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WO2025095955A1 - Procédé de modification de recyclats polymères et compositions fabriquées à partir de celui-ci - Google Patents

Procédé de modification de recyclats polymères et compositions fabriquées à partir de celui-ci Download PDF

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Publication number
WO2025095955A1
WO2025095955A1 PCT/US2023/036739 US2023036739W WO2025095955A1 WO 2025095955 A1 WO2025095955 A1 WO 2025095955A1 US 2023036739 W US2023036739 W US 2023036739W WO 2025095955 A1 WO2025095955 A1 WO 2025095955A1
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Prior art keywords
polymer
recyclate
equal
polarity
ethylene
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Inventor
William R. PODBORNY
Mick C. Hundley
Bo Li
Hrishikesh R. MUNJ
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Equistar Chemicals LP
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Equistar Chemicals LP
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Priority to PCT/US2023/036739 priority Critical patent/WO2025095955A1/fr
Publication of WO2025095955A1 publication Critical patent/WO2025095955A1/fr
Pending legal-status Critical Current
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    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

  • the present disclosure relates to methods for modifying polymer recy elates to improve one or more mechanical properties.
  • Polyolefin/barrier multilayer packaging materials are used to combine the respective performance of different polymers in different layers.
  • the multilayer structure package performs a combination of functions that is not possible with a single layer of one polymer.
  • the multilayer packaging is created to protect sensitive food products sufficiently and obtain extended shelf life.
  • a multilayer film typically comprises outer structural layers and one or more barrier layers disposed between the outer layers to provide a barrier to oxygen transmission.
  • Structural layers provide mechanical properties such as tear resistance and puncture resistance and typically comprise polyolefins or low polarity ethylene or propylene copolymers.
  • Barrier layers typically contain polymers containing polar groups such as, but not limited to, polyamide (nylon), polyester (PET), and/or ethylene vinyl alcohol (EVOH).
  • a polymer recyclate comprising a matrix phase of the polyolefins or low polarity ethylene or propylene copolymers having a dispersed phase of domains of the polymers containing polar groups.
  • the dispersed phase of domains of the polymers containing polar groups negatively affects the processability and mechanical properties of the polymer recyclate in comparison to analogous virgin polymers.
  • the present disclosure relates to a method for modifying a polymer recyclate, wherein the polymer recyclate comprises a matrix phase of a low polarity polymer and a dispersed phase of domains of a high polarity condensation polymer.
  • the polymer recyclate is mixed with a polar protic compound to contact at least a portion of the domains of the high polarity polymer under reaction conditions sufficient to produce a first modified polymer recyclate comprising a matrix phase of the low polarity' polymer and a dispersed phase of domains of a degraded high polarity condensation polymer, wherein the weight average molecular weight of the degraded high polarity' condensation polymer is less than the weight average molecular weight of the high polaritycondensation polymer.
  • Antioxidant agents means compounds that inhibit oxidation, a chemical reaction that can produce free radicals and chain reactions. Antioxidants are differentiated based on their reaction mechanisms and include: (1) primary antioxidants, and (2) secondary antioxidants.
  • Barrier layer means a layer used in a multilayer film to impart gas impermeability in addition to other desired properties to a multilayer structure.
  • Barrier layers herein comprise high polarity polymers.
  • “Compatibility,” as used herein, means the capability of the individual component substances in an immiscible polymer blend to exhibit interfacial adhesion, in which interfaces between phases or components are maintained by intermolecular forces, chain entanglements, or both, across the interfaces — i.e., holding together of two bodies by interfacial forces or mechanical interlocking on a scale of micrometers or less. Further discussion of miscibility can be found in D. W. Fox and R. B. Allen, “Compatibility’, Encyclopedia of Polymer Science and Engineering, 2nd Ed., J. I. Kroschwitz, ed., Wiley Interscience, New York, 1985, Vol. 3, p. 784. Work, W.
  • Compounding conditions means temperature, pressure, and shear force conditions implemented in an extruder to provide intimate mixing of two or more polymers and optionally additives to produce a substantially homogeneous polymer product. The compounding conditions will be such that the specific energy from the compounder from shear and/or added heat are sufficient to melt the polymer components and homogenize them.
  • “HDPE,” as used herein, means ethylene homopolymers and ethylene copolymers produced in a suspension, solution, slurry, or gas phase polymerization process and having a density in the range of 0.940 g/cm 3 to 0.970 g/cm 3 .
  • ‘‘High polarity polymer.” as used herein, means a polar polymer comprising a sufficiently high amount of polar monomer and/or comonomer to result in the polar polymer having a low oxygen vapor transmission rate (OVTR), as measured by ASTM D3985, such as less than or equal to 200 cc’pm/m 2 «day «atm. less than or equal to 150 cc»pm/m 2 »day»atm, less than or equal to 100 cc «pm/m 2 «dayatm, less than or equal to 50 cc «pm/m 2 «dayatm, or less than or equal to 2 cc»pm/m 2 »day*atm.
  • OVTR oxygen vapor transmission rate
  • LDPE ethylene homopolymers and/or ethylene copolymers produced in a high pressure free radical polymerization and having a density in the range of 0.90 g/cm 3 to 0.940 g/cm 3 .
  • LLCPE as used herein, means ethylene copolymers produced in a suspension, solution, slurry, or gas phase polymerization process and having a density in the range of 0.90 g/cm 3 to 0.940 g/cm 3 .
  • Low polarity polymer means a polymer having a sufficiently low amount of polar monomer or comonomer to result in the low polarity polymer having a high oxygen vapor transmission rate (OVTR), as measured by ASTM D3985, such as greater than or equal to 800 cc»pm/m 2 »day»atm, greater than or equal to 900 cc»pm/m 2 »day , atm, or greater than or equal to 1,000 cc»pm/m 2 »day»atm.
  • OVTR oxygen vapor transmission rate
  • the low polarity’ polymer comprises a polyolefin having no polarity', a copolymer of an olefin (such as ethylene or propylene) and an alpha mono-olefin comprising polar group, or a combination thereof.
  • Low polarity polymers have a high degree of miscibility' and/or compatibility with other low polarity polymers and are further characterized as providing one or more of high moisture barrier, high tensile strength, high tear strength, and high puncture resistance as measure by dart drop.
