WO2019234492A1 - Mélanges de polymères ayant une capacité d'absorption d'oxygène améliorée - Google Patents

Mélanges de polymères ayant une capacité d'absorption d'oxygène améliorée Download PDF

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WO2019234492A1
WO2019234492A1 PCT/IB2019/000560 IB2019000560W WO2019234492A1 WO 2019234492 A1 WO2019234492 A1 WO 2019234492A1 IB 2019000560 W IB2019000560 W IB 2019000560W WO 2019234492 A1 WO2019234492 A1 WO 2019234492A1
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composition
transition metal
additives
polymer
polyolefin
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PCT/IB2019/000560
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English (en)
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Anne Kunigunde NEUBIG
Uwe Bayer
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Trevira Holdings Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Definitions

  • the present invention relates generally to novel polymer compositions and films and rigid or semi-rigid articles made from these novel polymer compositions that provide improved gas barrier protections, oxygen absorption capacity, optical appearance and/or mechanical properties. More generally, the novel polymer compositions include a polyolefin, a polymer containing an oxidizable component, a transition metal compound or mixture of transition metal compounds, and one or more additives.
  • polyesters and polyolefins have been replacing glass and metal packaging materials due to lighter weight, decreased breakage compared to glass, and potentially lower cost.
  • Organic and inorganic oxygen scavenging materials have been developed partly in response to the food industry's goal of having longer shelf-life for packaged food. These oxygen scavenging materials are incorporated into at least a portion of the package and remove oxygen from the enclosed package volume thereby inhibiting spoilage and prolonging freshness.
  • Articles made of polyolefinic materials such as polyethylene (PE) and polypropylene (PP) films, plastic packaging, beverage bottles, etc., tend to display good moisture barrier and thermal processing performance, but perform poorly in preventing oxygen permeation across the wall that is in contact with the filled contents.
  • PE polyethylene
  • PP polypropylene
  • polypropylene in particular is typically used as a copolymer with ethylene to provide impact resistance and flexibility.
  • Adding co-monomers may lower the melting temperature and result in a higher oxygen transmission rate, both being undesirable in hot-filled, oxygen sensitive food packages.
  • PEs polyethylenes
  • MVTR moisture vapor transmission rate
  • PE and PP are generally co-extruded, laminated, layered and coated or surface-treated with polymers such as ethylene-vinyl alcohol (EVOH) to increase the oxygen barrier properties.
  • EVOH ethylene-vinyl alcohol
  • polypropylene as a single (mono)-layered material including passive (torturous path) technologies (such as blending in clays or“layered silicate” nanocomposites), or with addition of nanocomposites in situ.
  • passive path such as blending in clays or“layered silicate” nanocomposites
  • One method of addressing gas permeability involves incorporating an oxygen scavenger into the package structure itself.
  • oxygen scavenging materials constitute at least a portion of the package, and these materials remove oxygen from the enclosed package volume, thereby inhibiting spoilage and prolonging freshness in the case of food products.
  • Suitable oxygen scavenging materials include oxidizable organic polymers in which either the backbone or the side-chains of the polymer react with oxygen. Such oxygen scavenging materials are typically employed with a suitable catalyst, for example, an organic or inorganic salt of a transition metal such as cobalt.
  • a suitable catalyst for example, an organic or inorganic salt of a transition metal such as cobalt.
  • an oxidizable organic polymer is a poly ether.
  • the poly ether is typically used in low amounts of less than 10 weight percent of the packaging material. The poly ether is oftentimes dispersed in the polymer matrix and can form discrete domains.
  • United States Patent No. 5,641,825 relates to a composition of matter having oxygen scavenger capabilities, to a method of improving the oxygen scavenging capability of polymer-metal salt blends and to articles of manufacture formulated with such blends.
  • United States Patent Application No. 2014/0073741 Al relates to oxygen barrier polymers and, in particular, polyolefins with active oxygen scavenging systems.
  • United States Patent Application No. 2012/0252922A1 relates to a polymer composition comprising polypropylene, an adhesive polymer, and an oxygen-absorbing composition and its use for the manufacture of goods.
  • transition metal-based oxygen scavenging catalysts It may be possible to make significant oxygen barrier protection improvements by increasing the level of transition metal-based oxygen scavenging catalysts.
  • increasing the transition metal levels may impact the visual appearance and properties for the food and beverage containers.
