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WO2024081271A1 - Mélanges de polyéthylène contenant des matériaux hdpe vierges et recyclés - Google Patents

Mélanges de polyéthylène contenant des matériaux hdpe vierges et recyclés Download PDF

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Publication number
WO2024081271A1
WO2024081271A1 PCT/US2023/034869 US2023034869W WO2024081271A1 WO 2024081271 A1 WO2024081271 A1 WO 2024081271A1 US 2023034869 W US2023034869 W US 2023034869W WO 2024081271 A1 WO2024081271 A1 WO 2024081271A1
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WIPO (PCT)
Prior art keywords
hdpe
density polyethylene
virgin
blend
bimodal
Prior art date
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Ceased
Application number
PCT/US2023/034869
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English (en)
Inventor
Glendimar MOLERO
Elva LUGO
Xiaosong Wu
Cliff Mure
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to CN202380069540.2A priority Critical patent/CN119968429A/zh
Priority to EP23805234.4A priority patent/EP4587513A1/fr
Priority to KR1020257014677A priority patent/KR20250085790A/ko
Publication of WO2024081271A1 publication Critical patent/WO2024081271A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • This application relates to polyethylene polymers.
  • Plastics recycling is an important part of plastic waste management. Recycled plastics may not meet the physical property specifications that are needed for common end uses. As a result, recycled plastics are frequently blended with freshly made (“virgin”) plastic in order to provide a blend that can meet specifications needed for commercial use. Such blends desirably contain as much recycled plastic as practical, in order to maximize the amount of recycled plastic used and minimize the amount of virgin plastic needed.
  • High-density polyethylene is commonly used to make blow-molded items, such as jars, beverage bottles and other containers.
  • HDPE polymers need to have good melt strength, high rigidity (so that containers can be stacked without deforming) and resistance to cracking (so that containers will not crack and leak). Resistance to cracking is commonly measured by ASTM DI 693, which measures environmental stress crack resistance (ESCR), and/or ASTM F2136, which measures notched constant ligament stress (NCLS) resistance.
  • ASTM DI 693 which measures environmental stress crack resistance (ESCR)
  • ASTM F2136 which measures notched constant ligament stress (NCLS) resistance.
  • Recycled HDPE polymers may have crack resistance that is too low for use in blow- molded bottles. This may be especially true for post-consumer recycled (“PCR”) HDPE polymers. Some virgin polymers that can be blended to improve the crack resistance may also have the effect of reducing rigidity.
  • PCR post-consumer recycled
  • An aspect of the present invention is a high-density polyethylene (HDPE) blend comprising: (a) from 25 to 90 weight percent recycled HDPE; and (b) from 10 to 75 weight percent virgin bimodal HDPE having a density from 0.940 g/mL to 0.956 g/mL and a flow index (I21) from 25 g/10 min.to 40 g/10 min.
  • the HDPE blend is a post-reactor blend of the recycled HDPE and the virgin bimodal HDPE.
  • Another aspect of this invention is a shaped article comprising an HDPE blend of this invention.
  • Another aspect of this invention is a blow molding process comprising the steps of: (1) placing a quantity of molten HDPE blend in a mold cavity, (2) blowing a gas into the molten HDPE blend, causing it to expand and assume the approximate shape of the mold cavity, and (3) cooling the HDPE blend, wherein the HDPE blend is an HDPE blend of this invention.
  • Another aspect of this invention is a blow molded article prepared by the blow molding process.
  • FIG. 1 illustrates the melt strength over a range of draw velocities from 1 to 120 mm/s for three virgin HDPE polymers: two virgin bimodal HDPE polymers within the scope of the present invention and one virgin unimodal HDPE polymer that is comparative.
  • FIG.s 2 to 5 illustrate the melt strength under similar conditions for blends of the three virgin HDPE polymers with recycled HDPE, containing respectively 25 weight percent, 50 weight percent, 75 weight percent and 90 weight percent recycled HDPE.
  • FIG. 6 illustrates the molecular weight profiles of the two virgin bimodal HDPE polymers within the scope of the present invention and the one unimodal HDPE polymer that is comparative, as measured by Gel Permeation Chromatography.
  • Embodiments of this invention use high-density polyethylene polymers (HDPE) of the virgin type and HDPE polymers of the recycled type.
  • HDPE high-density polyethylene polymers
  • the HDPE is a polymer that predominantly contains repeating units derived from ethylene, optionally with repeating units derived from one or more unsaturated comonomers, and that has a density from 0.93 g/cc to 0.98 g/cc.
  • the HDPE is a homopolymer containing no measurable remnants of comonomer. In some embodiments, the HDPE is a copolymer in which a minor amount of repeating units are derived from unsaturated comonomers.
  • suitable comonomers used to make HDPE may include alpha-olefins.
  • Suitable alpha-olefins may include those containing from 3 to 20 carbon atoms (C3-C20).
  • the alpha-olefin may be a C4-C20 alpha-olefin, a C4-C12 alpha-olefin, a C3-C10 alphaolefin, a C3-C8 alpha-olefin, a C4-C8 alpha-olefin, or a Ce-Cs alpha-olefin.
  • the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l -pentene, 1 -heptene, 1 -octene, 1 -nonene and 1 -decene. In other embodiments, the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1 -octene. In further embodiments, the alpha-olefin is selected from the group consisting of 1-hexene and 1- octene.
  • an HDPE copolymer contains at least 95 weight percent repeating units derived from ethylene, or at least 96 weight percent or at least 97 weight percent or at least 98 weight percent or at least 99 weight percent or at least 99.5 weight percent, with the remaining repeating units derived from unsaturated comonomers. In some embodiments, an HDPE copolymer contains at least 4 weight percent repeating units derived from comonomers, or at least 3 weight percent or at least 2 weight percent or at least 1 weight percent or at least 99.5 weight percent, with the remaining repeating units derived from ethylene monomer. It is well known how to select comonomers and comonomer content to obtain the known molecular weight and other properties for an HDPE copolymer.
  • the comonomer content may be in the higher part of the range listed above. In some embodiments, wherein the comonomer is a lower molecular weight comonomer such as 1 -butene, the comonomer content may be in the lower part of the range listed above.
  • HDPE blends of the present invention contain recycled HDPE.
  • the recycled HDPE is pre-consumer recycled polyethylene, such as scraps and waste from HDPE manufacturing facilities or from HDPE fabricators.
  • the recycled HDPE polymer is post-consumer recycled (PCR) HDPE.
  • the recycled HDPE polymer is a post-industrial recycled HDPE.
  • pre-consumer recycled polyethylene and “post-industrial recycled HDPE” refer to polymers, including blends of polyethylene polymers, recovered from pre-consumer material, as defined by ISO-14021.
  • pre-consumer recycled polyethylene thus includes blends of polyethylene and other polymers recovered from materials diverted from the waste stream during a manufacturing process.
  • pre-consumer recycled polyethylene excludes the reutilization of polyethylene materials, such as rework, regrind, or scrap, generated in a process and capable of being reclaimed within the same process that generated it.
  • post-consumer recycled refers to a polyethylene material, such as the PCR HDPE, that includes materials previously used in a consumer or industry application i.e., pre-consumer recycled polyethylene and post-industrial recycled HDPE.
  • PCR polyethylene is typically collected from recycling programs and recycling plants.
  • the PCR polyethylene may include one or more contaminants.
  • the contaminants may be the result of the polyethylene material’s use prior to being repurposed for reuse.
  • contaminants may include paper, ink, food residue, or other recycled materials in addition to the polymer, which may result from the recycling process.
  • PCR polyethylene is distinct from virgin polyethylene.