  • MDPE means ethylene copolymers produced in a suspension, solution, slurry, or gas phase polymerization process and having a density in the range of 0.925 g/cm 3 to 0.940 g/cm 3 .
  • miscibility means the degree to which two polymers will mix to form a homogeneous polymer blends. Miscibility' is the capability of a mixture to form a single phase over certain ranges of temperature, pressure, and composition. Whether or not a single phase exists depends on the chemical structure, molar mass distribution, and molecular architecture of the components present. A single phase in a mixture may be confirmed by light scattering, x-ray scattering, and/or neutron scattering. For a two-component mixture, a necessary’ and sufficient condition for stable or metastable equilibrium of a homogeneous, single-phase is: d 2 mi X G ⁇
  • Multilayer film means a coextruded structure comprising at least a barrier layer, a structural layer, and a tie layer.
  • Nonpolar comonomer means a monomer unit containing only carbon and hydrogen.
  • Nonpolar polymer means a polymer or copolymer consisting of units derived from a nonpolar monomers.
  • Olefin as used herein, and alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • Poly monomer means monomers containing highly electronegative atoms, such as chlorine, fluorine, oxygen, nitrogen, or sulfur, that give rise to polymers that contain permanent electric dipoles.
  • Polymer means a polymer or copolymer comprising units derived from a polar monomer.
  • polar polymer refers to polymer formed from at least one monomer that comprises at least one heteroatom. Some examples of heteroatoms include O, N, P and S.
  • Polymer recy elate means post-consumer recycled (“PCR”) polymer and/or post-industrial recycled (“PIR”) polymer.
  • PCR post-consumer recycled
  • PIR post-industrial recycled
  • Polymer recy elate is derived from an end product that has completed its life cycle as a consumer item and would otherwise be disposed of as waste (e.g., a polyethylene water bottle) or from plastic scrap that is generated as waste from an industrial process.
  • Polymer recy elates herein are a mixture of a first low polarity polymer component and a high polarity polymer component comprising at least one polar monomer, such as produced by melting and mixing a barrier film having at least one layer of a first low polarity polymer component and at least on layer of a high polarity polymer component compnsing at least one polar monomer.
  • Polyolefin in some embodiments is a type of polymer with the general formula (CH2CHR)n where R is an alkyl group, including, but not limited to LDPE, LLDPE, MDPE, HDPE, and PP. Polyolefins are nonpolar polymers.
  • Primary antioxidants means compounds which function essentially as free radical terminators or scavengers. Primary antioxidants react rapidly with peroxy and alkoxy radicals. The majority of primary antioxidants for polymers are sterically hindered phenols.
  • Secondary antioxidants as used herein, means compounds which are preventive antioxidants that function by retarding chain initiation. Secondary antioxidants react with hydroperoxides to yield non-radical products and are, therefore, frequently called hydroperoxide decomposers.
  • “Structural layer,” as used herein, means a layer used in a multilayer film to impart desired mechanical properties and/or resistance to moisture to the multilayer structure.
  • the terms “monomer” and “comonomer” are used interchangeably.
  • the terms mean any compound with a polymerizable moiety' that is added to a reactor in order to produce a polymer.
  • a polymer is described as comprising one or more monomers, e.g., a polymer comprising propylene and ethylene
  • ethylene content of 35 wt.% to 55 wt.%
  • the mer unit in the copolymer is derived from ethylene in the polymerization reaction and the derived units are present at 35 wt.% to 55 wt.%. based upon the weight of the copolymer.
  • multilayer film is of particular concern and discussed throughout this description.
  • the description can use a slash to indicate that components to the left and right of the slash are in different layers and the relative position of components in layers can be so indicated by use of the slash to indicate layer boundaries.
  • Ionomer Copolymers of ethylene and unsaturated carboxylic acid comonomers such as but not limited to, EAA and EMAA
  • PA Polyamides such as nylon
  • PE Polyethylene an ethylene homopolymer or copolymer of a major portion of ethylene with one or more alpha-olefins and/or one or more polar comonomers
  • PVDC Poly vinylidene chloride also includes copolymers of vinylidene chloride, such as with vinyl chloride or methyl acrylate (MA)). wt% weight percent
  • Polymer recy elates herein have a matrix phase comprising a low polarity polymer with a dispersed phase of domains of a high polarity condensation polymer, wherein the low polarity polymer and the high polarity condensation polymer are incompatible.
  • Such polymer recyclate can be derived from multilayer films, multilayer molded containers, or a combination thereof.
  • each of one or more low polarity’ polymers comprise one or more polyolefins.
  • a low polarity polymer is a blend of two or more polyolefins such as, but not limited to, a blend of low density polyethylene (LDPE), linear low’ density polyethylene (LUDPE), medium density polyethylene, high density polyethylene (HDPE), and/or polypropylene (PP).
  • LDPE low density polyethylene
  • LLDPE linear low’ density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • a low polarity polymer is a blend of two or more polymers such as, but not limited to, a blend of EVA, ionomers (such as, but not limited to, EAA and EMAA), EMA, ethylene-based copolymers compatible with polyethylene, or a combination thereof.
  • a low polarity polymer is a blend of two or more of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene, high density polyethylene (HDPE), polypropylene (PP), EVA, ionomers (such as, but not limited to, EAA and EMAA), EMA, ethylene-based copolymers compatible with polyethylene, or a combination thereof.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • EVA ionomers
  • ionomers such as, but not limited to, EAA and EMAA
  • EMA ethylene-based copolymers compatible with polyethylene, or a combination thereof.
  • Suitable polyethylenes for a low polarity polymer include ethylene homopolymers and copolymers of units derived from ethylene and units derived from one or more of C3-C20 alphaolefins or mixtures thereof.
  • the units derived from the one or more Cs-Cs alpha-olefin comonomers are present in amounts up to 15 wt. %, based upon the total weight of the copolymer of ethylene.
  • the ethylene homopolymers and copolymers can be produced using either Ziegler Natta catalyst, chromium-based catalyst, or single-site catalyst, e.g., metallocene catalyst.
  • the ethylene homopolymers and copolymers can be produced using a gas phase process, high pressure process, slurry process, or solution process.
  • Ethylene homopolymers and ethylene- Cs-Cs alpha-olefin copolymers include very low density polyethylene (VLDPE), low density' polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE).