  • higher cobalt level could impart blue coloration to otherwise clear containers.
  • the cobalt levels could also lead to thermo-oxidative degradation of the container and subsequently result to e.g. changes in mechanical properties. The problem, therefore, is to bring improvements to the oxygen barrier performance without compromising the visual and mechanical properties of the food and beverage containers.
  • Application No. 0546546 Al disclosing a resin composition comprising a polyolefin, a thermoplastic resin, and transition metal catalyst, e.g. made into a film, sheet or container; United States Patent No. 8,962,740, disclosing an oxygen scavenging composition comprising polyolefin, oxidizable polymer, and transition metal catalyst, e.g. made into a film by“compression molding”; United States Patent No. 8,592,522, disclosing an oxygen absorbing resin composition comprising polyolefin, other resin“which acts as a trigger for oxidation”, and transition metal catalyst, e.g. made into a film, sheet or container; United States Patent No.
  • One aspect of the present invention is directed to a composition
  • a composition comprising: a) polyolefin, b) polymer containing an oxidizable component, said polymer selected from the group consisting of poly ethers, copoly ether esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof, c) a transition metal compound or mixture of transition metal compounds, and d) one or more additives, e.g.
  • the composition characterized in that when an article, for example film, semi-rigid or rigid structure, is formed therefrom, the article exhibits improved gas barrier, oxygen absorption capacity, optical appearance and/or mechanical properties as compared to a control
  • the polymer containing an oxidizable component is MXD6.
  • composition of claim 1 comprising:
  • polymer containing an oxidizable component selected from the group consisting of poly ethers, copoly ether esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof,
  • the polymer containing an oxidizable component is MXD6.
  • the composition is characterized in that when an experimental article, for example film, semi-rigid or rigid structure, is formed therefrom, the article exhibits improved gas barrier, oxygen absorption capacity, optical appearance and/or mechanical properties as compared to a control.
  • Another aspect of the present invention is directed to film having improved oxygen or carbon dioxide or both barrier properties
  • film having improved oxygen or carbon dioxide or both barrier properties comprising: a) polyolefin, b) polymer containing an oxidizable component, said polymer selected from the group consisting of poly ethers, copoly ether esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof, c) a transition metal compound or a mixture of transition metal compounds, and d) one or more additives, e.g. stabilizers, antioxidants, compatibilizing agents and/or promoters enhancing oxygen barrier properties, said film characterized in that it exhibits improved gas barrier, oxygen absorption capacity, optical appearance and/or mechanical properties as compared to a control film.
  • additives e.g. stabilizers, antioxidants, compatibilizing agents and/or promoters enhancing oxygen barrier properties
  • Another aspect of the present invention is directed to film comprising:
  • polymer containing an oxidizable component selected from the group consisting of poly ethers, copoly ether esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof,
  • the polymer containing an oxidizable component is MXD6.
  • the film exhibits improved gas barrier, oxygen absorption capacity, optical appearance and/or mechanical properties as compared to a control film.
  • Another aspect of the present invention is directed to a rigid or semi-rigid article comprising: a) polyolefin, b) polymer containing an oxidizable component, said polymer selected from the group consisting of poly ethers, copoly ether esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof, c) a transition metal compound or a mixture of transition metal compounds, and d) one or more additives, e.g. stabilizers, antioxidants, compatibilizing agents and/or promoters enhancing oxygen barrier properties, said article characterized in that it exhibits improved gas barrier, optical appearance and/or mechanical properties as compared to a control article.
  • additives e.g. stabilizers, antioxidants, compatibilizing agents and/or promoters enhancing oxygen barrier properties
  • Another aspect of the present invention is directed to a rigid or semi-rigid article comprising:
  • polymer containing an oxidizable component selected from the group consisting of poly ethers, copoly ether esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof,
  • the polymer containing an oxidizable component is MXD6.
  • the article exhibits improved gas barrier, oxygen absorption capacity, optical appearance and/or mechanical properties as compared to a control article.
  • barrier means a material formation or structure that prevents or obstructs movement, passage or access across the two sides that the barrier separates or divides.
  • Non-limiting examples of barrier are rigid or flexible container walls, rigid or flexible films, rigid or flexible membranes and separators.
  • improved gas barrier properties any detectable decrease in transmission of oxygen and/or carbon dioxide and/or preferential gas permeability of ethylene and carbon dioxide in composition or film of the present invention as compared to control compositions/films.