  • a virgin polyethylene does not include materials previously used in a consumer or industry application, whereas the PCR polyethylene does include them.
  • Virgin polyethylene material has not undergone, or otherwise has not been subject to, a heat process or a molding process, after the initial polymer manufacturing process.
  • the physical, chemical, and flow properties of PCR polyethylene polymers differ when compared to virgin polyethylene, which in turn can present challenges to incorporating PCR polyethylene into blends for commercial use.
  • PCR polyethylene means a PCR ethylene/alpha-olefin copolymer, such as a PCR high-density polyethylene; and optionally other components and additives.
  • PCR polyethylene includes various polyethylene compositions. PCR polyethylene may be sourced from HDPE packaging such as bottles (milk jugs, juice containers), LDPE/LLDPE packaging such as films. PCR polyethylene also includes residue from its original use, residue such as paper, adhesive, ink, nylon, ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and other odor-causing agents.
  • HDPE packaging such as bottles (milk jugs, juice containers), LDPE/LLDPE packaging such as films.
  • PCR polyethylene also includes residue from its original use, residue such as paper, adhesive, ink, nylon, ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and other odor-causing agents.
  • Sources of PCR polyethylene can include, for example, bottle caps and closures, milk, water or orange juice containers, detergent bottles, office automation equipment (printers, computers, copiers, etc.), white goods (refrigerators, washing machines, etc.), consumer electronics (televisions, video cassette recorders, stereos, etc.), automotive shredder residue (the mixed materials remaining after most of the metals have been sorted from shredded automobiles and other metal-rich products “shredded” by metal recyclers), packaging waste, household waste, rotomolded parts (kayaks/coolers), building waste and industrial molding and extrusion scrap.
  • office automation equipment printing, computers, copiers, etc.
  • white goods refrigerators, washing machines, etc.
  • consumer electronics televisions, video cassette recorders, stereos, etc.
  • automotive shredder residue the mixed materials remaining after most of the metals have been sorted from shredded automobiles and other metal-rich products “shredded” by metal recyclers
  • packaging waste household waste, rotomolded parts (kayaks/coolers),
  • the polyethylene of the PCR polyethylene comprises low density polyethylene, linear low density polyethylene, or a combination thereof.
  • the PCR polyethylene further comprises residue from its original use, such as paper, adhesive, ink, nylon, ethylene vinyl alcohol (EVOH), polyamide (PA), polyethylene terephthalate (PET), and other organic or inorganic material.
  • PCR polymers include KWR101-150 and KWR-102 commercially available from KW Plastics, and AVANGARDTM NATURA PCR-LDPCR-100 (“AVANGARDTM 100”) and AVANGARDTM NATURA PCR-LDPCR-150 (“AVANGARDTM 150”) (PCR polymer commercially available from Avangard innovative LP, Houston, Texas).
  • the PCR polyethylene is a PCR HDPE available as KWR 101-150 from KW Plastics.
  • KWR101-150 has the DSC properties shown in the table below, wherein: “1st Cool Delta H cryst” measures the enthalpy of crystallization during the first cooling curve; “1st Cool Tel” measures the crystallization temperature during the first cooling cycle; “2nd Heat Delta H melt measures the enthalpy of fusion during the second heating curve; and “2nd Heat Tml” measures the melting temperature during the second heating curve.
  • the PCR polyethylene has a heat of fusion in the range of from 130 to 170 Joule/gram (J/g), measured according to the DSC test method described below. All individual values and subranges of from 130 to 170 J/g are disclosed and incorporated herein; for example, the heat of fusion of the PCR polyethylene can be from 130 to 170 J/g, from 130 to 160 J/g, from 130 to 150 J/g, from 130 to 140 J/g, from 140 to 170 J/g, from 140 to 160 J/g, from 140 to 150 J/g, from 150 to 170 J/g, or from 155 to 170 J/g, when measured according to the DSC test method described below.
  • the PCR polyethylene has a peak melting temperature (Tm) of from 115°C to 137°C, when measured according to the DSC test method describe below. All individual values and subranges of from 115°C to 137°C are disclosed and incorporated herein; for example, the peak melting temperature (Tm) of the PCR polymer can be from 121°C to 135°C, from 131°C to 135°C, from 132°C to 135°C or from 133.0°C to 134.0°C, when measured according to the DSC test method described below.
  • the recycled HDPE has a density of at least 0.94 g/cc or at least 0.95 g/cc or at least 0.955 g/cc or at least 0.958 g/cc. In some embodiments, the recycled HDPE has a density of at most 0.97 g/cc or at most 0.965 g/cc.
  • the recycled HDPE has a characteristic optical defect, determined according to the Gel Characterization Test Method described later, of [TESTING IN PROGRESS— ADD DATA to PCT filing].
  • the melt index (H) of the recycled HDPE ranges from 0.01 g/10 min to 30 g/10 min. All individual values and subranges of 0.01 g/10 min to 30 g/10 min are included and disclosed herein.
  • the melt index (I2) of the recycled HDPE is at least 0.1 g/10 min or at least 0.3 g/10 min or at least 0.4 g/10 min or at least 0.5 g/10 min or at least 0.55 g/10 min.
  • the melt index (I2) of the recycled HDPE is at most 2 g/10 min or at most 1 g/10 min or at most 0.8 g/10 min or at most 0.7 g/10 min or at most 0.65 g/10 min.
  • the melt index (I5) of the recycled HDPE is at least 1 g/10 min or at least 2 g/10 min or at least 2.5 g/10 min or at least 2.75 g/10 min. In some embodiments, the melt index (I5) of the recycled HDPE is at most 5 g/10 min or at most 4 g/10 min or at most 3.5 g/10 min or at most 3.25 g/10 min.
  • the flow index (I21) of the recycled HDPE is at least 30 g/10 min or at least 40 g/10 min or at least 45 g/10 min or at least 50 g/10 min. In some embodiments, the flow index (I21) of the recycled HDPE is at most 100 g/10 min or at most 90 g/10 min or at most 80 g/10 min or at most 70 g/10 min or at most 60 g/10 min.
  • the melt flow ratio (I21/I5) of the recycled HDPE is at least 10 or at least 15 or at least 17 or at least 18. In some embodiments, the melt flow ratio (I21/I5) of the recycled HDPE is at most 30 or at most 25 or at most 23 or at most 21 or at most 20.
  • the number average molecular weight (Mn) of the recycled HDPE is at least 10,000 Da or at least 15,000 Da or at least 18,000 Da. In some embodiments, the number average molecular weight (Mn) of the recycled HDPE is at most 50,000 Da or at most 40,000 Da or at most 30,000 Da or at most 25,000 Da.
  • the weight average molecular weight (Mw) of the recycled HDPE is at least 80,000 Da or at least 100,000 Da or at least 110,000 Da. In some embodiments, the weight average molecular weight (Mw) of the recycled HDPE is at most 200,000 Da or at most 160,000 Da or at most 130,000 Da or at most 120,000 Da.
  • the molecular weight distribution (Mw/Mn) of the recycled HDPE is at least 3 or at least 4 or at least 5. In some embodiments, the molecular weight distribution (Mw/Mn) of the recycled HDPE is at most 10 or at most 8 or at most 7.
  • the tensile yield strength of the recycled HDPE is at least 2500 psi or at least 3000 psi or at least 3500 psi. In some embodiments, the tensile yield strength of the recycled HDPE is at most 7000 psi or at most 5000 psi or at most 4000 psi.