  • VLDPE is defined as having a density of 0.860 to 0.910 g/cm 3 , as measured by ASTM D-1505 “Column Method.”
  • LDPE and LLDPE are defined as having densities in the range of from 0.90 to 0.930 g/cm 3 .
  • MDPE is defined as having a density' of 0.925 to 0.940 g/cm 3 .
  • HDPE is defined as having a density of at least 0.945 g/cm 3 , preferably from 0.945 to 0.969 g/cm 3 .
  • the ethylene homopolymers and copolymers preferably have melt indexes (Mis), as measured by ASTM D 1238, condition 190° C./2.16 kg, from 0.01 to 400 dg/min., preferably, from 0.1 to 200 dg/min., more preferably from 1 to 100 dg/min.
  • LDPE is derived from ethylene homopolymers, copolymers of units derived from ethylene and units derived from one or more of C3-C12 alpha-olefins, copolymers of units derived from ethylene and units derived from one or more of alpha monoolefins comprising polar groups, or mixtures thereof.
  • LDPE homopolymers can be produced in a high pressure, free- radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof.
  • Operating conditions for the high-pressure process can include, but are not limited to, a pressure in the range of from 70 MPa to 700 MPa and a temperature in the range of from 150°C to 500°C.
  • Such homopolymers have a high degree of long-chain branching and a density in the range of from 0.910 g/cm' to 0.940 g/cm 3 .
  • LDPE copolymers of ethylene and C3-C12 alpha-olefins can be produced in a high pressure, free-radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof.
  • C3-C12 alpha-olefins include, but are not limited to, substituted or unsubstituted C3 to C12 alpha olefins such as propylene, butene, pentene, hexene, heptene, octene. nonene, decene, undecene, dodecane, and isomers thereof.
  • comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%.
  • Operating conditions for the high-pressure process can include, but are not limited to, a pressure in the range of from 70 MPa to 700 MPa and a temperature in the range of from 150°C to 500°C.
  • Such homopolymers have a high degree of long-chain branching and a density in the range of from 0.910 g/cm 3 to 0.940 g/cm 3 .
  • LDPE copolymers of ethylene and one or more of alpha monoolefins comprising polar groups can be produced in a high pressure, free-radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof.
  • alpha mono-olefins comprising polar groups include, but are not limited to, methacrylic acids, esters (e.g., acetate esters, such as vinyl acetate), nitriles, and amides, such as acrylic acid, methacrylic acid, cyclohexyl methacrylate, methyl acrylate, acrylonitrile, acrylamide, or mixtures thereof.
  • comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%.
  • Operating conditions for the high-pressure process can include, but are not limited to, a pressure in the range of from 70 MPa to 700 MPa and a temperature in the range of from 150°C to 500°C.
  • Such homopolymers have a high degree of long-chain branching and a density in the range of from 0.910 g/cm 3 to 0.940 g/cm 3 .
  • LDPE as described above can be characterized by having: i) a density in the range of from 0.90 g/cm 3 to 0.940 g/cm 3 or from 0.915 g/cm 3 to 0.935 g/cm 3 ; ii) a melt index (2.16 kg, 190°C) less than or equal to 5.0 g/10 min., less than or equal to 1.0 g/10 min., less than or equal to 0.5 g/10 min., less than or equal to 0.2 g/10 min., or less than or equal to 0.1 g/10 min.; iii) a molecular weight distribution (M w /M n ) greater than 4.0, greater than 8.0, or greater than 15, and/or less than 35, less than 30.
  • M w /M n molecular weight distribution
  • M w weight average molecular weight
  • M w weight average molecular weight
  • 600,000 daltons less than or equal to 500,000 daltons, less than or equal to 400,000 daltons, or less than or equal to 300,000 daltons
  • ER melt elasticity
  • Suitable polypropylenes for a low polarity polymer include propylene homopolymers and copolymers, including plastomers, having of units derived from propylene and units derived one or more of ethylene and C4-C20 alpha-olefins or mixtures thereof.
  • the units derived from one or more of ethylene and C4-C10 alpha-olefin comonomers are present in amounts up to 35 wt. %, based upon the total weight of the copolymer of propylene.
  • the propylene homopolymers and copolymers can be produced using either Ziegler Natta or single-site catalysts, e.g., metallocene catalysts.
  • the propylene homopolymers and copolymers can be produced using a gas phase process, slurry process, or solution process.
  • the propylene polymer when it is a copolymer, it preferably contains 2 to 6 wt. %, based upon the total weight of the copolymer, of ethylene derived units as a comonomer.
  • a first low polarity polymer component comprises a copolymer of ethylene and one or more polar comonomer, a copolymer of propylene and one or more polar comonomers, or a combination thereof, wherein the low first polarity polymer component has an oxygen vapor transmission rate (OVTR), as measured by ASTM D3895, of greater than or equal to 800 cc «pm/m 2 «dayatm. greater than or equal to 900 cc*pm/m 2 *dayatm, or greater than or equal to 1,000 cc’pm/m 2 «dayatm.
  • OVTR oxygen vapor transmission rate
  • a low polarity polymer can also be formed from a blend of two or more polyethylenes, two or more polypropylenes, or one or more polyethylenes and one or more polypropylenes.
  • a low polarity polymer can also be formed from a blend of two or more polyolefins, two or more olefin-based polymers (other than but compatible with polyolefins), or one or more polyolefins and one or more olefin-based polymers (other than but compatible with polyolefins).
  • a high polarity condensation polymer herein comprises a polymer having an oxygen vapor transmission rate (OVTR). as measured by ASTM D3895, of less or equal to 200 cc , pm/m 2 «day , atm, less than or equal to 150 cc»pm/m 2 »day»atm, less than or equal to 100 cc’pm/m 2 «day»atm, less than or equal to 50 cc’pm/m 2 «day»atm, or less than or equal to 2 cc «pm/m 2 «dayatm.
  • a barrier layer can include polyester, a polyamide, a polycarbonate, a polyvinyl alcohol, a polyurethane, an ethylene vinyl alcohol, or a combination thereof.
  • Polyesters are a category of polymers that contain the ester functional group in their main chain. While polyethylene terephthalate (PET) is the most common type of polyester used in packaging, several other polyesters also possess properties that can be useful in barrier layers in multilayer films or molded containers.