  • improved gas barrier properties are determined via measurement of a decrease in total oxygen over a selected time frame into a closed, rigid or flexible container or article of the present invention as compared to total oxygen in a control over the same time frame.
  • improved oxygen absorption capacity any detectable uptake of oxygen in composition or (powdered) article/film of the present invention as compared to control compositions/articles.
  • improved oxygen absorption capacity is determined via measurement of a decrease of total headspace oxygen over a selected time frame in closed cells as compared to total headspace oxygen in a control over the same time frame.
  • improved optical appearance properties it is meant to include, but is not limited to, any decrease in blue tinge and/or haze and/or any increase in clarity in a film or article produced from a composition of the present invention as compared to a control film or article which is measurable or observed visually by a skilled artisan.
  • improved mechanical properties it is meant to include, but is not limited to, any measurable increase in strength, toughness, heat stability and/or ease in recyclability in a film or article produced from a composition of the present invention as compared to a control film or article.
  • control or“control composition” or“control film” or“control article” it is meant a composition, film or article which does not contain all elements of the
  • compositions, films or articles of the present invention and/or contains elements in the compositions, films or articles at ranges less than or greater than those disclosed herein.
  • polyolefm(s) encompasses a class of thermoplastic polymers that are widely used in the consumer and petrochemicals industry.
  • Polyolefins are typically produced from a simple olefin (also called an alkene with the general formula Cnfkn) as a monomer.
  • polyethylene is the polyolefin produced by polymerizing the olefin ethylene (C2H4).
  • Polypropylene (PP) is another common polyolefin which is made from the olefin propylene (C3H6). Copolymers of ethylene and propylene are also useful thermoplastic polymers in accordance with the present disclosure.
  • polyolefins as used in the present disclosure, are described in United States Patent No. 8,981,013 B2. These may include, but are not limited to, ethylene-based polymers such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), homogeneously branched linear ethylene/a-olefin interpolymers or homogeneously branched substantially linear ethylene/a-olefin interpolymers; propylene-based polymers such as propylene homopolymers and propylene interpolymers that can be random or block copolymers, branched
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • propylene-based polymers such as propylene homopolymers and propylene interpolymers that can be random or block copolymers, branched
  • polypropylene or a propylene-based terpolymer
  • a blend of two of more polyolefins such as a blend of an ethylene-base polymer and a propylene-base polymer discussed above;
  • halogenated ethylene-based polymers such as chlorinated ethylene-based polymers and fluorinated ethylene-based polymers.
  • polyolefins may also include elastomeric polymers such as homopolymers of conjugated dienes, especially butadiene or isoprene, and random, or block, copolymers and terpolymers of at least one conjugated diene, especially butadiene or isoprene, with at least one aromatic a-olefin, especially styrene and 4- methylstyrene, aromatic diolefin, especially divinylbenzene.
  • elastomeric polymers such as homopolymers of conjugated dienes, especially butadiene or isoprene, and random, or block, copolymers and terpolymers of at least one conjugated diene, especially butadiene or isoprene, with at least one aromatic a-olefin, especially styrene and 4- methylstyrene, aromatic diolefin, especially divinylbenzene.
  • polyolefins may include natural or synthetic polyisoprene (PI) and polybutadiene (PB).
  • PI polyisoprene
  • PB polybutadiene
  • Polypropylene (PP) used may also be a bottle-grade resin such as PolyOne® 23N10A, a Flint Hills Resources polypropylene random copolymer.
  • suitable polypropylene base polymers may include VERSIFY® polymers (The Dow Chemical Company) and VISTAMAXX® polymers (ExxonMobil Chemical Co.), LICOCENE'" polymers (Clariant), EASTOFLEX® polymers (Eastman Chemical Co.), REXTAC® polymers (Hunstman), Basell-Polyolefin (Basell) and VESTOPLAST'” polymers (Degussa).
  • Other suitable polymers may include propylene-a-olefins block copolymers and
  • interpolymers polypropylene made from metallocene or post metallocene catalysts and catalytic processes, such as, but not limited to, suitable grades commercially available from TOTAL Petrochemicals, LyondellBasell and ExxonMobil , and other propylene based random, block, heterophasic, or otherwise suitable copolymer and interpolymers known in the art.
