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WO2025226645A1 - Polymères bimodaux à base d'éthylène - Google Patents

Polymères bimodaux à base d'éthylène

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Publication number
WO2025226645A1
WO2025226645A1 PCT/US2025/025717 US2025025717W WO2025226645A1 WO 2025226645 A1 WO2025226645 A1 WO 2025226645A1 US 2025025717 W US2025025717 W US 2025025717W WO 2025226645 A1 WO2025226645 A1 WO 2025226645A1
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WIPO (PCT)
Prior art keywords
based polymer
bimodal ethylene
ethylene
mol
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/025717
Other languages
English (en)
Inventor
Rafael HUACUJA
Philip P. Fontaine
Fawzi G. HAMAD
Frederik GEMOETS
Timothy W. Gambrel
Yusen QIAO
Christopher M. Thurber
Akanksha GARG
Kurt W. Olson
Taylor R. PODSIADLIK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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Filing date
Publication date
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Publication of WO2025226645A1 publication Critical patent/WO2025226645A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • Embodiments of the present disclosure generally relate to ethylene-based polymers, and more specifically to bimodal ethylene-based polymers.
  • MD tear refers to the resistance of a material to tear when a force is applied in the machine direction.
  • Dart impact measures the impact strength of a polymer, representing the drop performance of a film in a final article (e.g., a package).
  • the balance between MD tear and dart impact must be considered when designing polymer products.
  • MD tear and dart impact strengths are inversely correlated. Thus, producers generally seek a balance between these properties to ensure that the material can meet all strength requirements for the intended application. In particular, low MD tear often remains an issue, especially if the resulting film is processed at high MD orientation.
  • PCR post-consumer resins
  • Embodiments of the present disclosure meet this need by providing a bimodal ethylene-based polymer having a high density fraction (HDF) from 12.0% to 35.0%, where the high density fraction has a molecular weight of at least 120,000 g/mol.
  • a bimodal ethylene-based polymer having a high density fraction (HDF) from 12.0% to 35.0% and a molecular weight distribution skewed towards higher molecular weights, such as molecular weights of at least 120,000 g/mol results in an improved balance of material properties.
  • bimodal ethylene-based polymer with PCR reductions in material properties due to blending the bimodal ethylenebased polymer with PCR are reduced when a bimodal ethylene-based having a high density fraction (HDF) from 12.0% to 35.0%, where the high density fraction has a molecular weight of at least 120,000 g/mol is utilized, relative to conventional resins.
  • HDF high density fraction
  • Embodiments of the present disclosure include a bimodal ethylene-based polymer, the bimodal ethylene-based polymer being the polymerized reaction product of ethylene and one or more C3-C14 olefinic comonomers.
  • the bimodal ethylene-based polymer comprises: a high density fraction (HDF) from 12.0% to 35.0%, the HDF being defined as a ratio of the mass eluted at temperatures from 93 °C to 119 °C to the total mass eluted when measured using an improved comonomer content distribution (iCCD) curve of mass eluted versus temperature; an I10/I2 ratio from 5.5 to 7.0, wherein I2 is the melt index when measured according to ASTM D 1238 at a load of 2.16 kg and temperature of 190° C. and I10 is the melt index when measured according to ASTM D 1238 at a load of 10 kg and temperature of 190° C; and the high density fraction has a weight averaged molecular weight (Mw) of at least 120,000 g/mol.
  • Mw weight averaged molecular weight
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomer types.
  • Polyethylene or “ethylene-based polymer” shall mean polymers comprising greater than 50% by weight of units that have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more monomer types).
  • Common forms of polyethylene known in the art include Tow Density Polyethylene (TDPE); Tinear Tow Density Polyethylene (TTDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).
  • TDPE Tow Density Polyethylene
  • TTDPE Tinear Tow Density Polyethylene
  • ULDPE Ultra Low Density Polyethylene
  • VLDPE Very Low Density Polyethylene
  • m-LLDPE linear low Density Polyethylene
  • MDPE Medium Density Polyethylene
  • LDPE low density polymer
  • high pressure ethylene polymer or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see, for example, U.S. Patent No. 4,599,392, which is hereby incorporated by reference in its entirety).
  • LDPE resins typically have a density in the range of 0.916 g/cm 3 to 0.930 g/cm 3 .