  • a polyester comprises polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexylenedimethylene terephthalate (PCT), polytrimethylene terephthalate (PTT), polyglycolic acid (PGA), polylactic acid (PLA), polyethylene furanoate (PEF), or a combination thereof.
  • Polyamides often known as nylons, are a group of polymers that provide a good barrier against gases like oxygen and carbon dioxide, making them valuable in packaging, especially for food products that need protection from oxygen to ensure freshness and quality. They also have excellent mechanical properties, chemical resistance, and are typically used in combination with other materials in multilayer fdms to exploit these properties.
  • a polyester comprises PA 6 (nylon 6), PA 66 (nylon 6,6), PA 11, PA 12, PA 6/66 copolymer, PA 6/12 copolymer, PA 6/66/6T copolymer, PA 6I/6T, MXD6 (Polyamide MXD6), bio-based polyamides, or a combination thereof.
  • PC Polycarbonates
  • standard polycarbonate materials generally do not have exceptional barrier properties against gases like oxygen or carbon dioxide, which are often crucial for packaging applications. Still, they are used in multilayer structures for their other properties, often in combination with materials that do provide good gas barrier properties.
  • polycarbonates refers to a category of polymers that are characterized by the carbonate group in their chemical structures. The most common ty pe of polycarbonate is based on bisphenol A (BPA), but there are several other polycarbonates, including those developed to address concerns about the potential health effects of BPA.
  • BPA bisphenol A
  • a polycarbonate comprises bisphenol A polycarbonate (BPA-PC), bisphenol S polycarbonate (BPS-PC), bisphenol F polycarbonate (BPF-PC), bisphenol C polycarbonate (BPC- PC), bisphenol Z polycarbonate (BPZ-PC), bisphenol-free polycarbonates, polycarbonate copolymers, aliphatic polycarbonates, or a combination thereof.
  • BPA-PC bisphenol A polycarbonate
  • BPS-PC bisphenol S polycarbonate
  • BPF-PC bisphenol F polycarbonate
  • BPC- PC bisphenol C polycarbonate
  • BPZ-PC bisphenol Z polycarbonate
  • Polyvinyl alcohols are synthetic resins prepared by the polymerization of vinyl acetate, followed by hydrolysis of the polyvinyl acetate. They are used in a variety of applications due to their emulsifying and adhesive properties, as well as resistance to oil, grease, and solvents. They are also notable for their barrier properties, particularly in preventing gas and aroma permeabilities, making them useful as a barrier layer in multilayer films.
  • a polycarbonate comprises fully hydrolyzed PVA, partially hydrolyzed PVA, high molecular weight PVA, low 7 molecular weight PVA, modified PVA, copolymerized PVA, or a combination thereof.
  • PUs Polyurethanes
  • a polycarbonate comprises thermoplastic polyurethane (TPU), polyether polyurethane, polyester polyurethane, polycaprolactone polyurethane, aliphatic polyurethane, aromatic polyurethane, waterborne polyurethane, polyurethane foams, bio-based polyurethane, or a combination thereof.
  • Ethylene vinyl alcohol is a class of polymers known for its exceptional gas barrier properties, high resistance to oils and organic solvents, and flexibility . It is a copolymer of ethylene and vinyl alcohol. EVOH is typically coextruded with other materials in multilayer packaging for food, medical, pharmaceutical, cosmetic, and automotive fuel applications due to its ability to retain gases and flavors and prevent external contamination.
  • an ethylene vinyl alcohol comprises low ethylene content EVOH (typically around 24% to 32%), medium ethylene content EVOH (typically around 38% to 44%), high ethylene content EVOH (typically around 48% to 72%), or a combination thereof. Higher ethylene content provides more flexibility' and better moisture resistance, while higher vinyl alcohol content provides more rigidity and better gas barrier properties.
  • Polar protic compounds are a subset of molecules that possess both polarity and the ability to form hydrogen bonds, typically via a hydrogen atom attached to an electronegative element such as oxygen, nitrogen, or fluorine. These molecules’ polarity’ arises from the uneven distribution of electron density, resulting in a molecule with a distinct dipole moment, characterized by partial positive (5+) and negative (5-) charges.
  • the ‘protic’ aspect refers to these compounds’ proclivity to donate protons (H + ) in reactions, facilitated by the hydrogen atoms’ loosely held status, bonded to electronegative atoms.
  • a polar protic compound comprises water, an alcohol, a carboxylic acid, an amine, an amide, or a combination thereof.
  • water is a desirable polar protic compound due to its polarity, high dielectric constant, and capability for hydrogen bonding.
  • an alcohol is a desirable polar protic compound, and can include simple alcohols, polyols, or a combination thereof.
  • simple alcohols comprise a Ci-Ce alcohol, such as, but not limited to, methanol, ethanol, propanol, butanol, isopropyl alcohol, or a combination thereof.
  • polyols comprise a Ci-Ce polyol, such as, but not limited to, glycerol, propylene glycol, ethylene glycol, sorbitol polyethylene glycol, propylene glycol (PEG), ery thritol, or a combination thereof.
  • a carboxylic acid is a desirable polar protic compound, and can include Ci-Ce carboxylic acids, such as, but not limited to, acetic acid, formic acid, citric acid, or a combination thereof.
  • an amine is a desirable polar protic compound, and can include amines, such as, but not limited to, methylamine, ethylamine, aniline, or a combination thereof.
  • an amine is a desirable polar protic compound, and can include amides, such as, but not limited to, acetamide, benzamide, urea, or a combination thereof.
  • a polar protic compound comprises water, a Ci-Ce alcohol, a C1-C6 carboxylic acid, a Ci-Ce polyol, or a combination thereof.
  • the polymer recyclate is prepared for mixing with a polar protic compound.
  • the polar protic compound must contact at least a portion of the domains of the high polarity condensation polymer.
  • the polymer recyclate is modified in a solution process to produce a first modified polymer recyclate.
  • the polymer recyclate is modified in a compounding process to produce a first modified polymer recyclate. As the molecular weight of the high polarity condensation polymer is reduced, the dispersion of the high polarity polymer within the low polarity polymer matrix can be improved.
  • One advantage of this modification is the minimization of domain size of the dispersed high polarity polymer (or low gel level).