  • PE Polyethylene
  • PE polyethylene
  • ACP 6031D Hostalen a LyondellBasell random HDPE copolymer
  • Other suitable polyethylene base polymers may include AFFINITYTM polymers (The Dow Chemical Company) and
  • VISTAMAXX® polymers (ExxonMobil Chemical Co.), MARLEX ® polymers (Chevron Phillips Chemical) and VESTOPLAST'" polymers (Evonik).
  • Other suitable polymers may include ethylene alpha-olefin copolymers and interpolymers, polyethylene made from metallocene or post metallocene catalysts and catalytic processes, such as, but not limited to, suitable grades commercially available from TOTAL Petrochemicals, LyondellBasell and ExxonMobil , and other ethylene based random, block, heterophasic, or otherwise suitable copolymer and interpolymers known in the art.
  • the improved barrier properties of the present invention may be applicable to biopolymers, biopolymer alloys and biopolymer composites.
  • the composition providing improved gas barrier properties may comprise a polymer containing an oxidizable component selected from the group consisting of poly ethers, copoly ether-esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof.
  • the polymer containing an oxidizable component is MXD6.
  • the barrier may comprise > 10 % by weight and ⁇ 50 % by weight of the polymer containing an oxidizable component. In some embodiments, the barrier may comprise 15-35 % by weight of the polymer containing an oxidizable component. All percentages are on the weight basis, relative to the total composition.
  • the barrier may comprise > 1 and ⁇ 30 wt % of the polymer, for example, > 1.5 and ⁇ 10 wt % of the polymer.
  • the polymer (b) containing an oxidizable component may comprise one or more poly ether segments having a number- average molecular weight of from about 200 to about 5000 g/mol.
  • the polyether in the polymer composition may have a number-average molecular weight of from about 600 to about 3500 g/mol, and more specifically about 800 to about 3000 g/mol, that the polymer composition contains one or more polyether segments in an amount of about 5 to about 60 wt %, in particular about 10 to about 50 wt %.
  • the polymer (b) containing an oxidizable component is a copoly ether ester containing poly ether segments in an amount of about 15 to about 45 wt %, relative to the total polymer (b) composition.
  • the polymer (b) containing an oxidizable component is a copolymer of polyolefin and poly ether, containing poly ether segments in an amount of about 10 to about 95 wt %, relative to the total polymer (b) composition.
  • the copolymer may be obtainable by a melt compounding steps of the polyolefin and poly ether segments.
  • the polymer (b) containing an oxidizable component is a modified poly ether, containing poly ether segments in an amount of about 60 to about 99 wt %, relative to the total polymer (b) composition.
  • the polyether segment is a poly (C2-C6-alkylene) glycol segment.
  • the C2-C6-alkylene glycol may be a linear or branched aliphatic C2-C6-moiety.
  • the poly ether segment is a linear or branched poly (C2-C6-alkylene) glycol segment.
  • polymer compositions include poly (ethylene glycol), linear or branched poly (propylene glycol), linear or branched poly (butylene glycol), linear or branched poly (pentylene glycol), linear or branched poly (hexylene glycol), poly (tetramethylene ether) glycol, as well as mixed poly (C2-C6-alkylene) glycols obtained from two or more of the glycolic monomers used in preparing the above-mentioned examples.
  • the poly ether segment is a linear or branched poly (propylene glycol) or a linear or branched poly (butylene glycol).
  • Compounds having three hydroxyl groups (glycerols and linear or branched aliphatic triols) could also be used.
  • transition metal or transition metal mixture
  • transition metal means any of the set of metallic elements occupying Groups IVB-VIII, IB, and IIB, or 4-12 in the periodic table of elements.
  • Non-limiting examples are cobalt, manganese, copper, chromium, zinc, iron, nickel, and combinations or mixtures thereof.
  • the transition metals have variable chemical valence and a strong tendency to form coordination compounds.
  • transition metal compound means those transition metal compounds, also referred to as catalyst, that activate or promote the oxidation of the oxidizable component of the polymer by ambient oxygen.
  • suitable transition metal compounds include compounds comprising cobalt, manganese, copper, chromium, zinc, iron, or nickel and mixtures thereof. It is also possible that the transition metal compound is incorporated in the polymer matrix during extrusion for example.
  • the transition metal compound can be added during polymerization or compounded into suitable polymer thereby forming a masterbatch that can be added during the preparation of the article. In one nonlimiting embodiment, the transition metal compound is added as a liquid or together with a liquid carrier.
