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WO2014091309A2 - Composition polymère présentant des propriétés de barrière améliorées - Google Patents

Composition polymère présentant des propriétés de barrière améliorées Download PDF

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Publication number
WO2014091309A2
WO2014091309A2 PCT/IB2013/003129 IB2013003129W WO2014091309A2 WO 2014091309 A2 WO2014091309 A2 WO 2014091309A2 IB 2013003129 W IB2013003129 W IB 2013003129W WO 2014091309 A2 WO2014091309 A2 WO 2014091309A2
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WIPO (PCT)
Prior art keywords
filler
composition
mica
polyethylene
nucleating agent
Prior art date
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Ceased
Application number
PCT/IB2013/003129
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English (en)
Other versions
WO2014091309A3 (fr
Inventor
JR. Adair Rangel DE OLIVEIRA
Barbara Íria Silva MANO
Cristóvao DE LEMOS
Fabiana Pires DE CARVALHO
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Braskem SA
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Braskem SA
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Publication date
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Priority to BR112015009102A priority Critical patent/BR112015009102A2/pt
Publication of WO2014091309A2 publication Critical patent/WO2014091309A2/fr
Publication of WO2014091309A3 publication Critical patent/WO2014091309A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • Polyolefins such as polypropylene (PP) and polyethylene (PE), are the most widely used polymers in various applications and present many advantages including flexibility, light weight, low cost, easy processing and recyclability. Polyolefins are useful for the manufacture of a variety of articles, including molded articles, films, and others structures.
  • PP and PE are inferior gas barriers compared to other thermoplastic materials like polyamide (PA), polyethylene terephthalate (PET), ethylene vinyl alcohol (EVOH), etc..
  • PA polyamide
  • PET polyethylene terephthalate
  • EVOH ethylene vinyl alcohol
  • the barrier properties are strictly correlated to the intrinsic structure of the polymer such as degree of crystallinity, crystallinity/amorphous phase ratio, nature of polymer, thermal and mechanical treatment before and after food contact, chemical groups present in the polymer (polar or not), degree of crosslinking, and glass transition temperature.
  • a barrier function can be improved into a polyolefm packaging material with alternative technologies, such as the surface treatment of the polymer by fluorination or sulfonation, multilayer coextrusion (the addition of a layer of barrier material), mixing the barrier materials into the base polymer or by inclusion of impermeable lamellar fillers with sufficient aspect ratio to alter the diffusion path of gas-penetrant molecules.
  • the mineral fillers the most used are those that carry a high aspect ratio, such as clay, wollastonite, mica, graphene, carbon nanotubes, talcum, etc.
  • this type of filler is impermeable to gases, and its presence creates a tortuous path to the permeant, retarding the passage through the polymer.
  • the extent of permeation reduction depends, among others, on the filler anisotropy and dispersion in the polymer.
  • mica provides improvement in barrier properties
  • polyolefms filled with mica have gas barrier properties below required specifications.
  • Mica has established its applications in a wide variety of plastic polymer compounds, namely, Polyolefm, Polyamide, Polyester, Polyurethane/Polyurea, Polypropylene (PP), Polyethylene (PE), Poly (acrylonitrile, butadiene, styrene ) (ABS) , Polycarbonate (PC), Fluoro-polymers, Poly (p-phenylene oxide) (PPO) , Polysulfone, Polyurethane (PU)
  • plastic polymer compounds namely, Polyolefm, Polyamide, Polyester, Polyurethane/Polyurea, Polypropylene (PP), Polyethylene (PE), Poly (acrylonitrile, butadiene, styrene ) (ABS) , Polycarbonate (PC), Fluoro-polymers, Poly (p-phenylene oxide) (PPO) , Polysulfone, Polyurethane (PU)
  • thermoplastic resins and thermosets epoxy, phenolics, UPST (Unsaturated polyester), etc.
  • PP is, by far, the most popular use of mica.