  • mechanical properties of polymer recyclate can be improved, including, but not limited to, one or more of mechanical elongation, strength, toughness, environmental stress crack resistance (ESCR), structural integrity', puncture resistance, heat resistance, heat sealability', and/or abrasion resistance.
  • ESCR environmental stress crack resistance
  • polymer recyclate is prepared or provided as a particulate matter, such as, but not limited to, pellets, granules, or powder.
  • a quantity of polymer recyclate particles are immersed in a solution comprising the polar protic compound.
  • the size of the particles is selected to provide a desired ratio of surface area per unit volume of the particles of polymer recyclate.
  • a higher ratio of surface area per unit volume of the particles of polymer recyclate will enable the polar protic compound to contact a greater portion of the domains of the the high polarity condensation polymer to enable reducing the molecular weight of a greater proportion of the high polarity condensation polymer in the polymer recyclate.
  • a first modified polymer recyclate is recovered and separated from the solution.
  • the threshold time period is greater than or equal to 1 minute, greater than or equal to 5 minutes, or greater than or equal to 10 minutes.
  • the threshold time period is less than or equal to 3 hours, less than or equal to 2 hours, or less than or equal to 1 hour.
  • the solution comprising the polar protic compound and the polymer recyclate can be unagitated, intermittently agitated, or continuously agitated.
  • the temperature of the solution comprising the polar protic compound and the polymer recyclate during the threshold time period is in the range of from -10°C to just below the boiling point of the solution, from 0°C to 10°C below the boiling point of the solution, from 10°C to 20°C below the boiling point of the solution, or from 20°C to 30°C below the boiling point of the solution.
  • the polymer recyclate melt comprises the polar protic compound in an amount in the range of from 500 ppmw to 5 wt%, based on the total weight of the polymer recyclate melt and the polar protic compound.
  • the high polarity condensation polymer in the polymer recy clate has a first weight average molecular weight (M w i). and the degraded high polarity condensation polymer in the first modified polymer recyclate has a second weight average molecular weight (M W 2>, wherein M w ? is less than Mwi.
  • Mw Mwi is less than or equal to 0.9, less than or equal to 0.8, less than or equal to 0.7, less than or equal to 0.6, or less than or equal to 0.5.
  • the method further comprises blending the first modified polymer recyclate with a functionalized polymer as described below to form a second modified polymer recyclate.
  • the functionalized polymer is present in the blend of the first modified polymer recyclate and the functionalized polymer in an amount in the range of from 0.5 wt.% to 30 wt.%, or 1 wt.% to 20 wt.%, or 2 wt.% to 15 wt.%, or 5 wt. % to 15 wt. %, or 6 wt.% to 11 wt. %.
  • the functional groups of the functional polymer are compatible with the domains of degraded high polarity condensation polymer and act to more uniformly distribute the domains of degraded high polarity condensation polymer and/or to compatibilize the domains of degraded high polarity condensation polymer with the low polarity polymer matrix.
  • the polymer recyclate and a polar protic compound are fed to an extruder, a mixer, or any apparatus capable of compounding conditions sufficient to melt and mix the polymer recyclate.
  • compounding conditions are implemented in the compounding zone of an extruder or mixer and are tailored for mixtures of specific low polarity polymers and polar protic compounds.
  • Temperature, pressure, and shear force conditions are implemented in the extruder or mixer sufficient to provide intimate mixing of the w polarity polymers, graft agents, optionally one or more initiators, to produce polymer chains comprising free radicals and/or graft agents comprising free radicals.
  • compounding conditions will be such that the specific energy from the compounder from shear and/or added heat are sufficient to melt the polymer components and homogenize them with the other components in the mixture in the extruder or mixer.
  • compounding conditions comprise a temperature in the compounding zone of less than or equal to 300°C, less than or equal to 250°C or less than or equal to 200°C.
  • temperatures in the compounding zone can be in the range of from 125°C to 195°C, from 130°C to 180°C, or from 135°C to 165°C.
  • temperatures in the compounding zone can be in the range of from 175°C to 245°C, from 180°C to 230°C, or from 185°C to 215°C.
  • the polar protic compound reacts with the domains of the high polarity condensation polymer to reduce the molecular weight of the high polarity condensation polymer.
  • a first modified polymer recyclate is withdrawn from the extruder or mixer, wherein the first modified polymer recyclate comprises a matrix phase of the low polarity polymer and a dispersed phase of domains of the degraded high polarity condensation polymer.
  • the first modified polymer recyclate withdrawn from the extruder can be pelletized for later mixing a functionalized polymer as described below or can be blended in the melted state with such functionalized polymer to form a second modified polymer recyclate.
  • the functionalized polymer is present in the blend of the first modified polymer recyclate and the functionalized polymer in an amount in the range of from 0.5 wt.% to 30 wt.%, or 1 wt.% to 20 wt.%, or 2 wt.% to 15 wt.%, or 5 wt. % to 15 wt. %, or 6 wt.% to 11 wt.
  • the functional groups of the functional polymer are compatible with the domains of degraded high polarity' condensation polymer and act to more uniformly distribute the domains of degraded high polarity condensation polymer and/or to compatibilize the domains of degraded high polarity condensation polymer with the low polarity polymer matrix.
  • a functionalized polymer as disclosed herein comprises a modified polymer produced by reacting a polymer with functional groups or monomers, such as acid and/or acid derivative moi eties, wherein the polymer has the one or more functional groups or monomers grafted along the polymer chain.
  • the modified polymer is a functionalized polyolefin, functionalized low polarity polymer (including polyolefin), or a combination thereof.
  • the low' polarity' polymer and/or the polyolefin is a polymer recyclate.
  • the second low polarity polymer is a polyolefin such as a polyethylene homopolymer or copolymer.
  • the polyolefin is a polypropylene homopolymer or copolymer.
  • the polymer is a low polarity polymer (other than polyolefin).
  • the low polarity’ polymer is a copolymer of ethylene and one or more polar comonomers.
  • the low polarity polymer is a copolymer of propylene and one or more polar comonomers.
  • the functionalized polymer is formed by addition of one or more pendant functional groups to a polymer backbone comprising a low polarity polymer (including polyolefin).
  • the polyolefin can be an ethylene homopolymer or copolymer of ethylene and one or more alpha olefins.