  • LLDPE includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as “m-LLDPE”), phosphinimine, and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts).
  • LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S.
  • the LLDPE resins can be made via gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.
  • Multilayer structure or “multilayer film” means any structure having more than one layer.
  • the multilayer structure (for example, a film) may have two, three, four, five, six, seven, or more layers.
  • a multilayer structure may be described as having the layers designated with letters.
  • a three-layer structure designated as A/B/C may have a core layer, (B), and two external layers, (A) and (C).
  • bimodal refers to polymers produced from two polymer fractions, each polymer fraction being produced by a distinct catalyst in a distinct reaction environment.
  • compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
  • the term, “consisting essentially of’ excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability.
  • the term “consisting of’ excludes any component, step or procedure not specifically delineated or listed.
  • Recycled polymer refers to polymers, which were incorporated into products and subsequently re-melted to form a recycled polymer.
  • the term “recycled polymer” refers to mechanically recycled polymers, where the polymer is melted and reincorporated into a new product.
  • “Recycled polymer” does not include chemically recycled polymers, where the polymer is broken down into constituent monomers and incorporated into a new virgin polymer. Recycled polymers are defined in ISO 14021 7.8.1.1.
  • post-consumer recycled (or “PCR”), as used herein, refers to a recycled polymeric material that includes materials previously used in a consumer or industry application (i.e., pre-consumer recycled polymer and post-industrial recycled polymer).
  • PCR is typically collected from recycling programs and recycling plants.
  • the PCR ethylene-based polymer may include one or more ethylene-based polymers, such as TDPE, TTDPE, HDPE, or polyethylene.
  • the PCR may include one or more contaminants.
  • the contaminants may be the result of the polymeric 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 is distinct from virgin polymeric material.
  • a virgin polymeric material (such as a virgin polyethylene resin) does not include materials previously used in a consumer or industry application. Virgin polymeric 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 resins differ when compared to virgin polymeric resin, which in turn can present challenges to incorporating PCR into formulations for commercial use.
  • Post-consumer resin is defined in
  • Embodiments of the present disclosure relate to bimodal ethylene-based polymers.
  • the bimodal ethylene-based polymer may be the polymerized reaction product of ethylene and one or more C3-C14 olefinic comonomers.
  • Suitable C3-C14 olefinic comonomers may include, by way of example but not limitation, propylene, 1 -butene, 1 -pentene, 1 -hexene, 4-methyl-l -pentene, 1 -heptene, 1- decene and 1 -octene, as well as other monomer types such as styrene, alkyl-substituted styrenes, vinyl benzocyclobutane, dienes such as 1,4-hexadiene, 1,7-octadiene, 1,9- decadiene, and ethylidene norbornene and cycloalkenes (e.g., cyclopentene, cyclohexene and cyclooctene).
  • the bimodal ethylene-based polymer may comprise from 1 to 49 wt. % of the C3-C14 olefinic comonomers, on the basis of the total polymer weight of the bimodal ethylenebased polymer.
  • the bimodal ethylene-based polymer may comprise from 1 to 45 wt. %, from 1 to 35 wt. %, from 1 to 20 wt. %, from 1 to 5 wt. %, from 5 to 10 wt. %, from 10 to 15 wt. %, from 15 to 20 wt. %, from 20 to 25 wt. %, wt. %, from 25 to 30 wt. %, from 30 to 35 wt.
  • the bimodal ethylene-based polymer may have a high density fraction (HDF) from 12.0% to 35.0%. Generally, having an HDF from 12.0 % to 35.0% is believed to result in increased tear and dart performance. Generally, when the HDF is too low (e.g., less than 12.0 %), the resulting polymer has poor tear performance. Generally, when the HDF is too high (e.g., greater than 35.0 %), the resulting polymer has poor dart performance.
  • HDF high density fraction
  • the bimodal ethylene-based polymer may have a HDF from 12.0% to 30.0%, from 12.0% to 14.5%, from 14.5% to 17.5%, from 17.5% to 20.0%, from 20.0% to 22.5%, from 22.5% to 25.0%, from 25.0% to 27.5%, from 27.5% to 30.0%, from 30.0% to 32.5%, from 32.5% to 35%, or any combination of two or more of these ranges.