  • Mica- filled PP is chiefly used for reinforcement of RRIM (Reinforced Reaction Injection Moulded) automotive parts, such as fan blades, dashboard panels, floor and grill panels, plastic seats, ignition system parts, air-conditioning heater housing including fascia and fenders fixed next to steel parts, while maintaining a similar appearance and similar coefficient of thermal expansion.
  • RRIM Forced Reaction Injection Moulded
  • nucleating agent Another method that can improve barrier properties is the inclusion of nucleating agent into the polymer.
  • nucleating agents induce an increase in crystallinity in PP or PE.
  • the Milliken Company supplies a commercial nucleating agent, Hyperform® HPN-20E ("HPN-20E"), which may improve barrier properties in polyethylene by the changing orientation of the crystalline lamellae of the polymer.
  • HPN-20E additive product contains calcium of hexahydrophthalic acid combined with an acid scavenger
  • This product is designed for addition to polymers, and for dispersion of the additive into polymer.
  • Nucleating agents are employed as additive in polymer resin in the manufacture of plastic articles. Such manufacture may be various methods, including by injection or extrusion molding. [0009] Nucleating agents are commonly used in polypropylene. Such agents change crystallization temperature, spherulitic size, density, clarity, impact and tensile properties of polypropylene. Similarly, nucleating agents are also used in polyethylene, particularly in linear low density polyethylene (LLDPE) to improve optical, impact, and other physical properties. However, the use of nucleating agent in high density polyethylene (HDPE) is less common because HDPE readily crystallizes without nucleating agent. In general, nucleating agents do not significantly improve the barrier properties of HDPE films.
  • LLDPE linear low density polyethylene
  • HPN-20E product and other nucleating agents are disclosed in U.S. 2008/0227900.
  • This invention is a method for improving the barrier properties of a polyethylene film. The method comprises mixing a substantially linear HDPE with a nucleating agent and converting the mixture into a film. Large reduction in the moisture vapor transmission rate and oxygen transmission rate of the film are observed in the presence of the nucleating agent.
  • the barrier properties of injection molded are not predictive in this invention.
  • U.S. 2008/0118749 relates to barrier films prepared from a blend of two high density polyethylene blend components and a high performance organic nucleating agent.
  • the two high density polyethylene blend components have substantially different melt indices. Large reductions in the moisture vapor transmission rate of the film are observed in the presence of the nucleating agent when the melt indices of the two blend components have a ratio of greater than 10/1.
  • compositions having unexpected good oxygen barrier properties can result in compositions having unexpected good oxygen barrier properties.
  • additives which can be included in the compositions of the invention include, but are not necessarily limited to, pigments, stabilizers, processing aids, plasticizers, fire retardants, anti-fog, among others.
  • the present invention presents a polymeric composition with improved barrier to gases, volatile organic compounds and water vapor, comprising a polyolefin resin; a nucleating agent or a clarifying agent; and a filler.
  • the polyolefin resin may comprise polyethylene, polypropylene, or a mixture thereof.
  • the polyolefin resin may be from about 99.89% to 65% by weight, or about 99.47% to 82% or about 98.95% to 88% by weight.
  • the polyethylene may comprise a low density polyethylene, a medium density polyethylene, a high density polyethylene, or any combination thereof.
  • the polypropylene may comprise a propylene homopolymer, a propylene randomized copolymer or a propylene heterophasic copolymer, or any combination thereof.
  • the filler may comprise lamellar filler capable of changing the crystalline structure of polyolefin resin solidified from a molten state.
  • the filler may be organic or inorganic.