  • the transition metal compound is included in a liquid or solid masterbatch. In one nonlimiting embodiment, the transition metal compound is added as a melt. In one nonlimiting embodiment, a transition metal compound, such as a cobalt compound for example, may be physically separate from the polymer composition, for example a sheath core or side-by-side relationship, so as not to activate the polymer composition prior to melt blending into a film, article or preform.
  • the transition metal compound may include, but is not limited to, a transition metal salt of i) a metal comprising at least one member selected from the group consisting of cobalt, manganese, copper, chromium, zinc, iron, and nickel, and ii) an inorganic or organic counter ion comprising at least one member selected from the group of carboxylate, such as neodecanoates, octanoates, stearates, acetates, naphthalates, lactates, maleates, acetylacetonates, linoleates, oleates, palminates or 2-ethyl hexanoates, oxides, carbonates, chlorides, dioxides, hydroxides, nitrates, phosphates, sulfates, silicates, or mixtures thereof.
  • Such cobalt metal-containing compositions or mixtures of, for example cobalt-containing compositions and zinc-containing compositions may be added separately or
  • the transition metal catalyst carriers may include microcrystalline cellulose (MC) as a potential carrier for the transition metal.
  • MC microcrystalline cellulose
  • the oxidizable component in the polymer compositions comprising transition metals may be bio-resourced a-tocopherol, poly (alpha-pinene), poly (beta-pinene), poly (dipentene), and poly (d-limonene).
  • the transition metal catalyst may be a cobalt salt, in particular a cobalt carboxylate, and especially a cobalt C8-C20 carboxylate.
  • the C8-C20 carboxylate may be branched or unbranched, saturated or unsaturated.
  • the cobalt compound may be physically separate from the polymer composition, for example a sheath core or side-by-side relationship, so as not to activate the polymer composition prior to melt blending into a container.
  • compositions of the present invention further comprise one or more additives, e.g. stabilizers, antioxidants, compatibilizing agents and/or promoters enhancing oxygen barrier properties.
  • additives e.g. stabilizers, antioxidants, compatibilizing agents and/or promoters enhancing oxygen barrier properties.
  • an additive or additives is added separately.
  • the additive or additives is included in one or more masterbatches.
  • Nonlimiting examples of stabilizers which can be used include monomeric, oligomeric or polymeric hindered amine light stabilizers (HALS).
  • HALS may be a polymeric HALS, such as Uvinul ® 5050, Uvinul ® 4050, oligomeric or polymeric HALS, such as Uvinul ® 5062.
  • the HALS may be a mixture of compounds, such as Uvinul ® 4092.
  • HALS include but are not limited to Uvinul ® 4077, Uvinul ® 4092, Nylostab ® , Tinuvin ® , Hostavin ® , Nylostab ® S- EED ® and Chimassorb ® 944 FDL (CAS No. 70624-18-9).
  • antioxidants include, but are not limited to, phenolic antioxidants, aminic antioxidants, sulfur-based antioxidants and phosphites, and mixtures thereof.
  • Non-limiting examples of antioxidants are described in Plastics Additives, Pritchard, G., Ed. Springer Netherlands: 1998; Vol. 1, pp95-l07.
  • Non-limiting examples of such antioxidants include butylated hydroxy toluene (BHT), Ethanox ® 330, Ethanox ® 330G, IRGANOX 1330, Hostanox ® PEP-Q, tert-butyl phenols and mixtures thereof.
  • the antioxidant may be selected from the group consisting of hindered phenols, sulfur-based antioxidants, hindered amine light stabilizers and phosphites. In a further embodiment, the antioxidant may be selected from the group consisting of hindered phenols, sulfur-based antioxidants and phosphites.
  • antioxidants include, but are not limited to l,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-benzene (CAS: 1709-70-2), tetrakis(2,4-di-tert-butylphenyl)- 1,1 -biphenyl- 4, 4'-diylbisphosphonite (CAS: 38613-77-3) or pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate (CAS: 6683-19-8), (5R)-[(lS)-l,2-Dihydroxyethyl]-3,4- dihydroxyfuran-2(5H)-one (Ascorbic acid CAS: 50-81-7).
  • the antioxidant is a-tocopherol (vitamin E form antioxidant agent. CAS: 59-02-9) or DL-a-Tocopherol (CAS No. 10191-41-0).
  • more than one antioxidant is added.
  • DL-a-Tocopherol (CAS No. 10191-41-0) and Ethanox ® 330 are added.