  • the HDF is defined as a ratio of the mass eluted at temperatures from 93 °C to 119 °C to the total mass eluted when measured using an improved comonomer content distribution (iCCD) curve of mass eluted versus temperature.
  • iCCD improved comonomer content distribution
  • the HDF of the bimodal ethylene-based polymer may have a weight averaged molecular weight (Mw) of at least 120,000 g/mol.
  • Mw weight averaged molecular weight
  • greater Mw of the HDF is believed to correlate to improved MD-tear performance.
  • the Mw of the FDF will have to be reduced to achieve overall Mw targets. This reduction in the Mw of the LDF is believed to result in poor dart performance.
  • the HDF may have a molecular weight of at least 125,000 g/mol, at least 130,000 g/mol, at least 135,000 g/mol, at least 140,000 g/mol, at least 145,000 g/mol, at least 150,000 g/mol, at least 160,000 g/mol, from 120,000 g/mol to 130,000 g/mol, from 130,000 g/mol to 140,000 g/mol, from 140,000 g/mol to 150,000 g/mol, from 150,000 g/mol to 160,000/g/mol, from 160,000 g/mol to 190,000 g/mol, from 190,000 g/mol to 200,000 g/mol, or any combination of two or more of these ranges.
  • the HDF is defined as a ratio of the mass eluted at temperatures from 93 °C to 119 °C to the total mass eluted when measured using an improved comonomer content distribution (iCCD) curve of mass eluted versus temperature.
  • iCCD improved comonomer content distribution
  • the HDF may have a single peak in the temperature range of from 87 °C to 120 °C.
  • a “single peak” refers to an iCCD wherein a particular fraction include only a single peak. That is, in some embodiments, the iCCD of the HDF and/or the FDF includes only an upward sloping region followed by a downward sloping region to form the single peak.
  • the HDF may have a peak temperature of from 90 °C to 119 °C, from 90 °C to 92 °C, from 92 °C to 94 °C, from 94 °C to 96 °C, from 96 °C to 98 °C, from 98 °C to 100 °C, from 100 °C to 105 °C, from 105 °C to 110 °C, from 110 °C to 115 °C, from 115 °C to 119 °C, or any combination of two or more of these ranges.
  • polymers having an HDF with a single peak in this range e.g., from 87 °C to 120 °C will produce films having a higher MD-tear, relative to other polymers.
  • the bimodal ethylene-based polymer may have a low density fraction (FDF) of from 65.0% to 88.0%.
  • FDF low density fraction
  • the bimodal ethylene-based polymer may have a low density fraction of from 65.0% to 68.0%, from 68.0% to 71.0%, from 71.0% to 74.0%, from 74.0% to 77.0%, from 77.0% to 80.0%, from 80.0% to 83.0%, from 83.0% to 86.0%, from 86.0% to 88.0%, or any combination of two or more of these ranges.
  • the TDF may have a weight averaged molecular weight (Mw) of less than 120,000 g/mol.
  • Mw weight averaged molecular weight
  • the TDF may have a Mw of less than 118,000 g/mol, less than 115,000 g/mol, less than 113,000 g/mol, from 90,000 g/mol to 115,000 g/mol, from 90,000 g/mol to 92,500 g/mol, from 92,500 g/mol to 95,000 g/mol, from 95,000 g/mol to 97,500 g/mol, from 97,500 g/mol to 100,000 g/mol, from 100,000 g/mol to 102,500 g/mol, from 102,500 g/mol to 105,000 g/mol, from 105,000 g/mol to 107,500 g/mol, from 107,500 g/mol, from 107,500 g/mol to 110,000 g/mol, from 110,000 g/mol to 112,500 g/mol, from 112,500 g/mol to
  • the TDF may have a single peak in the temperature range of from 70 °C to 85 °C.
  • the TDF may have a peak temperature of from 76 °C °C to 85 °C, from 70 °C to 72.5 °C, from 72.5 °C to 75 °C, from 75 °C to 76 °C, from 76 °C to 78 °C, from 78 °C to 80 °C, from 80 °C to 82.5 °C, from 82.5 °C to 85 °C, or any combination of two or more of these ranges.
  • films made from polymers where the peak temperature of the TDF is within this range e.g., from 70 °C to 85 °C
  • the difference (A Mw) between the Mw of the HDF and the Mw of the TDF may be at least 30,000 g/mol.