  • the low polarity' polymer (other than polyolefin) can be a copolymer of ethylene and one or more alpha mono-olefins comprising polar groups or a copolymer of propylene and one or more alpha mono-olefins comprising polar groups.
  • functionalized polymer as disclosed herein comprises a modified low polarity polymer produced by reacting a low polarity' polymer with functional groups or monomers, such a carboxylic acid, a carboxylic acid derivative, an acid derivative, an anhydride, an anhydride derivative, and combinations thereof, wherein the low polarity' polymer has the one or more functional groups or monomers grafted along the polymer chain.
  • Functionalized polymers are generally formed by grafting a functional monomer onto the backbone (i.e., main chain) of a low polarity polymer.
  • the composition of the low polarity polymer can be a polyolefin comprising a single ethylene-based polymer, a single propylene-based polymer, a blend of two or more ethylene-based polymers, a blend of two or more propylene-based polymers, or a blend of at least one ethylene-based polymer and at least one propylene-based polymer. Suitable ethylene-based polymers and propylene-based polymers are described below.
  • the one or more polymers selected from ethylene-based polymers, propylene-based polymers, and combinations thereof selected for the composition of the olefin-base polymer can be the same as or different from those chosen for the composition of the polyolefin of the one or more structural layers of the multilayer barrier film.
  • the functional groups included in the functionalized polymer are selected for having miscibility’ and/or compatibility with the barrier layer composition.
  • the low polarity’ polymer portion of the functionalized polymer is selected for having miscibility and/or compatibility with the structural layer composition.
  • the functional monomer can be grafted onto the polarity polymer via processes known to one skilled in the art.
  • the graft may be formed via reactive extrusion processes.
  • Reactive extrusion processes generally include contacting the low polarity polymer with the functional monomer within an extruder or in a solution process to form the functionalized polymer.
  • the reactive extrusion processes may include any extrusion process known in the art.
  • raw 7 materials e.g., low polarity polymer and functional monomer
  • the reaction to form the functionalized low polarity polymer may occur in the twin screws extruder under constant mixing and kneading, for example.
  • the functionalized low polarity polymer generally includes a linear backbone of the polarity polymer with randomly distributed branches of the functional monomer, resulting in side chains that are structurally distinct from the main chain/backbone.
  • the low polarity polymer contacts the functional monomer in the presence of an initiator.
  • Initiators can be selected from those known to one skilled in the art, such as, but not limited to, organic peroxides. However, as discussed previously herein, grafting can take place under high temperature and high shear in absence of an initiator.
  • functionalized polymers of the invention are conveniently prepared by grafting the low polarity polymer in the substantial absence of solvent. This can be accomplished in a shear-imparting reactor, such as an extruder/reactor. Twin screw 7 extruder/reactors such as those manufactured by Coperion (formerly Wemer-Pfleiderer) under the designations ZSK.-53, ZSK-83 and ZSK-92 are commonly used. A free radical generating catalyst, such as an organic peroxide catalyst, can be employed but is not necessary. The grafting reaction is carried out at a temperature selected to minimize or avoid rapid vaporization and consequent losses of the graft monomer and any catalyst that may be employed.
  • a shear-imparting reactor such as an extruder/reactor.
  • Twin screw 7 extruder/reactors such as those manufactured by Coperion (formerly Wemer-Pfleiderer) under the designations ZSK.-53, ZSK-83 and ZSK-92 are commonly used.
  • a free radical generating catalyst such as an
  • the graft monomer concentration in the reactor is typically about 1 to about 5 wt. % based on the total reaction mixture w eight.
  • a temperature profile w here the temperature of the low polarity polymer melt increases gradually through the length of the extruder/reactor up to a maximum in the grafting reaction zone and then decreases toward the reactor exit is preferred.
  • the maximum temperature within the reactor should be such that significant vaporization losses and/or premature decomposition of any peroxide catalyst are avoided. For example, if di-t-butyl peroxide and 2,5-dimethyl-2,5-di-(t- butylperoxy) hexane are used, temperatures within the reactor are maintained at or below 7 about 220°C.
  • Examples of useful peroxide catalysts include: l,l-bis(t-butylperoxy)cyclohexane; n- butyl-4.4-bis(t-butylperoxy-valerate); l,l-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane: 2,2- bis(t-butyl-peroxy)butane; dicumylperoxide; t-butylcumylperoxide; alpha, alpha'-bis(t- butylperoxy-preoxy-isopropyl)benzene; di-t-butylperoxide; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; and the like.
  • grafting monomer and any catalyst used are preferably added in neat form to the extruder/reactor.
  • compounding conditions are implemented in the compounding zone of an extruder or mixer and are tailored for mixtures of specific low polarity polymers, graft agents, optionally one or more initiators, and optionally additives. Temperature, pressure, and shear force conditions are implemented in the extruder or mixer sufficient to provide intimate mixing of the w polarity polymers, graft agents, optionally one or more initiators, to produce polymer chains comprising free radicals and/or graft agents comprising free radicals.
  • compounding conditions will be such that the specific energy from the compounder from shear and/or added heat are sufficient to melt the polymer components and homogenize them with the other components in the mixture in the extruder or mixer.
  • compounding conditions comprise a temperature in the compounding zone of less than or equal to 300°C, less than or equal to 250°C or less than or equal to 200°C.
  • temperatures in the compounding zone can be in the range of from 125°C to 195°C. from 130°C to 180°C, or from 135°C to 165°C.
  • temperatures in the compounding zone can be in the range of from 175°C to 245°C, from 180°C to 230°C, or from 185°C to 215°C.
  • the polymer recyclate can be pelletized for later mixing a functionalized polymer as described below or can be blended in the melted state with such functionalized polymer.
  • the functionalized polymer i.e., functionalized low polarity polymer
  • the functionalized polymer is obtained by grafting an ethylenically unsaturated carboxylic acid or derivative, particularly MAH, onto the polymer backbone.
  • the grafting may be accomplished using know n procedures in solution, in a fluidized bed reactor, by melt grafting or by irradiation grafting.
  • the term grafting denotes covalent bonding of the grafting monomer to the polymer chain.