  • the ESCR (time to 50% failure rate under the test conditions listed below) of the recycled HDPE is at most 35 hours or at most 30 hours or at most 25 hours or at most 22 hours or at most 20 hours. In some embodiments, the ESCR (time to 50% failure rate under the test conditions listed below) of the recycled HDPE is at least 10 hours or at least 15 hours or at least 18 hours.
  • Suitable recycled HDPE streams are commercially available, such as from KW Plastics. Others can be prepared by know processes such as: (1) separating HDPE materials having desired properties from a recycle waste stream; (2) washing the separated HDPE materials; and (3) grinding the separated HDPE materials. An example of such a process is described in European Patent 2 697 025 Bl.
  • HDPE blends of the present invention also contain virgin bimodal high-density polyethylene (HDPE) polymer, which is a bimodal HDPE that has not been fabricated or used to make shaped articles after it was pelletized.
  • HDPE high-density polyethylene
  • the density of the virgin bimodal HDPE is from 0.94 g/cc to 0.956 g/cc. In some embodiments, the density of the virgin bimodal HDPE is at least 0.945 g/cc or at least 0.95 g/cc or at least 0.952 g/cc. In some embodiments, the density of the virgin bimodal HDPE is at most 0.955 g/cc or at most 0.954 g/cc.
  • the flow index (I21) of the virgin bimodal HDPE is from 25 g/10 min. to 40 g/10 min. In some embodiments, the flow index (I21) of the virgin bimodal HDPE is at least 27 g/10 min or at least 28 g/10 min or at least 29 g/10 min or at least 30 g/10 min. In some embodiments, the flow index (I21) of the virgin bimodal HDPE is at most 38 g/10 min or at most 36 g/10 min or at most 35 g/10 min or at most 34 g/10 min or at most 33 g/10 min or at most 32.5 g/10 min.
  • the melt index (I2) of the virgin bimodal HDPE is at least 0.05 g/10 min or at least 0.07 g/10 min or at least 0.09 g/10 min or at least 0.11 g/10 min or at least 0. 13 g/10 min. In some embodiments, the melt index (I2) of the virgin bimodal HDPE is at most 0.5 g/10 min or at most 0.4 g/10 min or at most 0.3 g/10 min or at most 0.25 g/10 min or at most 0.22 g/10 min or at most 0.2 g/10 min or at most 0.18 g/10 min.
  • the melt index (I5) of the virgin bimodal HDPE is at least 0.5 g/10 min or at least 0.7 g/10 min or at least 0.8 g/10 min or at least 0.9 g/10 min. In some embodiments, the melt index (I5) of the virgin bimodal HDPE is at most 5 g/10 min or at most 3 g/10 min or at most 2 g/10 min or at most 1.5 g/10 min or at most 1.3 g/10 min or at most 1.2 g/10 min.
  • the melt flow ratio (I21/I5) of the virgin bimodal HDPE is at least 15 or at least 20 or at least 25 or at least 27 or at least 28 or at least 29. In some embodiments, the melt flow ratio (I21/I5) of the virgin bimodal HDPE is at most 50 or at most 40 or at most 35 or at most 34 or at most 33. In some embodiments, the melt strength of the virgin bimodal HDPE at 190°C is at least 8 cN or at least 9 cN or at least 10 cN. In some embodiments, the melt strength of the virgin bimodal HDPE at 190°C is at most 15 cN or at most 13 cN or at most 11 cN.
  • the number average molecular weight (Mn) of the virgin bimodal HDPE is at least 15,000 Da or at least 17,000 Da or at least 18,000 Da or at least 19,000 Da or at least 20,000 Da. In some embodiments, the number average molecular weight (Mn) of the virgin bimodal HDPE is at most 30,000 Da or at most 28,000 Da or at most 26,000 Da or at most 24,000 Da or at most 22,000 Da.
  • the weight average molecular weight (Mw) of the virgin bimodal HDPE is at least 200,000 Da or at least 250,000 Da or at least 300,000 Da or at least 325,000 Da. In some embodiments, the weight average molecular weight (Mw) of the virgin bimodal HDPE is at most 400,000 Da or at most 350,000 Da or at most 340,000 Da or at most 330,000 Da.
  • the molecular weight distribution (Mw/Mn) of the virgin bimodal HDPE is at least 10 or at least 12 or at least 13 or at least 14 or at least 15. In some embodiments, the molecular weight distribution (Mw/Mn) of the virgin bimodal HDPE is at most 25 or at most 20 or at most 19 or at most 18 or at most 17.
  • the Z average molecular weight (Mz) of the virgin bimodal HDPE is at least 2,500,000 Da or at least 3,000,000 Da or at least 3,500,000 Da or at least 4,000,000 Da or at least 4,500,000 Da or at least 5,000,000 Da. In some embodiments, the Z average molecular weight (Mz) of the virgin bimodal HDPE is at most 7,000,000 Da or at most 6,000,000 Da or at most 5,700,000 Da or at most 5,500,000 Da.
  • the ratio (Mz/Mw) of the virgin bimodal HDPE is at least 14 or at least 14.5 or at least 15 or at least 15.5 or at least 16. In some embodiments, the ratio (Mz/Mw) of the virgin bimodal HDPE is at most 24 or at most 20 or at most 18 or at most 17.
  • the virgin bimodal HDPE has a bimodal molecular weight distribution, meaning that it comprises a higher molecular weight (HMW) component, and a lower molecular weight (LMW) component.
  • the weight average molecular weight (Mw) of the HMW component is higher than the weight average molecular weight (Mw) of the LMW component.
  • the molecular weight profile of a virgin bimodal HDPE may form two distinct peaks, as explained and illustrated in US Patent 6,787,608B2 at column 4, lines 4-37 and Figure 1C.
  • the molecular weight profile of a virgin bimodal HDPE may form a single peak with a shoulder, as explained and illustrated in US Patent 6,787,608B2 at column 4, lines 4-37 and Figure IB.
  • the molecular weight profile of a virgin bimodal HDPE may form a single peak with a tail, as explained and illustrated in US Patent 6,787,608B2 at column 4, lines 4-37 and Figure 1A.
  • the LMW Component makes up more than 50 weight percent of the virgin bimodal HDPE or more than 60 weight percent or more than 70 weight percent or more than 75 weight percent.
  • the molecular weight profile of a virgin bimodal HDPE shows the HMW component as a shoulder on the LMW component peak.
  • the bimodal nature of the virgin bimodal HDPE is reflected in a high molecular weight distribution (Mw/Mn) or ratio of Mz/Mw, as compared to similar unimodal HDPE.
  • the tensile yield strength of the virgin bimodal HDPE is at least 3200 psi or at least 3500 psi or at least 3650 psi. In some embodiments, the tensile yield strength of the virgin bimodal HDPE is at most 4500 psi or at most 4000 psi or at most 3850 psi.
  • the viscosity of the virgin bimodal HDPE at a shear rate of 0.1 rad/s (“low shear viscosity” or “1)0.1”) is at least 40,000 pascal-seconds (Pa-s) or at least 60,000 Pa-s or at least 70,000 Pa-s. In some embodiments, the viscosity of the virgin bimodal HDPE at a shear rate of 0.1 rad/s (“low shear viscosity” or “r
  • the viscosity of the virgin bimodal HDPE at a shear rate of 100 rad/s (“high shear viscosity” or “TJIOO”) is at least 1220 Pa-s or at least 1250 Pa-s or at least 1300 Pa-s. In some embodiments, the viscosity of the virgin bimodal HDPE at a shear rate of 100 rad/s (“high shear viscosity” or “rpoo”) is at most 1500 Pa-s or at most 1450 Pa-s or at most 1400 Pa-s.