  • a Mw may be at least 31 ,000 g/mol, at least 35,000 g/mol, at least 40,000 g/mol, at least 45,000 g/mol, at least 50,000 g/mol, or from 30,000 g/mol to 90,000 g/mol.
  • the difference (A T) between the peak temperature of the HDF and the peak temperature of the TDF may be at least 15 °C.
  • a T peak temperature of the TDF
  • the difference (A T) between the peak temperature of the HDF and the peak temperature of the TDF may be at least 15 °C.
  • greater A T of the bimodal ethylene-based polymer results in greater tear resistance of the resulting film.
  • the A T may be at least 16 °C, at least 17 °C, at least 18 °C, from 15 °C to 30 °C, from 15 °C to 17.5 °C, from 17.5 °C to 20 °C, from 20 °C to 22.5 °C, from 22.5 °C to 25 °C, from 25 °C to 27.5 °C, from 27.5 °C to 30 °C, or any combination of two or more of these ranges.
  • the bimodal ethylene-based polymer may have a soluble fraction (SF) less than 2.0%.
  • the bimodal ethylene-based polymer may have an SF less than 1.8%, less than 1.6%, less than 1.4%, less than 1.2%, less than 1.0%, less than 0.8%, less than 0.6%, or less than 0.4%.
  • the SF is defined as a ratio of the mass eluted at temperatures less than 35 °C to the total mass eluted when measured according to iCCD.
  • the bimodal ethylene-based polymer may have a molecular weight Mn (conventional) of at least 40,000 g/mol.
  • the bimodal ethylene-based polymer may have a Mn (conventional) of from 40,000 g/mol to 42,000 g/mol, from 42,000 g/mol to 44,000 g/mol, from 44,000 g/mol to 46,000 g/mol, from 46,000 g/mol to 48,000 g/mol, from 48,000 g/mol to 50,000 g/mol, from 50,000 g/mol to 52,000 g/mol, from 52,000 g/mol to 54,000 g/mol, or any combination of two or more of these ranges.
  • the bimodal ethylene-based polymer may have a density of from 0.900 g/cc to 0.925 g/cc.
  • the bimodal ethylene-based polymer may have a density of from 0.900 g/cc to 0.905 g/cc, from 0.905 g/cc to 0.910 g/cc, from 0.910 g/cc to 0.915 g/cc, from 0.915 g/cc to 0.920 g/cc, from 0.920 g/cc to 0.925 g/cc, or any combination of two or more of these ranges.
  • the bimodal ethylene-based polymer may have a melt index (I2) from 0.5 g/10 mins to 7.0 g/10 mins.
  • the bimodal ethylene-based polymer may have an I2 from 0.5 g/10 mins to 6.0 g/10 mins, from 0.5 g/10 mins to 5.0 g/10 mins, from 0.5 g/10 mins to 4.0 g/10 mins, from 0.5 g/10 mins to 3.0 g/10 mins, from 0.5 g/10 mins to 2.0 g/10 mins, from 0.5 g/10 mins to 1.5 g/10 mins, from 0.5 g/10 mins to 1.0 g/10 mins, from 0.5 g/10 mins to 0.95 g/10 mins, from 0.5 g/10 mins to 0.7 g/10 mins, from 0.7 g/10 mins to 0.9 g/10 mins, from 0.9 g/10 mins to 0.98 g/10 mins, from 0.98 g/10 mins to 2 g/10
  • the bimodal ethylene-based polymer may have an I10/I2 ratio from 5.5 to 7.0. In embodiments, the bimodal ethylene-based polymer may have an I10/I2 ratio from 5.5 to 6.7 or from 5.5 to 6.0.
  • the bimodal ethylene-based polymer may have a viscosity ratio (Vo 1/V100) of from 2 to 4.
  • the bimodal ethylene-based polymer may have a viscosity ratio (Vo 1/V100) of from 2.5 to 4, from 2 to 2.2, from 2.2 to 2.4, from 2.4 to 2.6, from 2.6 to 2.8, from 2.8 to 3.0, from 3.0 to 3.2, from 3.2 to 3.4, from 3.4 to 3.6, from 3.6 to 3.8, from 3.8 to 4, or any combination of two or more of these ranges.
