisfy equations (2-3) in the above reference. In the Janzen & Colby methodology, the zero shear viscosity of the material is compared with that of a perfectly linear polymer (LCB / 10 6 The ratio η0 / η of the zero shear viscosity (C=0) 0,線形 But LCB / 10 6 It shows a maximum at a certain value of C, and therefore η0 / η 0,線形 For all values of , such a ratio is possible. 6 It is predicted that there are two levels or values of C. In this calculation, LCB / 10 6 The minimum value of C is always within the given ratio η0 / η 0,線形 was selected. raw materials

[0103] The raw materials used herein are listed in Tables 1-5 below. BM1-BM3 identify and characterize benchmark polymers used to establish the ESCR targets achieved by the HDPE blends disclosed herein. FHC1 and FHC2 identify and characterize the first HDPE component used in the HDPE blends disclosed herein. SHC1-SHC6 identify and characterize the second HDPE component used in the HDPE blends disclosed herein. P1-P7 identify and characterize other HDPE polymers used for comparison to the HDPE blends disclosed herein.

[0104] Table 1 lists the raw material composition types and grade numbers, as well as the label identifiers used in the examples in Tables 2-25 below. [Table 1] 1 Available from LyondellBasell (Houston, TX) 2 Available from Envision Plastics, Reedsville, North Carolina 3Available from Chevron Phillips Chemical, Houston, TX

[0105] Table 2 lists the density, I2, I5, HLMI, ESCR F50, 100% Igepal, and die swell for the polymers identified in Table 1. [Table 2]

[0106] Table 3 lists the M of the polymers identified in Table 1. w , M n , M w / M n (MWD), M. z / M w , M z , and M z+1 is stated. [Table 3]

[0107] Table 4 lists the ER, PDR, ETA0, ETA*100, ETA*1000, and IV for the polymers identified in Table 1. [Table 4]

[0108] Table 5 lists the bulk comonomer, bulk IV, viscosity ratio, LCBI, and LCB / 10 for the polymers identified in Table 1. 6 C is listed. [Table 5] Examples 1-3

[0109] Examples 1-36 in Tables 6-11 show the parameters and properties of blends containing FHC1 and one or more of each of SHC1, SHC2, SHC3, SHC4, SHC5, SHC6, P2, P3, P4, and P7.

[0110] Table 6 shows the weight percentages of polymers FHC1, SHC1, SHC2, SHC3, SHC4, SHC5, SHC6, P2, P3, P4, and P7 used in blend examples 1 through 36. The properties of these blends are shown in Tables 7 through 11. [Table 6]

[0111] Table 7 lists the densities, I2, I5, HLMI, ESCR F50, 100% Igepal, and die swell for the example blends shown in Table 6. Figure 2 shows a comparison of ESCR performance from the data shown in Table 7. [Table 7] [Table 7-2]

[0112] Table 8 lists the M of the example blends identified in Table 6. w , M n , M w / M n (MWD), M. z / M w , M z , and M z+1 is stated. [Table 8] [Table 8-2]

[0113] Table 9 lists the ER, PDR, ETA0, ETA*100, ETA*1000, and IV for the example blends identified in Table 6. [Table 9] [Table 9-2]

[0114] Table 10 lists the bulk comonomers, bulk IV, viscosity ratio, LCBI, and LCB / 10 for the polymers identified in Table 6. 6 C, LCB-SHC, LCB-FHC, %FHC, and linear LCB blends are listed. [Table 10] [Table 10-2] [Table 10-3]

[0115] Table 11 lists the SHC ETA0, SHC IV, FHC ETA0, FHC IV, blend ETA0, IV, and LCBI for the example blends identified in Table 6. [Table 11] Examples 42-61

[0116] Examples 42-61 in Tables 12-17 show the parameters and properties of blends containing FHC2 and one or more of each of SHC1, SHC3, SHC4, SHC5, SHC6, P2, and P7.