  • IOO) for the virgin bimodal HDPE is at least 30 or at least 40 or at least 45 or at least 50. In some embodiments, the ratio of low shear viscosity to high shear viscosity (r
  • Die swell of polymers can be compared using a “timed swell test” as described in PCT Publication WO 2020/223191 at Paragraph [0074], The polymers are extruded through a specific die having a set aperture under a specific set of conditions (temperature, extrusion rate, shear, etc.), and the time required for the extrudate to reach a specified length is recorded. Polymer that swells more out of the die takes longer to reach the specified length and therefor has more die swell. In this application, the specified length is 25.4 cm.
  • the timed die swell of the virgin bimodal HDPE under the test conditions listed below at a shear rate of 300 s 1 is at least 23 seconds or at least 24 seconds or at least 25 seconds In some embodiments, the timed die swell of the virgin bimodal HDPE under the test conditions listed below at a shear rate of 300 s 1 is at most 30 seconds or at most 28 seconds or at most 27 seconds or at most 26 seconds.
  • the timed die swell of the virgin bimodal HDPE under the test conditions listed below at a shear rate of 1000 s 1 is at least 7.5 seconds or at least 8.0 seconds or at least 8.3 seconds. In some embodiments, the timed die swell of the virgin bimodal HDPE under the test conditions listed below at a shear rate of 1000 s 1 is at most 10.0 seconds or at most 9.5 seconds or at most 9.0 seconds.
  • the ESCR (time to 50% failure rate under the test conditions listed below) of the virgin bimodal HDPE is at least 100 hours or at least 200 hours or at least 300 hours or at least 350 hours or at least 400 hours or at least 500 hours. There is no maximum desirable ESCR performance, but ESCR over 1000 hours may be unnecessary.
  • the NCLS (time to 50% failure rate under the test conditions listed below) of the virgin bimodal HDPE is at least 50 hours or at least 75 hours or at least 100 hours or at least 150 hours or at least 200 hours or at least 300 hours or at least 500 hours. There is no maximum desirable NCLS performance, but NCLS over 1000 hours may be unnecessary.
  • the virgin bimodal HDPE copolymer comprises from 22.0 weight percent (wt%) to 29.9 wt% of a higher molecular weight ethylene/1 -hexene copolymer component (HMW copolymer component) and from 78.0 wt% to 70.1 wt%, respectively, of a lower molecular weight ethylene/1 -hexene copolymer component (LMW copolymer component), wherein the wt% of the HMW copolymer component and the wt% of the LMW copolymer component are based on the total weight of the HMW and LMW components.
  • the weight percent of the HMW component is sometimes called a “split” of the virgin bimodal HDPE copolymer.
  • a particularly useful virgin bimodal HDPE copolymer comprises from 22.5 weight percent (wt%) to 29.4 wt% of a higher molecular weight ethylene/1 -hexene copolymer component (HMW copolymer component) and from 77.5 wt% to 70.6 wt%, respectively, of a lower molecular weight ethylene/1 -hexene copolymer component (LMW copolymer component), and wherein the virgin bimodal HDPE has each of properties (a) to (g): (a) a density from 0.940 g/cc to 0.956 g/cc; (b) a flow index (I21) from 25.0 g/10 min.to 40.0 g/10 min.; (c) a ratio of Abs Mw/Mn from 12 to 14 or a ratio of Abs Mz/Mw of 7.0 to 8.0 or both ratios, wherein Mw is weight-average molecular weight and Mn is number- average molecular weight and Mz is z-average
  • this virgin bimodal high-density polyethylene has a timed die swell (time to reach 25.4 cm diameter) at a shear rate of 300 per second (s’ 1 ) from 8.0 seconds to 9.5 seconds.
  • the virgin bimodal HDPE copolymer has a split of 23.5 wt% to 25.4 wt% of the HMW component, and consequently has from 76.5 wt% to 74.6 wt% of the LMW component.
  • the virgin bimodal HDPE copolymer has a split of 28.0 wt% to 29.4 wt% of the HMW component, and consequently from 72.0 wt% to 70.6 wt% of the LMW component.
  • HMW and LMW are used in reference to each other and merely mean that the weight-average molecular weight of the HMW component (M w _ HMW) ' s g rea t er than the weight- average molecular weight of the LMW component (M W .LM ⁇ V), i.e., M W .HMW > M W-LMW-
  • Embodiments of the present invention also include the virgin bimodal HDPE, such as the particularly useful virgin bimodal HDPE copolymer described in the immediately preceding paragraph.
  • the virgin bimodal HDPE polymer may be easier to produce using a single reactor with such a bimodal catalyst system.
  • the virgin bimodal HDPE polymer is a so-called reactor copolymer because it is made in a single polymerization reactor using a bimodal catalyst system effective for simultaneously making the HMW and LMW copolymer components in situ.
  • this bimodal HDPE copolymer is useful as the sole polymer for blow-molding applications. It has good melt-strength, crack resistance and other physical properties. Narrower specific embodiments may optionally be as previously described for the virgin bimodal HDPE.
  • the PRODIGYTM BMC 300 catalyst system comprises, or is made from, a zirconium-containing metallocene catalyst, a zirconium-containing postmetallocene catalyst, a support material, and an activator.
  • the zirconium-containing metallocene catalyst is bis(n-butylcyclopentadienyl)zirconium X2 of formula wherein each R 1 is -CH2CH2CH2CH and each X is a leaving group. In some embodiments of formula (I) each X is Cl or each X is methyl.
  • the zirconium-containing post-metallocene catalyst is bis(2- (pentamethylphenylamido)ethyl)amine zirconium dibenzyl, which is sometimes referred to in the ail as “HN5 dibenzyl” and is a compound of formula (II) wherein M is
  • Zr and each R is benzyl (“Bn”). Both catalysts are well known in the art.
  • the zirconium-containing post-metallocene catalyst may be made by procedures described in the art or obtained from Univation Technologies, LLC, Houston, Texas, USA, a wholly-owned entity of The Dow Chemical Company, Midland, Michigan, USA.
  • Representative Group 15-containing metal compounds, including bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl, and preparation thereof can be as discussed and described in U .S. Pat. Nos.
  • the PRODIGYTM BMC-300 embodiment of the bimodal catalyst system was used to make virgin bimodal HDPE polymer number 1, called “Virgin Bimodal HDPE 1“ in the EXAMPLES.
  • Another suitable embodiment of the bimodal catalyst system is made from the same constituents as used to make the BMC-300 type catalyst system except wherein the bis(n- butylcyclopentadienyl)zirconium X2 of formula (I) is replaced by (cyclopentadienyl)(l,5- dimethylindenyl)zirconium X2, which is a zirconium-containing metallocene of formula (III): , wherein M is Zr and each X is a leaving group. In some embodiments of formula (III) each X is Cl or each X is methyl.
  • This other suitable bimodal catalyst system thus comprises, or is made from, the zirconium-containing metallocene of formula (III), the HN5 dibenzyl, the support, and an activator.
  • this other embodiment of the bimodal catalyst system is called “BMC Analog’’.
  • the BMC Analog embodiment of the bimodal catalyst system was used to make virgin bimodal HDPE polymer number 2, called “Virgin Bimodal HDPE 2” in the EXAMPLES.
  • the support material used in these bimodal catalyst systems may be an inorganic oxide material.
  • support and “support material” are the same as used herein and refer to a porous inorganic substance or organic substance.
  • desirable support materials may be inorganic oxides that include Group 2, 3, 4, 5, 13 or 14 oxides, alternatively Group 13 or 14 atoms.