  • Embodiments of the present disclosure relate to polymer blends.
  • the polymer blends generally comprise the bimodal ethylene-based polymer described hereinabove and postconsumer recycled (PCR) ethylene-based polymer.
  • the bimodal ethylene-based polymer may be a virgin polymer.
  • the incorporation of PCR ethylene-based polymers into a blend results in reduced material properties (e.g., reduced MD-Tear and/or dart), relative to a virgin polymer.
  • the bimodal ethylene-based polymers of the present disclosure do not experience the same reduction in material properties as conventional ethylene-based polymers, when blended with PCR ethylene-based polymer.
  • the PCR ethylene-based polymer may be an ethylene-based polymer having a density of 0.910 to 0.930 g/cc, such as from 0.910 to 0.915, from 0.915 to 0.920, from 0.920 to 0.925, from 0.925 to 0.930, or any combination of two or more of these ranges.
  • the PCR ethylene-based polymer may be an ethylene-based polymer having a melt index (I2) of 0.3 to 2 dg/min, such as from 0.3 to 0.5 dg/min, from 0.5 to 0.8 dg/min, from 0.8 to 1.1 dg/min, from 0.1 to 1.4 dg/min, from 1.4 to 1.7 dg/min, from 1.7 to 2.0 dg/min, or any combination of two or more of these ranges.
  • the PCR ethylene-based polymer may comprise an EDPE, an HDPE, an EEDPE, or a blend thereof.
  • the PCR ethylene-based polymer resin comprise at least 50 wt. %, at least 75 wt.
  • Suitable PCR ethylenebased polymers include AVANGARDTM NATURA PCR-LDPCR-100 (“AVANGARDTM 100”) and AVANGARDTM NATURA PCR-LDPCR-150 (“AVANGARDTM 150”) (PCR commercially available from Avangard innovative LP, Houston, Texas).
  • the polymer blend may comprise from 10 to 50 wt.% PCR ethylene-based polymer, such as from 10 to 15 wt. %, from 15 to 20 wt. %, from 20 to 25 wt. %, from 25 to 30 wt. %, from 30 to 35 wt. %, from 35 to 40 wt. %, from 40 to 45 wt. %, from 45 to 50 wt. %, or any combination of two or more of these ranges.
  • 10 to 50 wt.% PCR ethylene-based polymer such as from 10 to 15 wt. %, from 15 to 20 wt. %, from 20 to 25 wt. %, from 25 to 30 wt. %, from 30 to 35 wt. %, from 35 to 40 wt. %, from 40 to 45 wt. %, from 45 to 50 wt. %, or any combination of two or more of these ranges.
  • the above-described bimodal ethylene-based polymers, the polymer blends, or films produced therefrom may further include one or more additives as known to those of skill in the art such as, for example, plasticizers, stabilizers including viscosity stabilizers, hydrolytic stabilizers, primary and secondary antioxidants, ultraviolet light absorbers, anti-static agents, dyes, pigments or other coloring agents, inorganic fillers, fire-retardants, lubricants, reinforcing agents such as glass fiber and flakes, synthetic (for example, aramid) fiber or pulp, foaming or blowing agents, processing aids, slip additives, anti-block agents such as silica or talc, release agents, tackifying resins, or combinations of two or more thereof.
  • additives as known to those of skill in the art such as, for example, plasticizers, stabilizers including viscosity stabilizers, hydrolytic stabilizers, primary and secondary antioxidants, ultraviolet light absorbers, anti-static agents, dyes, pigments or other coloring agents,
  • the bimodal ethylene-based polymers, the polymer blends, or films produced therefrom may comprise from 0 to 40 wt. %, such as from 0 to 30 wt. %, from 0 to 20 wt. %, from 0 to 10 wt. %, from 1 to 40 wt. %, from 1 to 30 wt. %, from 1 to 20 wt. %, or from 1 to 10 wt. % of additives.
  • the films may include the bimodal ethylene-based polymers and/or polymer blends described herein.
  • the films may comprise at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or at least 99 wt. % of the bimodal ethylene-based polymers and/or polymer blends described herein.
  • the film is substantially free of any other polymeric component.
  • the film of may be a monolayer or multilayer film, such as a film having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 layers.
  • One or more of the layers of a multilayer film may comprise the bimodal ethylene-based polymers and/or polymer blends described herein.