  • the filler may be any one component selected from a natural or synthetic filler chosen among mica, clay, graphite or graphene; more preferably, filler includes muscovite, phlogopite, vermiculite, montmorillonite, kaolinite, laponite, wollastonite, hectorite, expanded graphite, oxidized graphite or any combination thereof.
  • the mineral filler can range from about 0.1 % to 30% by weight, with about 0.5%> to 15% by weight preferred and about 1%) to 10%) by weight particularly preferred.
  • the nucleating agent may be a one metal salt from a saturated bicyclic dicarboxylate, hexahydrophthalic acid, dibenzylidene sorbitol and dibenzylidene sorbitol derivatives, or sodium benzoate.
  • the nucleating agent for this invention is one that is capable of changing the orientation of crystalline lamellae and/or modifies the crystal size of the polyolefin.
  • the nucleating agent can range from 0.01% to 5% by weight, with about 0.03% to 3%) by weight preferred, and about 0.05%> to 2% by weight particularly preferred.
  • Lamellar filler is a material composed of aggregates of fine sheets of material held adjacent to one another, characterized by their flattened or squamous shape.
  • the inorganic substance mica is the denomination given to a lamellar filler group of hydrated silicate of potassium, which displays differences in their chemical compositions and physical properties, constituting a phyllosilicate based on potassium, sodium, aluminum, magnesium, and/or iron in its structure.
  • Mica may be natural or synthetic.
  • the inorganic substance clay is the denomination of a group of lamellar filler composed of hydrated silicates of aluminum and magnesium, and may contain other elements, such as iron, sodium, potassium, lithium, etc.
  • mica is construed to include hydrated silicates of potassium, which displays differences in their chemical compositions and physical properties, constituting a phyllosilicate based on potassium, sodium, aluminum, magnesium, and/or iron in its structure. Micas can have basal cleavage and are capable of peeling apart into thin platelets.
  • Naturally occurring mica may include: Muscovite or potassium mica (H 2 KAl 3 (Si0 4 ) 3 ); Phlogopite or magnesium mica (H 2 KMg 3 Al(Si04)3); Paragonite or sodium mica (H 2 NaAl 3 (Si04) 3 ); Lepidolite or lithium mica (KLiAl(OH,F) 2 Al(Si04) 3 ); Biotite or magnesium iron mica [(H 2 K)(Mg,
  • Zinnwaldite or lithium iron mica Li 2 K2Fe 2 Al 4 Si70 24 ) and others; Synthetic mica may include fluorphlogopites (Mg 3 K(AlF 2 0(Si0 3 ) 3 ) and may be coated, e.g. with titanium dioxide.
  • clay comprises hydrated silicates of aluminum, and may contain other elements, like magnesium, iron, sodium, potassium, lithium, etc.
  • Clay is construed to include hydrous aluminum phyllosilicates, sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations. Clays includes:
  • Kaolin Al 2 Si 2 0 5 (OH) 4
  • Smectite (Ca,Na,H)(Al,Mg,Fe,Zn) 2 (Si,Al) 4 0io(OH) 2 xH 2 0)]
  • Chlorite [(Mg,Fe) 3 (Si,Al) 4 Oio]
  • Attapulgite (Mg,Al) 2 Si 4 Oi 0 (OH) ⁇ 4( ⁇ 2 0)] .
  • Examples include vermiculite, montmorillonite, kaolinite, laponite, and hectorite.
  • the nucleating agent is a substance that modifies the crystallization of the polymer or polymeric composition.
  • the nucleating agent may be a one metal salt from a saturated bicyclic dicarboxylate, hexahydrophthalic acid, dibenzylidene sorbitol and
  • dibenzylidene sorbitol derivatives or sodium benzoate.
  • examples include cis-endo- bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, disodium salt (Hyperform® HPN-68L),
  • hexahydrophthalic acid, calcium salt Hyperform® HPN-20E
  • l,3:2,4-bis (3,4 dimethyl benzylidene sorbitol) Millad® 3988 and/or Millad® 3988i
  • bis(4-propylbenzylidene) propyl sorbitol Millad® NXTM 8000.
  • the lamellar filler disperses and/or exfoliates in the molten polymer and forms planes that may be oriented in the parallel direction to the shearing stress applied in the molten polymer during its processing, that is, in the direction of the flow of injection for injection molded items, or in the longitudinal direction for blown plastic articles.
  • the filler acts as a physical barrier to a permeating agent (e.g., gases, volatile organic compounds, and water vapor), creating a tortuous path that delays the passage of the permeating agent.