  • Nonlimiting examples of compatibilizing agents include sodium stearate, magnesium stearate, mixtures thereof and alkenyl succinic anhydride. Additional nonlimiting examples of compatibilizing agents include blends of poly-a-olefm and polyester that can be made using reactive compounding techniques using maleated polypropylene or
  • anhydrides of unsaturated dicarboxylic acids such as maleic, citraconic and itaconic acids, acrylic-modified olefmic ionomers containing sodium, zinc, cobalt, and a variety of metals and those further described in International Review of Chemical Engineering 2011, Vol. 3, r153-215.
  • Methods for producing compatibilizing agents for use herein, such as extrusion of hot melt resins, the solvothermal method, mixed monomer systems synthesis, free radical grafting by irradiation or other, are known in the art.
  • Oligomeric polyethers modified with sulfonic acid groups such as disclosed in U.S. Patent 9,447,321, which is incorporated herein by reference, also provide useful compatibilizers or interfacial agents for improving compatibility/dispersability of the oxidizable component in the polymer (polyolefin) matrix. Higher molecular weight polyethers can also be used.
  • the compatibilizers or interfacial agents can be added directly or for example pre-reacted with the polyether compound to form a modified polyether.
  • the oligomeric polyether compounds or higher molecular weight poly ethers can be modified e.g. end-capped or reacted at each end or just one end. Possible reactants can be anhydrides or carboxylic acids.
  • modified oligomeric poly ether compounds can be obtained directly in a pre-reaction step or e.g. when producing a masterbatch in an extrusion step.
  • Nonlimiting examples of promoters enhancing oxygen barrier properties also referred to as ionic compatibilizers as described in EP 1663630, teachings of which are incorporated herein by reference include copolyesters containing a metal sulfonate salt group.
  • the metal ion of the sulfonate salt may be Na+, LH-, K+, Zn++, Mn-H-, Ca ⁇ and the like.
  • the sulfonate salt group is attached to an aromatic acid nucleus such as a benzene, naphthalene, diphenyl oxy diphenyl, sulfonyldiphenyl. or raeihylenediphenyl nucleus.
  • the aromatic acid nucleus is sulfophthalic acid, suifoterephtharie acid, sulfoisophihalic acid, 4-suffonaphthaiene-2,7-di carboxylic acid, or an ester thereof.
  • the sulfornonomer is 5-sodiurnsulfoisopbthalic acid or .5- zincsulfoisophthalic acid and a diaikyl ester thereof such as the dimethyl ester (SIM) or glycol ester (SIPEG).
  • the promoter is 5-sulfoisophthalic acid dimethyl ester sodium salt (SIM ester) or a counterion such as Li, Na, K and Zn, the free acid with no ester, or a different ester, such as, but not limited to, methyl, ethyl and ethylene glycol.
  • SIM ester 5-sulfoisophthalic acid dimethyl ester sodium salt
  • a counterion such as Li, Na, K and Zn
  • the free acid with no ester or a different ester, such as, but not limited to, methyl, ethyl and ethylene glycol.
  • Embodiments of some aspects of the invention may further comprise additional additives, such as, for example, fillers; branching agents; reheat agents; anti blocking agents; anti-static agents; biocides; blowing agents; coupling agents; anti-foaming agents; flame retardants; heat stabilizers; impact modifiers; crystallization aids; clarifiers; lubricants; plasticizers; processing aids; buffers; colorants; slip agents; and combinations thereof.
  • additional additives such as, for example, fillers; branching agents; reheat agents; anti blocking agents; anti-static agents; biocides; blowing agents; coupling agents; anti-foaming agents; flame retardants; heat stabilizers; impact modifiers; crystallization aids; clarifiers; lubricants; plasticizers; processing aids; buffers; colorants; slip agents; and combinations thereof.
  • additional additives such as, for example, fillers; branching agents; reheat agents; anti blocking agents; anti-static agents; biocides; blowing agents; coupling agents
  • an additive or additives is added separately to the composition.
  • an additive or additives are incorporated by liquid dosing.
  • the additive or additives is included in one or more masterbatches used to prepare the compositions.
  • the one or more masterbatches with or without additives used in the composition may be homogeneous or blended.