  • inorganic oxide-type support materials are silica, alumina, titania, zirconia, thoria, and mixtures of any two or more of such inorganic oxides. Examples of such mixtures are silica-chromium, silica-alumina, and silica-titania.
  • the inorganic oxide support material is porous and has variable surface area, pore volume, and average particle size.
  • the surface area is from 50 to 1000 square meter per gram (m ⁇ /g) and the average particle size is from 20 to 300 micrometers (pm).
  • the pore volume is from 0.5 to 6.0 cubic centimeters per gram (cc/g) and the surface area is from 200 to 600 m-/g.
  • the pore volume is from 1.1 to 1.8 cc/g and the surface area is from 245 to 375 m ⁇ /g.
  • the pore volume is from 2.4 to 3.7 cc/g and the surface area is from 410 to 620 m ⁇ /g.
  • the pore volume is from 0.9 to 1.4 cc/g and the surface area is from 390 to 590 m ⁇ /g.
  • the support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica (e.g., from 500 to 1000 m ⁇ /g).
  • silica alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica (e.g., from 500 to 1000 m ⁇ /g).
  • silicas are commercially available from several sources including the Davison Chemical Division of W.R. Grace and Company (e.g., Davison 952 and Davison 955 products), and PQ Corporation (e.g., ES70 product).
  • the silica may be in the form of spherical particles, which are obtained by a spraydrying process.
  • MS3050 product is a silica from PQ Corporation that is not spray- dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support
  • the support material Prior to being contacted with a catalyst, such as the HN5 dibenzyl and the zirconium- containing metallocene, the support material may be pre-treated by heating the support material in air to give a calcined support material.
  • the pre-treating comprises heating the support material at a peak temperature from 350° to 850° C., alternatively from 400° to 800° C., alternatively from 400° to 700° C., alternatively from 500° to 650° C. and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making a calcined support material.
  • the support material may be a calcined support material.
  • the method of making the virgin bimodal HDPE using the bimodal catalyst system may further employ a trim catalyst, typically in the form of a trim catalyst solution comprising the aforementioned zirconium-containing metallocene of formula (I) or (III) and an additional quantity of activator.
  • a trim catalyst typically in the form of a trim catalyst solution comprising the aforementioned zirconium-containing metallocene of formula (I) or (III) and an additional quantity of activator.
  • the trim catalyst is fed in solution in a hydrocarbon solvent (e.g., mineral oil, heptane, or isopentane).
  • the trim catalyst may be used to vary, within limits, the amount of the zirconium-containing metallocene used in the method relative to the amount of the zirconium-containing post-metallocene (e.g., HN5 dibenzyl) of the bimodal catalyst system, so as to adjust the properties of the inventive HDPE blend.
  • Each catalyst of the bimodal catalyst system is activated by contacting it with an activator.
  • Any activator may be the same or different as another and independently may be a Lewis acid, a non-coordinating ionic activator, or an ionizing activator, or a Lewis base, an alkylaluminum, or an alkylaluminoxane (alkylalumoxane).
  • the alkylaluminum may be a trialkylaluminum, alkylaluminum halide, or alkylaluminum alkoxide (diethylaluminum ethoxide).
  • the trialkylaluminum may be trimethylaluminum, triethylaluminum (“TEA1”), tripropylaluminum, or tris(2-methylpropyl)aluminum.
  • the alkylaluminum halide may be diethylaluminum chloride.
  • the alkylaluminum alkoxide may be diethylaluminum ethoxide.
  • the alkylaluminoxane may be a methylaluminoxane (MAO), ethylaluminoxane, 2-methylpropyl-aluminoxane, or a modified methylaluminoxane (MMAO).
  • Each alkyl of the alkylaluminum or alkylaluminoxane independently may be a (C C lalkyl, alternatively a (C i -Cfpalkyl, alternatively a (Cl
  • the molar ratio of activator’ s metal (Al) to a particular catalyst compound’s metal (catalytic metal, e.g., Zr) may be 1000:1 to 0.5:1, alternatively 300:1 to 1: 1, alternatively 150:1 to 1: 1. Suitable activators are commercially available.
  • the activator species may have a different structure or composition than the catalyst and activator from which it is derived and may be a by-product of the activation of the catalyst or may be a derivative of the by-product.
  • the corresponding activator species may be a derivative of the Lewis acid, non-coordinating ionic activator, ionizing activator, Lewis base, alkylaluminum, or alkylaluminoxane, respectively.
  • An example of the derivative of the by-product is a methylaluminoxane species that is formed by devolatilizing during spray-drying of a bimodal catalyst system made with methylaluminoxane.
  • Each contacting step between activator and catalyst independently may be done either in a separate vessel outside of a gas phase polymerization (GPP) reactor, such as outside of a floatingbed gas phase polymerization (FB-GPP) reactor, or in a feed line to the GPP reactor.
  • the bimodal catalyst system once its catalysts are activated, may be fed into the GPP reactor as a dry powder, alternatively as a slurry in a non-polar, aprotic (hydrocarbon) solvent.
  • the activator(s) may be fed into the GPP reactor in “wet mode” in the form of a solution thereof in an inert liquid such as mineral oil or toluene, in slurry mode as a suspension, or in dry mode as a powder.
  • Each contacting step may be done at the same or different times.
  • the gas phase polymerization reactor may be a fluidized-bed gas phase polymerization (FB-GPP) reactor and the effective polymerization conditions may comprise the following reaction conditions: the FB-GPP reactor having a fluidized bed at a bed temperature from 80 to 110 degrees Celsius (° C.); the FB-GPP reactor receiving feeds of respective independently controlled amounts of ethylene, 1-alkene characterized by a 1-alkene-to-ethylene (C x /C2, wherein subscript x indicates the number of carbon atoms in the 1-alkene; for example, when the 1-alkene is 1-hexene, the C x /C2 ratio is the 1 -hexene- to-ethylene ratio, which may be written as a C5/C2 ratio) molar ratio, the bimodal catalyst system, optionally a trim catalyst solution, optionally hydrogen gas (H2) characterized by a hydrogen-to-ethylene (H2/C2) molar ratio or by a weight parts per million H2 to mole percent C2 ratio (H2
  • reaction conditions are those described in the EXAMPLES for making Virgin Bimodal HDPE 1 or Virgin Bimodal HDPE 2, plus-or-minus ( ⁇ ) 10%.
  • the HDPE blend is a post-reactor blend of the recycled HDPE and the virgin bimodal HDPE.
  • the recycled HDPE and the virgin bimodal HDPE are melt-blended together in a relative amount of from 25 to 90 weight percent recycled HDPE and from 10 to 75 weight percent virgin bimodal HDPE.
  • the blending can be accomplished by any known means, such as coextruding the two polymers in known extruders or melt blending in known mixers such as from Hakke, Brabender or Banbury.
  • the HDPE blend contains at least 35 weight percent recycled HDPE or at least 45 weight percent or at least 55 weight percent or at least 65 weight percent or at least 70 weight percent or at least 75 weight percent or at least 80 weight percent. In some embodiments, the HDPE blend contains at most 85 weight percent recycled HDPE or at most 80 weight percent or at most 75 weight percent or at most 65 weight percent or at most 55 weight percent. For example, the HDPE blend may contain 45 to 80 weight percent recycled HDPE, or 45 to 65 weight percent, or 65 to 80 weight percent, or 70 to 90 weight percent.