  • the layer or layers comprising the bimodal ethylene-based polymers and/or polymer blends may each comprise at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or at least 99 wt. % of the bimodal ethylene-based polymers and/or polymer blends described herein.
  • the films of the present disclosure can have a variety of thicknesses.
  • the thickness of the film may depend on a number of factors including, for example, the number of layers in the film, the composition of the layers in the multilayer film, the desired properties of the film, the desired end-use application of the film, the manufacturing process of the film, and others.
  • the film may have a thickness of 0.5 to 5 mils, from 1 to 4 mils, from 1 to 3 mils, from 1.5 to 2.5 mils, from 1.7 to 2.3 mil, or about 2 mil.
  • the film may have a haze of less than 25%, such as less than 20%, less than 15%, or less than 10%.
  • the film may have an MD-Tear of greater than 800 gf, such as greater than 825 gf, greater than 850 gf, or greater than 870 gf.
  • the film may have a dart impact of at least 500 g, such as at least 525 g, at least 550 g, at least 575 g, at least 600 g, at least 650 g, at least 700 g, at least 750 g, at least 800 g, at least 850 g, at least 900 g, or at least 1000 g.
  • Film properties are measured at a thickness of 2 mil.
  • the process of manufacturing the film may include cast film extrusion or blown film extrusion.
  • Embodiments of the present disclosure also relate to articles, such as packages, formed from the films of the present disclosure.
  • the films of the present disclosure are particularly useful in articles where good tear strength and dart strength are desired.
  • Examples of such articles can include flexible packages, pouches, stand-up pouches, and pre-made packages or pouches.
  • Various methods of producing embodiments of articles from the films disclosed herein would be familiar to one of ordinary skill in the art.
  • Samples for density measurement are prepared according to ASTM D 1928. Polymer samples are pressed at 190 °C and 30,000 psi for three minutes, and then at 21 °C and 207 MPa for one minute. Measurements are made within one hour of sample pressing using ASTM D792, Method B.
  • Melt index, or I2 (grams/10 minutes or dg/min) is measured in accordance with ASTM D 1238, Condition 190 °C/2.16 kg, Procedure B.
  • Melt index, or I10 (grams/10 minutes or dg/min) is measured in accordance with ASTM D 1238, Condition 190 °C/10 kg, Procedure B.
  • Haze is measured using a Byk Haze-Gard I. After thickness measurement, the film sample is hold against the lens at the integrating sphere end of the Haze-Gard I where it measures an Illuminant A value in accordance with ASTM DI 003. This test is performed first, since it is non-destructive.
  • IDI is measured according ASTM D7192. This standard requires a probe assembly of l2.70 ⁇ 0.13 mm diameter with hemispherical end of the same diameter.
  • the probe used has a 4500 N range with 1.1 mV/N sensitivity and is designed for dynamic measurements.
  • the dart probe assembly is mounted atop a TinMot linear motor, which is an electromagnetic direct drive motor in tubular form. It has a maximum velocity of 5.4 m/s and maximum force of 1650 N.
  • MD Tear was tested according to ASTM DI 922- 15, covering the average force required to propagate tearing through a specified length of plastic film after the tear has been started using an Elmendorf type tearing tester.
  • the final reactor effluent (second reactor effluent for dual series, the combined effluent for dual parallel, or the single reactor effluent) entered a zone where it was deactivated with the addition of, and reaction with, water. At this same reactor exit location other additives were added for polymer stabilization (Octadecyl 3,5-Di-Tert-Butyl-4- Hydroxyhydrocinnamate, Tetrakis (Methylene(3,5-Di-Tert-Butyl-4-
  • the reactor effluent entered a devolatization system where the polymer was removed from the non-polymer stream.
  • the non-polymer stream was removed from the system.
  • the isolated polymer melt was pelletized and collected.
  • EXCEEDTM 1018 a metallocene catalyst ethylene/hexane copolymer having an E of 1 g/10 minutes and density of 0.918 g/cm 3 , and commercially available from ExxonMobil Chemical was utilized as comparative example Cl.
  • DOWLEXTM GM 8090 a linear low density polyethylene (LLDPE) having a density of 0.916 g/cc and melt index (12) of 1.0 g/10 min, and commercially available from The Dow Chemical Company (Midland, MI), was utilized as comparative example C2.