[0117] Table 12 shows the weight percentages of polymers FHC2, SHC1, SHC3, SHC4, SHC5, SHC6, P2, and P7 used in blend examples 42-61. The properties of these blends are shown in Tables 13-17. [Table 12]

[0118] Table 13 lists the density, I2, I5, HLMI, ESCR F50, 100% Igepal, and die swell for the example blends shown in Table 12. Figure 3 shows the ESCR performance comparisons in Table 13. [Table 13] [Table 13-2]

[0119] Table 14 shows the M of the example blends identified in Table 12. w , M n , M w / M n (MWD), M. z / M w , M z , and M z+1 is stated. [Table 14] [Table 14-2]

[0120] Table 15 lists the ER, PDR, ETA0, ETA*100, ETA*1000, and IV for the example blends identified in Table 12. [Table 15] [Table 15-2]

[0121] Table 16 lists the bulk comonomers, bulk IV, viscosity ratio, LCBI, and LCB / 10 for the polymers identified in Table 12. 6 C, LCB-SHC, LCB-FHC, %FHC, and linear LCB blends are described. [Table 16] [Table 16-2]

[0122] Table 17 lists the SHC ETA0, SHC IV, FHC ETA0, FHC IV, blend ETA0, IV, and LCBI for the example blends identified in Table 12. [Table 17] [Table 17-2] Examples 37-41

[0123] Examples 37-41 in Tables 18-22 show the parameters and properties of blends of FHC1 and BM1 with SHC1, SHC3, SHC4, SHC5, and SHC6, respectively. In these ternary blends, FHC1 and BM1 form the first HDPE component, and the density of the FHC1 and BM1 blend is 0.955 g / cm. 3 Exceeds.

[0124] Table 18 shows the weight percentages of polymers FHC1, SHC1, SHC3, SHC4, SHC5, SHC6, and BM1 used in blend examples 37-41. The properties of these blends are shown in Tables 19-22. [Table 18]

[0125] Table 19 lists the densities, I2, I5, HLMI, ESCR F50, 100% Igepal, and die swell for the example blends identified in Table 18. [Table 19]

[0126] Table 20 lists the M of the example blends identified in Table 18. w , M n , M w / M n (MWD), M. z / M w , M z , and M z+1 is stated. [Table 20]

[0127] Table 21 lists the ER, PDR, ETA0, ETA*100, ETA*1000, and IV for the example blends identified in Table 18. [Table 21]

[0128] Table 22 lists the bulk comonomers, bulk IV, viscosity ratio, LCBI, and LCB / 10 for the polymers identified in Table 18. 6 C, LCB-SHC, LCB-FHC, %FHC, and linear LCB blends are described. [Table 22] Diameter Swell

[0129] Table 23 compares blends of FHC2 and SHC1 disclosed herein with the benchmark polymer BM1. [Table 23]

[0130] Table 24 compares the die swell performance of Example 63 with that of Benchmark Example 62. Diameter swell and weight swell were measured on a Uniloy 350R2 single-head blow molding machine. The machine was started running virgin BM1 on a 1-gallon center-fill bottle, targeting a swell of 90 grams and a diameter of 9.0 cm, as measured by the graduated handle on the mold. BM1 is a general-purpose Cr-HDPE (manufactured using a chromium catalyst) widely used for blow molding and serves as a processability control for this test.

[0131] The FHC2 / SHC1 blend was introduced "on top" of the BM1 control, mimicking a commercial-type conversion. Bottle weight variations occur due to differences in parison thickness and tail flash length. This bottle weight variation is defined as "weight swell" and is the first thing operators notice when switching materials. The die gap is then manually adjusted to bring the bottle weight back to the target value of 90 grams.

[0132] Once the prototype returns to the target weight, measure the diameter swell with the graduated handle on the mold. Large deviations from the target diameter swell may require tooling changes to produce a wider or narrower parison. The target range for weight swell is -20g to +20g, and the target range for diameter swell is 8.0cm to 10.0cm. Example 63 was within the target range. This comparison is tabulated in Table 24 and graphically shown in Figure 4. [Table 24] 1 gram weight change 2 Measured at the handle (cm)

[0133] For brevity, only certain ranges are explicitly disclosed herein. However, in addition to the stated ranges, any lower limit can be combined with any upper limit to describe a range not expressly stated. Similarly, a range from any lower limit can be combined with any other lower limit to describe a range not expressly stated. Similarly, a range from any upper limit can be combined with any other upper limit to describe a range not expressly stated. Furthermore, a range includes every point or individual value between its endpoints, even if not expressly stated. Thus, every point or individual value can be combined with any other point or individual value, or with other lower or upper limits, to serve as its own lower or upper limit and describe a range not expressly stated.