  • the HDPE blend contains at most 65 weight percent virgin bimodal HDPE or at most 55 weight percent or at most 45 weight percent or at most 35 weight percent or at most 30 or at most 25 weight percent or at most 20 weight percent weight percent. In some embodiments, the HDPE blend contains at least 15 weight percent virgin bimodal HDPE or at least 20 weight percent or at least 25 weight percent or at least 35 weight percent or at least 45 weight percent. For example, the HDPE blend may contain 20 to 55 weight percent virgin bimodal HDPE, or 35 to 55 weight percent, or 20 to 35 weight percent, or 10 to 30 weight percent.
  • the HDPE blend may contain additives.
  • Additives for polyolefin polymers are described in numerous publications, such as the pamphlet: Tolinski, “Additives for Polyolefins. Getting the Most out of Polypropylene, Polyethylene and TPO (Second Edition)” published by the Plastics Design Library in 2015.
  • common additives include antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, nucleators, slip agents such as erucamide, antiblock agents such as talc, and combinations thereof.
  • additives make up no more than 5 weight percent of the HDPE blend or no more than 4 weight percent or no more than 3 weight percent or no more than 2 weight percent or no more than 1 weight percent. In some embodiments, additives make up essentially 0 weight percent of the HDPE blend.
  • the density of the HDPE blend is at least 0.94 g/cc or at least 0.945 g/cc or at least 0.95 g/cc or at least 0.955 g/cc or at least 0.957 g/cc. In some embodiments, the density of the HDPE blend is at most 0.97 g/cc or at most 0.965 g/cc or at most 0.963 g/cc or at most 0.961 g/cc or at most 0.96 g/cc.
  • the melt index (L) of the HDPE blend is at least 0.1 g/10 min or at least 0.15 g/10 min or at least 0.16 g/10 min or at least 0.17 g/10 min. In some embodiments, the melt index (I2) of the HDPE blend is at most 2 g/10 min or at most 1 g/10 min or at most 0.8 g/10 min or at most 0.7 g/10 min or at most 0.6 g/10 min or at most 0.5 g/10 min.
  • the flow index (I21) of the HDPE blend is at least 20 g/10 min or at least 25 g/10 min or at least 28 g/10 min or at least 30 g/10 min or at least 31 g/10 min. In some embodiments, the flow index (I21) of the HDPE blend is at most 90 g/10 min or at most 80 g/10 min or at most 70 g/10 min or at most 60 g/10 min or at most 58 g/10 min or at most 56 g/10 min.
  • the melt flow ratio (I21/I2) of the HDPE blend is at least 15 or at least 18 or at least 20 or at least 21. In some embodiments, the melt flow ratio (I21/I2) of the HDPE blend is at most 45 or at most 40 or at most 36 or at most 34 or at most 32.
  • the tensile yield strength of the HDPE blend is at least 3000 psi or at least 3500 psi or at least 3700 psi or at least 3900 psi or at least 4000 psi or at least 4100 psi. In some embodiments, the tensile yield strength of the HDPE blend is at most 7000 psi or at most 6000 psi or at most 5000 psi or at most 4500 psi.
  • the ESCR (time to 50% failure rate under the test conditions listed below) of an HDPE blend that contains at least 45 weight percent recycled HDPE is at least 30 hours or at least 40 hours or at least 50 hours or at least 60 hours or at least 70 hours or at least 80 hours. In some embodiments, the ESCR (time to 50% failure rate under the test conditions listed below) of an HDPE blend that contains at least 70 weight percent recycled HDPE is at least 15 hours or at least 20 hours or at least 22 hours or at least 25 hours. There is no maximum desired ESCR, but performance over 100 or 200 hours may be unnecessary.
  • the Notched Constant Ligament Stress (time to 50% failure rate under the test conditions listed below) of an HDPE blend that contains at least 45 weight percent recycled HDPE is at least 30 hours or at least 40 hours or at least 50 hours or at least 60 hours or at least 70 hours or at least 80 hours.
  • the NCLS (time to 50% failure rate under the test conditions listed below) of the HDPE blend that contains at least 70 weight percent recycled HDPE is at least 15 hours or at least 21 hours or at least 25 hours or at least 27 hours. There is no maximum desired NCLS, but performance over 100 or 200 hours may be unnecessary.
  • the Charpy impact resistance of the HDPE blend is at least
  • the strain hardening modulus of the HDPE blend is at least 6 MPa or at least 8 MPa or at least 9 MPa or at least 11 MPa or at least 13 MPa or at least 15 MPa or at least 17 MPa or at least 18 MPa. In some embodiments, the strain hardening modulus of the HDPE blend is at most 20 MPa or at most 16 MPa or at most 13 MPa or at most 4500 psi.
  • the melt strength of the HDPE blend that contains at least 45 weight percent of the recycled HDPE is at least 8.0 cN or at least 8.5 cN or at least 9 cN. In some embodiments, the melt strength of the HDPE blend that contains at least 45 weight percent of the recycled HDPE is at most 12 cN or at most 10 cN.
  • the melt strength of the HDPE blend that contains at least 70 weight percent of the recycled HDPE is at least 7.0 cN or at least 7.5 cN or at least 8 cN. In some embodiments, the melt strength of the HDPE blend that contains at least 70 weight percent of the recycled HDPE is at most 10 cN or at most 9 cN.
  • HDPE blends of the present invention can be used in common blow molding processes, such as extrusion blow-molding, injection blow molding or injection stretch blow molding. All three processes use the following steps: (1) placing a quantity of molten HDPE blend in a mold cavity, (2) blowing air or a neutral gas such as nitrogen into the molten HDPE blend, causing it to expand and assume the approximate shape of the mold cavity, and (3) cooling the HDPE blend.
  • an extrusion blow molding process the HDPE blend is melted and extruded as a hollow tube, called a parison.
  • the parison is enclosed in a cooled metal mold for a shaped article such as a bottle, container, or part. Air or a neutral gas such as nitrogen is then blown into the parison, inflating it into the shape of the mold. After the HDPE blend has cooled sufficiently, the mold is opened, and the part is ejected.
  • the HDPE blend is melted and injected into a metal mold for a shaped article such as a bottle, container, or part. Air or a neutral gas such as nitrogen is then blown into the mold, inflating the HDPE blend into the shape of the mold. After the HDPE blend has cooled sufficiently, the mold is opened, and the part is ejected.
  • a preform of the HDPE blend is made by injection molding.
  • the final neck features for the final molded item (such as threading on a bottle neck) are made on the preform.
  • the molten preform is placed in a mold. Air or a neutral gas such as nitrogen is then blown into the preform, inflating it into the shape of the mold.
  • the mold is opened, and the part is ejected.
  • the preform may be blown immediately after it is formed, or it may be cooled and then reheated and blown later.
  • the temperature of the molten HDPE blend is at least 150°C or at least 155°C or at least 160°C. In some embodiments, the temperature of the molten HDPE blend is at most 210°C or at most 190°C or at most 180°C.
  • the product of the blow-molding is a shaped article.
  • the shaped article is a liquid container, such as ajar or bottle.
  • the liquid container has a capacity of at most 10 L or at most 5 L or at most 2 L or at lost 1 L or at most 0.75 L or at most 0.5 L or at most 0.4 L or at most 0.3L.
  • the liquid container has a capacity of at least 0.1 L or at least 0.3 L or at least 0.5 L or at least 0.75 L or at least 1 L.
  • the liquid container is smaller, having a capacity from 1 to 100 mL.
  • the high-density polyethylene blend comprises: (a) from 25 to 90 weight percent of a recycled high-density polyethylene; and (b) from 10 to 75 weight percent of a virgin bimodal high-density polyethylene having a density from 0.940 gram per cubic centimeter (g/cc) to 0.956 g/cc and a flow index (I21) from 25 grams per 10 minutes (g/10 min.) to 40 g/10 min.