  • DOWEEXTM GM 8090 is an ethylene-based polymer as that term is defined herein.
  • Two mil blown films were made using a monolayer Dr. Collin blown film line.
  • the line utilizes a 30:1 L/D single screw extruder, equipped with grooved feed zones, and a 30 mm screw diameter.
  • the annular die was 60 mm in diameter and used a dual lip air ring cooling system.
  • the die lip gap was 2 mm and the blow up ratio (BUR) was 2.0.
  • the lay flat width was around 48 cm.
  • the frost line height was 5-6 inches.
  • the total output rate was 5-8 kg/hour.
  • the melt temperature was 200-220 °C, and the die temperature was set at 225 °C.
  • Two mil blown films were made by using a gravimetric feeders to dose resin formulations into a Labtech LTE20-32 twin screw extruder at rate of 15 Ibs/hr. From the extruder, the resin formulation was conveyed into the 2” die diameter die with gap of 1.0 mm. The Labtech feed throat was set to 193 °C and the remaining barrel, conveying portion, and die temperature were set and maintained to 215 °C. Pressurized ambient air was used to inflate the film bubble to a 2.5 blow-up ratio. A dual lip air ring driven by a variable speed blower was used for all experiments. The frost line height (FLH) was maintained between 8.8 and 10.8 inches. Film thickness was targeted at 2 mils and was controlled within ⁇ 15% by adjusting the nip roller speed. The films are wound up into a roll.
  • FLH frost line height
  • Two mil blown films were made on a single 3.5 inch diameter 30:1 L/D Sterling ran at a rate of 250 Ibs/hr. Film was fabricated using an 8 inch die diameter using 1BC (internal bubble cooling). External cooling was provided by a Hosokowa Alpine air ring which operated in sequence with a Kundig gauge scanner to control gauge variation. Film then passed on to a single turret Gloucester high speed (1000 ft/min max) winder where it was collected on a 3” core for sampling. The blow up ratio (BUR) was 2.0 with film thickness targeted at 2 mils.
  • the bimodal ethylene-based polymer films of the present disclosure have improved tear resistance, relative to the comparative films. Additionally, higher AT is correlated with higher MD Tear.
  • AVANGARDTM NATURA PCR-EDPCR-100 a PCR commercially available from Avangard innovative EP, Houston, Texas (hereinafter “PCR”), is a post-consumer recycled ethylene-based polymer with a melt index (E) of 2 dg/min and a density of 0.914 g/cc.
  • DOWEEXTM 2045 G a monomodal EEDPE produced in a single reactor, with a melt index (I2) of 1 dg/min, and a density of 0.92 g/cc, commercially available from Dow Inc. Midland MI, was used as comparative resin CR-1.
  • INNATETM ST50 an LLDPE with a melt index (I2) of 0.83 dg/min, and a density of 0.918 g/cc, commercially available from Dow Inc. Midland MI, was used as comparative resin CR-2.
  • Examples E5 and E6 were used as the bimodal ethylene-based polymers.
  • 2 mil films containing blends of PCR and bimodal ethylene-based polymers in varying ratios were prepared on Line 2 as described above. Additionally, films comprising other LLDPEs and PCR, as well as virgin resin controls were prepared. The Dart and Tear performance of the films was then tested.
  • Table 7 discloses the ASTM normalized dart drop impact, Elmendorf MD-Tear, and instrumented dart impact performance of virgin bimodal ethylene-based polymers and mixtures of 75 wt. % virgin ethylene-based polymer with 25 wt. % PCR.
  • the bimodal ethylene-based polymer E5 shows a slight increase in MD-Tear when PCR is incorporated.
  • Table 8 shows the effect on Haze of incorporating PCR into the polymers of Example E6 and comparative resins CR-1 and CR-2.