[0134] While the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made therein without departing from the spirit and scope of the invention, as defined by the appended claims. Furthermore, the scope of this application is not intended to be limited to the particular embodiments of the processes, machines, film structures, layer configurations, means, methods, and / or steps described herein. As will be readily apparent from this disclosure, those skilled in the art can utilize, in accordance with the present invention, currently existing or later-developed processes, machines, film structures, layer configurations, means, methods, and / or steps that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein. Accordingly, the appended claims are intended to include within their scope such processes, machines, film structures, layer configurations, means, methods, and / or steps.

Claims

1. 1. A composition comprising a blend, said blend comprising: a) 40% to 95% by weight of a first high density polyethylene (“HDPE”) component; i) 0.955g / cm ３ ~0.966g / cm ３ and a density in the range ii) a melt index (I ５ )and, iii) an Environmental Stress Crack Resistance ("ESCR") F50 of less than 24 hours at 100% Igepal; b) 5% to 60% by weight of a second HDPE component, i) 0.947g / cm ３ ~0.954g / cm ３ and a density in the range ii) I in the range of 0.10 g / 10 min to 1.50 g / 10 min ５ and, iii) an ESCR F50 of 1,000 hours or greater on 100% Igepal; The weight percentages are based on the combined weight of the first HDPE component and the second HDPE component.

2. 10. The composition of claim 1, wherein the first HDPE component is present in an amount ranging from 50% to 90% by weight and the second HDPE component is present in an amount ranging from 10% to 50% by weight.

3. 3. The composition of claim 2, wherein the first HDPE component is present in an amount ranging from 60% to 85% by weight and the second HDPE component is present in an amount ranging from 15% to 40% by weight.

4. The second HDPE component is a) at least 0.003 g / cm greater than the density of the first HDPE component ３ Low density, b) I of the first HDPE component ５ At least 0.02 g / 10 min lower than I ５ , and 10. The composition of claim 1, wherein said first HDPE component has one or more of: c) an ESCR F50 at 100% Igepal that is at least 100 hours greater than the ESCR F50 at 100% Igepal of said first HDPE component.

5. The first HDPE component is a) has a number average molecular weight (M ｎ ), b) has a weight average molecular weight (M ｗ ), c) molecular weight distribution (MWD; M) in the range of 5 to 14 ｗ / M ｎ ), d) a high load melt index (HLMI) in the range of 35 g / 10 min to 70 g / 10 min; and e) a 2% flexural modulus in the range of 170,000 psi (1,172 MPa) to 230,000 psi (1,586 MPa).

6. The first HDPE component is a) 1.1 x 10 ７ ~1.6 x 10 ７ The zero shear viscosity (η ０ ), b) a bulk intrinsic viscosity ([η]) in the range of 1.40 to 1.75, and c) a long chain branching index (LCBI) in the range of 0.6 to 2.

0.

7. 10. The composition of claim 1, wherein prior to blending with the second HDPE component, the first HDPE component is treated with peroxide carried out in an extruder at a temperature in the range of 150°C to 270°C under conditions of pressure and shear sufficient to increase the melt strength of the composition compared to a corresponding blend of the first HDPE component and the second HDPE component, where the first HDPE component has not been treated with peroxide.

8. The second HDPE component is a) a number average molecular weight (M) in the range of 9,000 g / mol to 25,000 g / mol ｎ ), b) a weight average molecular weight (M) in the range of 150,000 g / mol to 350,000 g / mol ｗ ), c) molecular weight distribution (MWD) in the range of 10 to 40; d) a high load melt index (HLMI) in the range of 5 g / 10 min to 40 g / 10 min; and e) a 2% flexural modulus in the range of 120,000 psi (827 MPa) to 170,000 psi (1,172 MPa).