  • the functionalized polymer may include the functional monomer in a range of from 0.10 wt% to 2.9 wt%, from 0.45 wt% to 2.8 wt%, from 0.70 wt% to 2.7 wt%, from 1.05 wt% to 2.6 wt%, from 1.50 wt% to 2.5 wt%, wherein weight percentages are based on the total weight of the functionalized polymer.
  • the functionalized polymer has a melt index (b) in the range of from 0.5 dg/min. to 600 dg/min., 1.0 dg/min. to 500 dg/min., from 3.0 dg/min. to 400 dg/min., from 5.0 dg/min. to 300 dg/min., from 7.0 dg/min. to 200 dg/min., or from 9.0 dg/min. to 100 dg/min.
  • the functionalized polymer has a density in the range of from 0.850 g/cm’ to 0.960 g/cm 3 , from 0.855 g/cnT to 0.950 g/cn , from 0.860 g/cm 3 to 0.940 g/cm 3 , from 0.865 g/cm 3 to 0.930 g/cm 3 , or from 0.870 g/cm 3 to 0.920 g/cm 3 .
  • the functionalized polymer has a melt elasticity (ER) in the range of from 0.30 to 3.00, from 0.31 to 2.35, from 0.32 to 1.70, from 0.33 to 1.05, or from 0.34 to 0.40.
  • the functionalized polymer has a melting temperature (Tm) in the range of from 50°C to 170 °C, from 51°C to 145°C, from 52°C to 125°C, from 53°C to 105°C, from 54°C to 85°C, or from 55°C to 65°C.
  • Tm melting temperature
  • the first modified polymer recy elate and/or the second modified polymer recyclate can by used in place of or in a blend with an analogous virgin polymer to form a film, a layer of a multilayer film, a molded container, or a layer of a multilayer molded container.
  • the method comprises providing a polymer recyclate comprising a matrix phase of a low polarity polymer and a dispersed phase of domains of a high polarity condensation polymer.
  • the polymer recyclate is mixed with a polar protic compound.
  • the polar protic compound is contacted with at least a portion of the domains of the high polarity polymer under reaction conditions sufficient to produce a first modified polymer recyclate comprising a matrix phase of the low polarity polymer and a dispersed phase of domains of a degraded high polarity condensation polymer.
  • the high polarity condensation polymer in the polymer recyclate has a first weight average molecular weight (Mwi), and the degraded high polarity' condensation polymer in the first modified has a second weight average molecular weight (M W 2), and M W 2 is less than M w i.
  • the method is further characterized by one or more of the following: a) M shadow2/Mwi is less than or equal to 0.9, less than or equal to 0.8, less than or equal to 0.7, less than or equal to 0.6, or less than or equal to 0.5; b) the high polarity polymer has an oxygen vapor transmission rate (OVTR) less than or equal to 200 cc*pm/m 2 *day»atm, and the low polarity polymer has an OVTR greater than or equal to 800 cc’pm/m 2 «day»atm; c) the high polarity condensation polymer comprises a polyester, a polyamide, a polycarbonate, a polyvinyl alcohol, a polyurethane, ethylene vinyl alcohol, or a combination thereof; d) the polar protic compound comprises water, a Ci-Ce alcohol, a Ci-Ce carboxylic acid,
  • the method for producing a modified polymer recy elate product is a solution process comprising one or more of the above limitations of the method for producing a modified polymer recyclate product, wherein the reaction conditions of the solution process comprise immersion of particles of the polymer recyclate in a solution of the polar protic compound for a time period in the range of from 1 minute to 3 hours.
  • the reaction conditions further comprise a reaction temperature in the range of from -10°C to just below the boiling point of the solution.
  • the method for producing a modified polymer recyclate product is a compounding process comprising one or more of the above limitations of the method for producing a modified polymer recyclate product, wherein the reaction conditions of the compounding process comprise heat and/or mechanical shear sufficient to form a polymer recyclate melt, wherein the polymer recyclate melt further comprises the polar protic compound in an amount in the range of from 500 ppmw to 5 wt%, based on the total weight of the polymer recyclate melt and the polar protic compound.
  • the method for producing a modified polymer recyclate product, the solution process, or the compounding process further comprises blending the first modified polymer recyclate with a functionalized polymer to form a second modified polymer recyclate, wherein the functionalized polymer comprises a base polymer grafted with one or more functional groups, and the base polymer is compatible with the low polarity polymer of the polymer recyclate.
  • the blending step is further characterized by one or more of the following: a) the one or more functional groups are selected from the group consisting of a carboxylic acid, a carboxylic acid derivative, an acid derivative, an anhydride, an anhydride derivative, and combinations thereof; b) the functionalized polymer comprises one or more functional groups in an amount in the range of from 0.10 wt% to 2.9 wt%, from 0.45 wt% to 2.8 wt%, from 0.70 wt% to 2.7 wt%, from 1.05 wt% to 2.6 wt%, from 1.50 wt% to 2.5 wt%, wherein weight percentages are based on the total weight of the functionalized polymer; and c) the functionalized polymer is present in an amount up to 30 wt%, in the range of from 0.5 wt.% to 30 wt.%, or 1 wt.% to 20 wt.%, or 2 wt.% to 15 wt
  • Densities are determined in accordance with ASTM D-792 and ASTM D-1505/ISO-1183.
  • Shear rheological measurements are performed in accord with ASTM 4440-95a, which characterize dynamic viscoelastic properties (storage modulus, G', loss modulus, G” and complex viscosity, r/ as a function of oscillation frequency, co).
  • a rotational rheometer (TA Instruments) is used for the rheological measurements.
  • a 25 mm parallel-plate fixture was utilized. Samples were compression molded in disks ( ⁇ 29 mm diameter and ⁇ 1.3 mm thickness) using a hot press at 190 °C.
  • An oscillatory frequency sweep experiment (from 398.1 rad/s to 0.0251 rad/s) was applied at 190°C. The applied strain amplitude is - 10% and the operating gap is set at 1 mm. Nitrogen flow was applied in the sample chamber to minimize thermal oxidation during the measurement.
  • Elongation at break (%) Elongation at break was measured according to ASTM D-638.
  • Haze (%) Film haze measurements were made following ASTM D1003.