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Abstract

Des modes de réalisation de la présente divulgation concernent un polymère bimodal à base d'éthylène, ce polymère bimodal à base d'éthylène étant le produit de réaction polymérisé d'éthylène et d'un ou de plusieurs comonomères oléfiniques en C3-C14. Ledit polymère bimodal à base d'éthylène comprend : une fraction haute densité (HDF) de 12,0 % à 35,0 %, la fraction HDF étant le rapport entre la masse éluée à des températures de 93 °C à 119 °C et la masse totale éluée, mesuré à l'aide d'une courbe de distribution de teneur en comonomères améliorée (iCCD) de la masse éluée en fonction de la température ; un rapport I10/I2 de 5,5 à 7,0, I2 étant l'indice de fusion mesuré selon la norme ASTM D 1238 à une charge de 2,16 kg et une température de 190 °C et I10 étant l'indice de fusion mesuré selon la norme ASTM D 1238 à une charge de 10 kg et une température de 190 °C ; et la fraction haute densité présente un poids moléculaire d'au moins 120000 g/mol.
PCT/US2025/025717 2024-04-26 2025-04-22 Polymères bimodaux à base d'éthylène Pending WO2025226645A1 (fr)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3645992A (en) 1967-03-02 1972-02-29 Du Pont Canada Process for preparation of homogenous random partly crystalline copolymers of ethylene with other alpha-olefins
US3914342A (en) 1971-07-13 1975-10-21 Dow Chemical Co Ethylene polymer blend and polymerization process for preparation thereof
US4076698A (en) 1956-03-01 1978-02-28 E. I. Du Pont De Nemours And Company Hydrocarbon interpolymer compositions
US4599392A (en) 1983-06-13 1986-07-08 The Dow Chemical Company Interpolymers of ethylene and unsaturated carboxylic acids
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5582923A (en) 1991-10-15 1996-12-10 The Dow Chemical Company Extrusion compositions having high drawdown and substantially reduced neck-in
US5733155A (en) 1995-07-28 1998-03-31 The Whitaker Corporation Female contact
US5854045A (en) 1994-05-12 1998-12-29 The Rockefeller University Transmembrane tyrosine phosphatase and methods of use thereof
WO2019241475A1 (fr) 2018-06-15 2019-12-19 Dow Global Technologies Llc Polymères bimodaux à base d'éthylène ayant des fractions de haute densité de haut poids moléculaire
WO2019241518A1 (fr) 2018-06-15 2019-12-19 Dow Global Technologies Llc Films soufflés comprenant des polymères à base d'éthylène bimodaux ayant des fractions de haute densité de poids moléculaire élevé
WO2023064761A1 (fr) * 2021-10-15 2023-04-20 Dow Global Technologies Llc Mélanges de polymères comprenant une résine recyclée après consommation
US20230407065A1 (en) * 2021-01-26 2023-12-21 Dow Global Technologies Llc Polyethylene compositions, films, and articles

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076698A (en) 1956-03-01 1978-02-28 E. I. Du Pont De Nemours And Company Hydrocarbon interpolymer compositions
US4076698B1 (fr) 1956-03-01 1993-04-27 Du Pont
US3645992A (en) 1967-03-02 1972-02-29 Du Pont Canada Process for preparation of homogenous random partly crystalline copolymers of ethylene with other alpha-olefins
US3914342A (en) 1971-07-13 1975-10-21 Dow Chemical Co Ethylene polymer blend and polymerization process for preparation thereof
US4599392A (en) 1983-06-13 1986-07-08 The Dow Chemical Company Interpolymers of ethylene and unsaturated carboxylic acids
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5582923A (en) 1991-10-15 1996-12-10 The Dow Chemical Company Extrusion compositions having high drawdown and substantially reduced neck-in
US5854045A (en) 1994-05-12 1998-12-29 The Rockefeller University Transmembrane tyrosine phosphatase and methods of use thereof
US5733155A (en) 1995-07-28 1998-03-31 The Whitaker Corporation Female contact
WO2019241475A1 (fr) 2018-06-15 2019-12-19 Dow Global Technologies Llc Polymères bimodaux à base d'éthylène ayant des fractions de haute densité de haut poids moléculaire
WO2019241518A1 (fr) 2018-06-15 2019-12-19 Dow Global Technologies Llc Films soufflés comprenant des polymères à base d'éthylène bimodaux ayant des fractions de haute densité de poids moléculaire élevé
US20230407065A1 (en) * 2021-01-26 2023-12-21 Dow Global Technologies Llc Polyethylene compositions, films, and articles
WO2023064761A1 (fr) * 2021-10-15 2023-04-20 Dow Global Technologies Llc Mélanges de polymères comprenant une résine recyclée après consommation

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