9. The second HDPE component is a) 1.0 x 10 ５ ~1.0 x 10 ８ The zero shear viscosity (η ０ ), b) a bulk intrinsic viscosity ([η]) in the range of 1.80 to 3.00, and c) a long chain branching index (LCBI) in the range of 0.1 to 2.

0.

10. 10. The composition of claim 1, wherein prior to blending with the first HDPE component, the second HDPE component is treated with peroxide carried out in an extruder at a temperature in the range of 150°C to 270°C under conditions of pressure and shear sufficient to increase the melt strength of the composition compared to a corresponding blend of the first HDPE component and the second HDPE component, where the second HDPE component has not been treated with peroxide.

11. The blend comprises: a) 0.951g / cm ３ ~0.962g / cm ３ Density in the range b) a melt index (I) in the range of 0.60 g / 10 min to 2.50 g / 10 min ５ ), and c) an Environmental Stress Crack Resistance ("ESCR") F50 ranging from 24 hours to 1,000 hours at 100% Igepal, and / or from 24 hours to 84 hours at 10% Igepal.

12. The blend comprises: a) 0.956g / cm ３ ~0.960g / cm ３ Density in the range b) a melt index (I) in the range of 0.80 g / 10 min to 1.80 g / 10 min ５ ), and c) a number average molecular weight (M) in the range of 10,000 g / mol to 20,000 g / mol ｎ ), d) a weight average molecular weight (M) in the range of 130,000 g / mol to 230,000 g / mol ｗ ), e) molecular weight distribution (MWD) in the range of 8 to 20; f) a high load melt index (HLMI) in the range of 15 g / 10 min to 45 g / 10 min; g) an overall polydispersity ratio (PDR) in the range of 15 to 60; h) 1.0 x 10 ６ ~3.0 x 10 ７ The zero shear viscosity (η ０ ), i) a bulk intrinsic viscosity ([η]) in the range of 1.5 to 2.5; j) a long chain branching index (LCBI) in the range of 0.3 to 1.3, and k) a 2% flexural modulus in the range of 165,000 psi (1,138 MPa) to 215,000 psi (1,482 MPa).

13. The blend comprises: a) a weight average molecular weight (M) in the range of 156,000 g / mol to 194,000 g / mol ｗ ), b) molecular weight distribution (MWD) in the range of 10 to 15; c) a high load melt index (HLMI) in the range of 20 g / 10 min to 40 g / 10 min; and d) a 2% flexural modulus in the range of 175,000 psi (1,207 MPa) to 205,000 psi (1,413 MPa).

14. 10. The composition of claim 1, wherein the first HDPE component comprises one or more HDPE homopolymers, one or more HDPE copolymers, or a combination thereof.

15. 15. The composition of claim 14, wherein the first HDPE component comprises one or more HDPE recycles, one or more virgin HDPEs, or a combination thereof.

16. 10. The composition of claim 1, wherein during or after blending the first HDPE component with the second HDPE component, the blend is treated with a peroxide carried out in an extruder at a temperature in the range of 150°C to 270°C under conditions of pressure and shear sufficient to increase the melt strength of the composition compared to a corresponding blend of the first HDPE component with the second HDPE component.

17. 10. The composition of claim 1, wherein the second HDPE component comprises one or more virgin HDPE homopolymers, one or more virgin HDPE copolymers, or a combination thereof.

18. 10. The composition of claim 1, wherein the first HDPE component and the second HDPE component are melt blended at a temperature ranging from 150°C to 270°C.

19. 10. The composition of claim 1, wherein the blend further comprises a primary antioxidant, a secondary antioxidant, or a combination thereof.

20. 20. The composition of claim 19, wherein the primary antioxidant is present in the blend in an amount of 1,900 ppm or less and the secondary antioxidant is present in the blend in an amount of 1,900 ppm or less, the ppm values being based on the total weight of the first HDPE component and the second HDPE component.

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