  • ER Melt elasticity
  • MWD molecular weight distribution
  • Mn weight-average molecular weight, M w , and z-average molecular weight, M z are determined using a high temperature Polymer Char gel permeation chromatography (“GPC”), also referred to as size exclusion chromatography (“SEC”), equipped with a filter-based infrared detector, IR5. a four-capillary differential bridge viscometer, and a Wyatt 18-angle light scattering detector.
  • GPC Polymer Char gel permeation chromatography
  • IR5 size exclusion chromatography
  • M n , M w , M z ,MWD, and short chain branching (SCB) profiles are reported using the IR detector, whereas long chain branch parameter, g’, is determined using the combination of viscometer and IR detector at 145°C.
  • Three Agilent PLgel Olexis GPC columns are used at 145°C for the polymer fractionation based on the hydrodynamic size in 1,2,4- trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) as the mobile phase. 16 mg polymer is weighted in a 10 mL vial and sealed for the GPC measurement.
  • the dissolution process is obtained automatically (in 8 ml TCB) at 160°C for a period of 1 hour with continuous shaking in an Agilent autosampler. 20 pL Heptane was also injected in the vial during the dissolution process as the flow marker. After the dissolution process, 200 pL solution was injected in the GPC column.
  • the GPC columns are calibrated based on twelve monodispersed polystyrene (PS) standards (provided by PSS) ranging from 578 g/mole to 3,510,000 g/mole.
  • PS monodispersed polystyrene
  • the comonomer compositions are reported based on different calibration profiles obtained using a series of relatively narrow polyethylene (polyethylene w ith 1 -hexene and 1- octene comonomer were provided by Polymer Char, and polyethylene with 1 -butene were synthesized internally) with known values of CH3/IOOO total carbon, determined by an established solution NMR technique. GPC one software was used to analyze the data.
  • Oxygen gas transmission rate can be measured by ASTM D3985.
  • Narrow Angle Scatter Film NAS measurements were made following ASTM D1746 (2015) Standard Test Method for Transparency of Plastic Sheeting. Multi-layer film specimens can be cut into 10 cm x 10 cm squares and adhered to the test unit in front of the light source by air suction. Films can be oriented in the same direction and tested in the same fashion to minimize testing variables. A minimum of six specimens can be run for each sample.
  • Polar polymer domain size (in the examples herein. EV OH) was measured by Scanning Electron Microscopy (SEM) which is described, for example, in an article to F. Mirabella, et al. entitled “Morphological Explanation of the Extraordinary Fracture Toughness of Linear Low Density Polyethylenes", J. Polymer Science: Part B: Polymer Physics, Vol. 26, No. 9, August 1988, pp. 1995-2005. Specifically, the following procedure was employed in the present invention to determine the volume percent polar polymer in the barrier film recyclate resin comprising a mixture of nonpolar polymer and polar polymer.
  • Tensile stress at break was measured according to ASTM D-638. This test is dependent on film sample thickness. For the measurements provided here, a thickness of about 46 pm to 55 pm was used.
  • a proxy for polymer recyclate could be prepared melt blending HDPE and nylon as shown in Table 2. Each of the polymer recyclate proxies is tested to determine the molecular weight of the high polarity condensation polymer PCP1 in the dispersed phase of the polymer blend. GPC or SEC can be used to measure the molecular weight of high polarity polymers in polymer blends or multilayer structures. A solvent that selectively dissolves the high polarity polymer but not the low polarity polymers, such as formic acids or acetyl chloride, is used to recover the high polarity polymer from the polymer blend. After selective extraction of high polarity' polymer from polymer blends or multilayer structures, GPC or SEC is used to determine its molecular weight.
  • Polymer recyclate proxies are then compounded at 250°C with 1,000 ppmw of water to produce a first modified polymer recyclate as shown in Table 3.
  • Each of the first modified polymer recyclates is tested to determine the molecular weight of the degraded high polarity condensation polymer d-PCPl in the dispersed phase of the polymer blend.
  • d-MWl is less than MW1, d-MW2 is less than MW2, and d-MW3 is less than MW3. It is further believed that each of m-PCRl, m-PCR2, and m-PCRl, when compared to PCR1, PCR2, and PCR1, respectively, would demonstrate reduced gel levels resulting in improved mechanical properties, including, but not limited to, one or more of mechanical elongation, strength, toughness, environmental stress crack resistance (ESCR), structural integrity 7 , puncture resistance, heat resistance, heat sealability, and/or abrasion resistance.
  • ESCR environmental stress crack resistance

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Abstract

L'invention concerne un procédé de modification d'un recyclat polymère pour améliorer une ou plusieurs propriétés mécaniques, le recyclat polymère comprenant une phase matricielle d'un polymère à faible polarité et une phase dispersée de domaines d'un polymère de condensation à polarité élevée. Le recyclat polymère est mélangé avec un composé protique polaire pour entrer en contact avec au moins une partie de la phase dispersée pour réduire le poids moléculaire du polymère de condensation à polarité élevée.
PCT/US2023/036739 2023-11-03 2023-11-03 Procédé de modification de recyclats polymères et compositions fabriquées à partir de celui-ci Pending WO2025095955A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4620032A (en) * 1984-12-11 1986-10-28 Celanese Corporation Depolymerization of condensation polymers involving a pre-molecular weight reduction step
JP2004091775A (ja) * 2002-08-09 2004-03-25 Kuraray Co Ltd オレフィン系重合体組成物
US20180311944A1 (en) * 2016-07-07 2018-11-01 Jms International Packaging Inc. Polymeric blends and uses thereof for making transparent rigid and heat-resistant thermoplastic workpieces
WO2023186687A1 (fr) * 2022-03-28 2023-10-05 Pointbreak As Procédé et système de traitement de déchets de polymère comprenant des polymères hétéroatomiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4620032A (en) * 1984-12-11 1986-10-28 Celanese Corporation Depolymerization of condensation polymers involving a pre-molecular weight reduction step
JP2004091775A (ja) * 2002-08-09 2004-03-25 Kuraray Co Ltd オレフィン系重合体組成物
US20180311944A1 (en) * 2016-07-07 2018-11-01 Jms International Packaging Inc. Polymeric blends and uses thereof for making transparent rigid and heat-resistant thermoplastic workpieces
WO2023186687A1 (fr) * 2022-03-28 2023-10-05 Pointbreak As Procédé et système de traitement de déchets de polymère comprenant des polymères hétéroatomiques

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