  • the recycled high-density polyethylene is a post-consumer recycled polymer.
  • the virgin bimodal high-density polyethylene has a density from 0.945 g/cc to 0.955 g/cc.
  • the virgin bimodal high-density polyethylene has a flow index (I21) from 28 g/10 min to 35 g/10 min.
  • the virgin bimodal high-density polyethylene has a timed die swell (time to reach 25.4 cm diameter) at a shear rate of 300 per second (s’ 1 ) from 23 seconds to 30 seconds.
  • the high-density polyethylene blend has a density from 0.950 g/cc to 0.965 g/cc, or a flow index (I21) from 28 g/10 min. to 60 g/10 min., or both properties.
  • the high-density polyethylene blend contains at least 45 weight percent of the recycled high-density polyethylene. In some embodiments the high-density polyethylene blend also has an ESCR of at least 30 hours as measured according to ASTM D 1693-13, Condition B, with at 10% surfactant in water; or which has a melt strength of at least 8.5 cN; or which has the ESCR of at least 30 hours and the melt strength of at least 8.5 cN.
  • the high-density polyethylene blend contains at least 70 weight percent recycled high-density polyethylene. In some embodiments the high-density polyethylene blend also has an NCLS of at least 21 hours as measured according to ASTM F2136; or which has a melt strength of at least 7.5 cN; or which has the NCLS of at least 21 hours and the melt strength of at least 7.5 cN.
  • the virgin bimodal high-density polyethylene (HDPE) copolymer comprises from 22.5 weight percent (wt%) to 29.4 wt% of a higher molecular weight HDPE copolymer component (HMW copolymer component) and from 77.5 wt% to 70.6 wt%, respectively, of a lower molecular weight HDPE copolymer component (LMW copolymer component), wherein the copolymer has each of properties (a) to (g): (a) a density from 0.940 g/cc to 0.956 g/cc; (b) a flow index (I21) from 25.0 g/10 min.to 40.0 g/10 min.; (c) a ratio of Mw/Mn from 12 to 18, wherein Mw is weight- average molecular weight and Mn is numberaverage molecular weight, both measured by Conventional Gel Permeation Chromatography (GPC); (d) a melt strength of at least 9 centinewtons (cN), measured at
  • the shaped article such as the blow molded article, comprises this high-density polyethylene blend.
  • Density Density is measured according to ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, e.g., in liquid 2-propanol). Report results in units of grams per cubic centimeter (g/cc).
  • DSC Differential Scanning Calorimetry
  • pellet-form samples are first loaded into a 1 in. diameter chase of 0.13 mm thickness and compression molded into a film under 25,000 lbs. of pressure at 190°C for approximately 10 seconds.
  • the resulting film is then cooled to room temperature, after which the film is subjected to a punch press in order to extract a disk that will fit the aluminum pan supplied by TA Instruments.
  • the disk is then weighed individually (note: sample weight is approximately 4-8mg) and placed into the aluminum pan and sealed before being inserted into the DSC test chamber.
  • the DSC test is conducted using a heat-cool- heat cycle.
  • the sample is equilibrated at 180°C and held isothermally for 5 min to remove thermal and process history.
  • the sample is then quenched to -40°C at a rate of 10°C/min and held isothermally once again for 5 min during the cool cycle.
  • the sample is heated at a rate of 10°C/min to 150°C for the second heating cycle.
  • the melting temperatures and enthalpy of fusion is extracted from the second heating curve, whereas the enthalpy of crystallization is taken from the cooling curve.
  • the enthalpy of fusion and crystallization were obtained by integrating the DSC thermogram from -20°C to the end of melting and crystallization, respectively.
  • the tests are performed using the TA Instruments Q2000 and Discovery DSCs, and data analyses were conducted via TA Instruments Universal Analysis and TRIOS software packages.
  • Flow index (I21) is measured according to ASTM D1238-13, Condition 190°C/21.6 kg, and is reported in g/lOmin. Melt index I5 and I2 are measured following the same procedure using 5.0kg and 2.16 kg load conditions, respectively. Melt Flow Ratio (I21/I5) is calculated based on the results.
  • Melt Strength testing is conducted on either Rheotester 2000 or Rheograph 25 capillary rheometers paired with a Rheotens model 71.97, all of which are manufacture by Gottfert.
  • the die used for testing has a diameter of 2 mm, length of 30 mm, and an entry angle of 180 degrees. Each test is performed isothermally at 190° C. Prior to initiating the test, the sample pellets are loaded into the capillary barrel and allowed to equilibrate at the testing temperature for 10 min.
  • ESCR Environmental Stress Crack Resistance
  • IGEPAL CO-630 is an ethoxylated branched-nonylphenol of structural formula 4-(branched- C9H19)-phenyl-[OCH2CH2]n-OH, wherein subscript n is a number such that the branched ethoxylated nonylphenol has a number- verage molecular weight of about 619 grams/mole.
  • NCLS Notched Constant Ligament Stress
  • Charpy Impact Resistance Charpy impact strength is tested at -40° C. according to ISO
  • Tensile Strength is measured using ASTM D638-14. The average of five specimens tested at a speed of 2 in/min is reported.
  • strain hardening modulus The ISO 18488 standard is followed to determine strain hardening modulus (“SHM”). Polymer pellets are compression molded into sheets of 0.3 mm thickness following molding conditions described in Table 1 of the ISO 18488 standard. After molding, the sheets are conditioned at 120 °C for one hour followed by controlled cooling at a rate of 2 °C/min to room temperature. Five tensile bars (dog bone shaped) are punched out of the compression molded sheets. The tensile test is conducted in a temperature chamber at 80 °C. Each specimen is conditioned for at least 30 minutes in the temperature chamber prior to starting the test. The test specimen is clamped top and bottom and a pre-load of 0.4 MPa with a speed of 5 mm/min is applied.
  • SHM strain hardening modulus
  • the load and the elongation sustained by the specimen are measured.
  • X draw ratio
  • the plot of true stress vs. draw ratio is used to calculate the slope between a draw ratio of 8.0 and 12.0. If failure occurred before a draw ratio of 12.0, then the draw ratio corresponding to the failure strain is considered as upper limit for the slope calculation. If failure occurred before a draw ratio of 8.0, then the test is considered invalid.
  • Die Swell Polymer swell is characterized in terms of “timed swell” by a capillary rheometer. In this approach, the time required for an extruded polymer strand to travel a distance of 10 in. (25.4 cm) is determined. The more the polymer swells, the slower the free end of the strand travels, and the longer it takes to cover the distance.
  • a 12 mm barrel Gbttfert Rheotester 2000 equipped with a 30/1 (mm/mm) L/D capillary die is used for the measurement. The measurement is carried out at 190°C at two fixed shear rates: 300 s 1 and 1000 s’ 1 . The time measure of swell is reported as the t300 and tlOOO values, respectively.
  • Dynamic oscillatory shear measurements are conducted over a range of 0.1 rad s-1 to 100 rad s-1 at a temperature of 190°C and 10% strain with stainless steel parallel plates of 25 mm diameter on the strain controlled rheometer ARES/ARES- G2 by TA Instruments.
  • the rheometer is preheated for at least 30 minutes at 190°C. Place the disk prepared by the Compression Molded Plaque Preparation Method between two “25 mm’’ parallel plates in the oven. Slowly reduce the gap between the “25 mm” parallel plates to 2.0 mm. Allow the sample to remain for exactly 5 minutes at these conditions. Open the oven, and carefully trim excess sample from around the edge of the plates. Close the oven.