  • a permeating agent e.g., gases, volatile organic compounds, and water vapor
  • the lamellar filler is an anisotropic particle and also orientates the crystalline lamellae in the transversal direction to the shearing stress applied in the molten polymer during its processing, showing a secondary effect that may decrease the permeability of gases, volatile organic compounds, and water vapor of the polyolefin.
  • the nucleating agent for this invention is also capable of orienting the crystalline lamellae, change the crystallinity degree and/or modify the crystal size of the polyolefin. As described previously, the changing of crystalline orientation creates a more tortuous path for permeating agent delaying the passage of gases, volatile organic compounds, and water vapor. Besides, it is expected that reduction of crystal size improves the barrier to gases, volatile organic compounds, and water vapor by minimizing the defects in the interface between crystals.
  • nucleating agents with lamellar fillers presents a synergic effect, which is governed by two mechanisms: physical barrier and crystalline orientation of polymeric resin.
  • the polymer may be obtained in the reactor, for different technologies, followed by dosing of additives and a nucleating agent and filler in e.g., a twin-screw extruder.
  • the present invention may find utility in rigid and flexible packaging for drink, foods and non-foods that require a barrier to permeation of oxygen gas. As a result, the shelf life of stored food will tend to be lengthened through the use of products of the present invention.
  • the filler was tested for dependency upon the base resin. The tests were accomplished with two PE resin types: 1) high density polyethylene (HDPE), MFI of 20 g/10 min (190 °C; 2.16 kg, according to ASTM D1238) and 2) low density polyethylene (LDPE), MFI of 22 g/10 min (190 °C; 2.16 kg, according to ASTM D1238), both with 3 wt% of filler.
  • the samples were injection molded into 2 mm thick specimens.
  • the permeability results obtained with mica in different polyethylene grades, expressed as oxygen transmission rate (OTR), are displayed in Table 2. The greatest reduction in OTR was obtained with Ml 50 mica, regardless of the base resin.
  • the particle size can range from about 0.01 ⁇ to 200 ⁇ , with about 0.1 ⁇ to 100 ⁇ preferred and about 0.1 ⁇ to 30 ⁇ particularly preferred.
  • the fillers were tested for dependency upon the type (talc or mica) and aspect ratio (high or low) in HDPE resin, and results are shown in Table 3 and can be compared to Table 2.
  • Talc T2 displays an aspect ratio of 130, higher than that of mica M150, and therefore equal or lower permeation values than the mica M150 were expected.
  • the samples were injection molded into 0.6 mm thick plaques.
  • mice was tested for dependency upon its content in HDPE.
  • the samples were injection molded into 2 mm thick specimens and the results are shown in Table 4. A significant reduction in OTR with higher amount of mica is evidenced.
  • An additive that operates with the same proposed mechanism for mica, that is, modifying the orientation of crystalline lamellae, is the nucleating agent HPN-20E from
  • HPN-20E nucleating agent improved considerably the oxygen barrier property of polyethylene, revealing that the effect of orientation of the HDPE crystalline lamellae plays an important role in the reduction of oxygen permeability. According to the results, above 0.1 wt% of HPN-20E product did not bring about additional oxygen barrier improvement, inferring that the crystalline lamellae orientation of HDPE reached a steady state.
  • HPN-20E nucleating agent is an organic compound, it does not offer the effect of physical barrier on the permeating agent as the filler does. Additionally, it is believed that mica acts either in the physical barrier as well as in the orientation of the crystalline polyethylene lamellae. Note that the use of these two components in isolation does not result in proper barrier levels for markets like cardboard packages for milk, BOPP films, PE films for refrigerated and perishable products, fuel tanks and agrochemical containers.
  • HPN-20E nucleating agent HPN-20E nucleating agent

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention porte sur une composition polymère comprenant une composition de polyoléfine de première qualité comprenant un mélange d'un agent de nucléation et d'une charge ajouté pour obtenir une perméabilité réduite. La composition selon la présente invention présente des propriétés améliorées comme barrière à des gaz, des composés organiques volatils et la vapeur d'eau.
PCT/IB2013/003129 2012-10-24 2013-10-23 Composition polymère présentant des propriétés de barrière améliorées Ceased WO2014091309A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BR112015009102A BR112015009102A2 (pt) 2012-10-24 2013-10-23 composição polimérica

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261717971P 2012-10-24 2012-10-24
US61/717,971 2012-10-24

Publications (2)

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WO2014091309A2 true WO2014091309A2 (fr) 2014-06-19
WO2014091309A3 WO2014091309A3 (fr) 2014-11-27

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3162844A1 (fr) * 2015-10-26 2017-05-03 SABIC Global Technologies B.V. Composition de polypropylène comprenant une composition de nucleation comprenant un silicate d'aluminium et un agent de nucleation organique
US20170152102A1 (en) * 2015-11-30 2017-06-01 Sabic Global Technologies B.V. Use of polypropylene composition
IT201800005319A1 (it) * 2018-05-14 2019-11-14 Composizione polimerica a migliorate proprieta’ barriera
WO2019222890A1 (fr) * 2018-05-21 2019-11-28 广州特种承压设备检测研究院 Matériau de mélange maître composite de graphène modifié/polybutylène, procédé de préparation s'y rapportant et son utilisation
CN111269485A (zh) * 2018-12-05 2020-06-12 中国石油化工股份有限公司 一种高阻隔性聚乙烯组合物以及制备方法和薄膜与应用
CN111269484A (zh) * 2018-12-05 2020-06-12 中国石油化工股份有限公司 一种高阻隔性聚乙烯组合物以及制备方法和薄膜与应用
WO2020157619A1 (fr) * 2019-01-31 2020-08-06 Nova Chemicals (International) S.A. Compositions de polyéthylène et articles présentant de bonnes propriétés barrière
US10738182B2 (en) 2018-04-23 2020-08-11 Dow Global Technologies Llc Molded articles and methods thereof
US20220049073A1 (en) * 2018-10-05 2022-02-17 Dow Global Technologies Llc Dielectrically-enhanced polyethylene formulation
US12398248B2 (en) * 2023-02-03 2025-08-26 National Industrialization Company (Tasnee) Pressure pipes with improved barrier properties to CO2

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6005034A (en) * 1995-08-31 1999-12-21 Chisso Corpoation Propylene-ethylene copolymer composition and process for producing the same
WO2003093004A1 (fr) * 2002-05-01 2003-11-13 Exxonmobil Corporation Film thermoplastique a base de polypropylene
CA2605363A1 (fr) * 2005-04-26 2006-11-02 Exxonmobil Oil Corporation Film de polypropylene permeable

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3162844A1 (fr) * 2015-10-26 2017-05-03 SABIC Global Technologies B.V. Composition de polypropylène comprenant une composition de nucleation comprenant un silicate d'aluminium et un agent de nucleation organique
US20170152102A1 (en) * 2015-11-30 2017-06-01 Sabic Global Technologies B.V. Use of polypropylene composition
US10738182B2 (en) 2018-04-23 2020-08-11 Dow Global Technologies Llc Molded articles and methods thereof
IT201800005319A1 (it) * 2018-05-14 2019-11-14 Composizione polimerica a migliorate proprieta’ barriera
WO2019220303A1 (fr) * 2018-05-14 2019-11-21 Versalis S.P.A. Composition de polymères présentant des propriétés barrière ameliorées
WO2019222890A1 (fr) * 2018-05-21 2019-11-28 广州特种承压设备检测研究院 Matériau de mélange maître composite de graphène modifié/polybutylène, procédé de préparation s'y rapportant et son utilisation
US20220049073A1 (en) * 2018-10-05 2022-02-17 Dow Global Technologies Llc Dielectrically-enhanced polyethylene formulation
US12173141B2 (en) * 2018-10-05 2024-12-24 Dow Global Technologies Llc Dielectrically-enhanced polyethylene formulation
CN111269484A (zh) * 2018-12-05 2020-06-12 中国石油化工股份有限公司 一种高阻隔性聚乙烯组合物以及制备方法和薄膜与应用
CN111269485A (zh) * 2018-12-05 2020-06-12 中国石油化工股份有限公司 一种高阻隔性聚乙烯组合物以及制备方法和薄膜与应用
WO2020157619A1 (fr) * 2019-01-31 2020-08-06 Nova Chemicals (International) S.A. Compositions de polyéthylène et articles présentant de bonnes propriétés barrière
US12163012B2 (en) 2019-01-31 2024-12-10 Nova Chemicals (International) S.A. Polyethylene compositions and articles with good barrier properties
US12398248B2 (en) * 2023-02-03 2025-08-26 National Industrialization Company (Tasnee) Pressure pipes with improved barrier properties to CO2

Also Published As

Publication number Publication date
AR093107A1 (es) 2015-05-20
WO2014091309A3 (fr) 2014-11-27
BR112015009102A2 (pt) 2017-07-04

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