  • the chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) and 4- capillary viscometer (DV) coupled to a Precision Detectors (Now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040. For all absolute Light scattering measurements, the 15 degree angle is used for measurement.
  • the autosampler oven compartment was set at 160° Celsius and the column and detector compartment were set at 150° Celsius.
  • the columns used were 4 Agilent “Mixed A” 30cm 20-micron linear mixed-bed columns.
  • the chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT).
  • BHT butylated hydroxytoluene
  • the solvent source was nitrogen sparged.
  • the injection volume used was 200 microliters and the flow rate was 1.0 milliliters/minute.
  • Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights.
  • the standards were purchased from Agilent Technologies.
  • the polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000.
  • the polystyrene standards were pre-dissolved at 80 °C with gentle agitation for 30 minutes then cooled and the room temperature solution is transferred cooled into the autosampler dissolution oven at 160°C for 30 minutes.
  • Equation 1 The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).: where M is the molecular weight, A has a value of 0.4389 and B is equal to 1.0.
  • a fifth order polynomial was used to fit the respective polyethylene-equivalent calibration points.
  • the total plate count of the GPC column set was performed with decane which was introduced into blank sample via a micropump controlled with the PolymerChar GPC-IR system.
  • the plate count for the chromatographic system should be greater than 18,000 for the 4 Agilent “Mixed A” 30cm 20-micron linear mixed-bed columns.
  • Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 2 mg/ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 2 hours at 160° Celsius under “low speed” shaking.
  • a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system.
  • This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear shift in flowrate (Flowrate(effective)) for the entire run.
  • the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 5. Processing of the flow marker peak was done via the PolymerChar GPCOneTM Software. Acceptable flowrate correction is such that the effective flowrate should be within +/-
  • Flowrate(effective) Flowrate(nominal) * (RV(FM Calibrated) / RV(FM Sample)) (EQ5) Triple Detector GPC (TDGPC)
  • the mass detector response (IR5) and the light scattering constant (determined using GPCOneTM) should be determined from a linear standard with a molecular weight in excess of about 50,000 g/mole.
  • the viscometer calibration (determined using GPCOneTM) can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (available from National Institute of Standards and Technology (NIST)).
  • SRM Standard Reference Materials
  • a viscometer constant (obtained using GPCOneTM) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity.
  • the chromatographic concentrations are assumed low enough to eliminate addressing 2nd viral coefficient effects (concentration effects on molecular weight).
  • the absolute weight average molecular weight (MW(Abs)) is obtained (using GPCOneTM) from the Area of the Light Scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area.
  • the molecular weight and intrinsic viscosity responses are linearly extrapolated at chromatographic ends where signal to noise becomes low (using GPCOneTM).
  • Other respective moments, Mn(Abs) and Mz(Abs) are be calculated according to equations 8-10 as follows :
  • Virgin Bimodal HDPE 1 is an embodiment of the virgin bimodal HDPE polymer made using ethylene (“C2”) monomer and 1 -hexene (“Ce”) comonomer and PRODIGYTM BMC-300 bimodal catalyst system from Univation Technologies, LLC.
  • Virgin Bimodal HDPE 2 is another embodiment of the virgin bimodal HDPE polymer made using ethylene (“C2”) monomer and 1- hexene (“Ce”) comonomer and BMC Analog bimodal catalyst system, described earlier.
  • Each of Virgin Bimodal HDPE 1 and Virgin Bimodal HDPE 2 independently comprises a higher molecular weight component that is an ethylene/ 1 -hexene copolymer and a lower molecular weight constituent that is an ethylene/1 -hexene copolymer.
  • Both Virgin Bimodal HDPEs 1 and 2 are made in a fluidized-bed gas phase polymerization (FB-GPP) reactor with an isopentane (“iCs”) feed, under conditions shown in Table 1.
  • Table 1 For comparative purposes, a virgin unimodal HDPE polymer that is commonly blended with recycled polyethylene (UNIVALTM DMDA-6200 polyethylene from The Dow Chemical Company) is obtained.
  • UNIVALTM DMDA-6200 polyethylene from The Dow Chemical Company
  • I and Virgin Bimodal HDPE 2 and DMDA-6200 contain 0.06 wt.% of Irganox- 1010 antioxidant and 0.10 wt.% of Irgafos-168 antioxidant.
  • the PCR polymer is melt-blended with each of the virgin polymers in quantities of 25 weight percent PCR polymer, 50 weight percent PCR polymer, 75 weight percent PCR polymer and 90 weight percent PCR polymer to form HDPE blends.
  • the melt-blending is carried out on a Coperion ZSK 25 mm twin-screw extruder having
  • the motor is rated at 40 horsepower.
  • the gearbox ratio is 1 :89, and the maximum screw speed is 1 ,200 RPM. Maximum torque for this line is 106 Nm.
  • Barrel length is 1125 mm per with 11 barrels comprising the entire process section. Screw diameter is 25.5 mm. Extruder barrel I.D. is 25 mm. Nitrogen padding (9.5 SCFH) is maintained at the feed throat during the entire compounding process.
  • the screw design is the ZSK- 25 mild screw.
  • the screw RPM is 300.
  • Polymers are fed to the extruder using a single auger screw K-tron T-20 polymer feeder.
  • the feed rate is 30 Ibs./hr.
  • the compounded materials are extruded through a 3mm, 2 hole die into a 6 foot long chilled water bath.
  • the strands are passed thru a Huestis Air Block to remove excess water.
  • the cooled and dried strands are pelletized with the Conair strand pelletizer.
  • each HDPE blend is measured.
  • properties of each virgin polymer are measured.
  • inventive examples have higher ESCR and NCLS performance as compared with comparative HDPE blends that contain the same level of virgin polymer.
  • the melt strengths at 190°C for the samples are shown in FIG.s 1 through 5.
  • Table 3 the reported melt strength for each sample is the average melt strength observed in the range of velocities for which the sample shows a rough melt strength plateau. It can be observed that for the virgin polymers and the HDPE blends that contain only 10 percent virgin polymer, the melt strength between in inventive and comparative examples are roughly similar. On the other hand, for HDPE blends that contain 25, 50 and 75 weight percent virgin polymer, the inventive HDPE blends have higher melt strength than comparative HDPE blends that contain the same level of virgin polymer.
  • cN centinewtons
  • ksi kilopounds per square inch
  • psi pounds per square inch
  • kJ/m ⁇ kilojoules per square meter
  • MPa megapascals
  • hr hours.
  • N/k means not known.
  • Table 3 Continued. Properties of Polymers and HDPE/PCR blends.
  • N/k means not known.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Mélange de polyéthylène haute densité contenant de 25 à 90 % en poids de polyéthylène haute densité recyclé et de 10 à 75 % en poids de polyéthylène haute densité bimodal vierge, présentant une densité de 0,94 g/mL à 0,956 g/mL et un indice d'écoulement (I21) de 25 g/10 min. à 40 g/10 min, présentant de bonnes propriétés physiques pour les articles moulés par soufflage, notamment une bonne résistance à la fusion, une bonne rigidité et une bonne résistance à la fissuration.
PCT/US2023/034869 2022-10-11 2023-10-11 Mélanges de polyéthylène contenant des matériaux hdpe vierges et recyclés Ceased WO2024081271A1 (fr)

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EP23805234.4A EP4587513A1 (fr) 2022-10-11 2023-10-11 Mélanges de polyéthylène contenant des matériaux hdpe vierges et recyclés
KR1020257014677A KR20250085790A (ko) 2022-10-11 2023-10-11 버진 및 재활용 hdpe 물질을 함유하는 폴리에틸렌 블렌드

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