  • the one or more additives included in the compositions may be incorporated via the same method, e.g. both in a single masterbatch, both by separate addition, or both in a liquid dosing mixture, or via different methods, e.g. one or more additives in a single masterbatch and one or more separate additives, or one or more additive in one masterbatch and one or more additive in a second masterbatch, into the compositions of the present invention.
  • an ionic compatibilizer may be a separately added additive.
  • a transition metal catalyst may be a separately added additive.
  • the melting point of the composition providing gas barrier properties of the present invention can be conveniently controlled by adjusting various characteristics or parameters of the composition, as known to those skilled in the art. For instance, one skilled in the art may opt to suitably select the molecular weight of the polyolefin, to adjust the melting point. It is also possible to select different types of polyolefin to adjust the melting point. Thus, one skilled in the art may select or mix suitable polyolefins to reliably adjust the melting point of the polymer composition. For instance, the chain length and the presence or absence of a side chain influences the melting point of the polymer composition. A further possibility is to use a modified polyolefin as described herein. A further possibility is the addition of additives. Another possibility is the molecular weight distribution obtained by combining or otherwise mixing varying polyolefins to provide a melting range that may be in favor of thermal transitions suited to the article being formed.
  • One embodiment of the composition providing gas barrier properties is liquid at 25° C.
  • the optical appearance and mechanical properties of the resulting film or article can be conveniently controlled by adjusting various characteristics or parameters of the composition of the present invention, as known to those skilled in the art.
  • one skilled in the art may opt to suitably select the molecular weight of the polyolefin to adjust the optical appearance and mechanical properties.
  • one skilled in the art may select or mix suitable polyolefins to reliably adjust the optical appearance of the polymer composition.
  • a further possibility is to use a modified polyolefin as described herein.
  • Other options include suitably selecting the type of polyolefin. For instance, the chain length and the presence or absence of a side chain influences the optical appearance of a film or article produced from the polymer composition.
  • a further possibility is the addition of additives.
  • the composition for imparting improved gas barrier, oxygen absorption capacity, optical appearance and/or mechanical properties comprises: a) from 80 to 97 parts polyolefin, b) from 1 to 15 parts polymer containing an oxidizable component, said polymer selected from the group consisting of poly ethers, copoly ether esters, copoly ether amides, at least partially aromatic polyamides, and combinations thereof, c) from 10 to 1000 parts per million (ppm) or mg/kg of transition metal added via a transition metal compound or mixture of transition metal compounds, for example >10 ppm or mg/kg to ⁇ 600 ppm or mg/kg, for example >10 ppm or mg/kg to ⁇ 400 ppm or mg/kg, of transition metal, e.g.
  • cobalt added via a transition metal compound or mixture of transition metal compounds, e.g. cobalt carboxylate or stearate or mixtures of cobalt carboxylate or stearate and zinc stearate or acetate, and d) >0 to 5 parts of one or more additives, e.g. stabilizers, such as, for example, a monomeric, oligomeric or polymeric hindered amine light stabilizer (HALS), compatibilizing agents such as, for example, sodium and/or magnesium stearate or alkenyl succinic anhydride, promoters such as, for example, SIM ester and antioxidants such as DL-a-Tocopherol (CAS No. 10191-41-0) and/or
  • HALS hindered amine light stabilizer
  • compatibilizing agents such as, for example, sodium and/or magnesium stearate or alkenyl succinic anhydride
  • promoters such as, for example, SIM ester and antioxidants such as DL-a-Tocopherol (
  • Ethanox ® 330 where the sum of all parts is 100.
  • the composition is characterized in that when an experimental article, for example film, semi-rigid or rigid structure, is formed therefrom and oriented in the x and/or y direction from 50 to 400 % or in a machine direction (MD) of 1 :5 to 1: 10 equal to 500% to 1000% or a transverse direction (TD) of 1 :5 to 1: 10 equal to 500% to 1000% (see Nentwig Kunsstoff Folien, Hanser 2000, page 109), the article exhibits lower oxygen and/or carbon dioxide transmission than a comparative article formed from a control composition when oriented in the x and/or y direction from 50 to 400 %, or in a machine direction (MD) of 1:5 to 1: 10 equal to 500% to 1000% or a transverse direction (TD) of 1 :5 to 1: 10 equal to 500% to 1000% or from a composition with the same components as the instant invention when not oriented in the x and/or y direction from 50 to 400 % or in
  • the article has been oriented at least 50 % in the x direction and/or at least 50 % in the y direction. In other embodiments of the present invention, the article has been oriented at least 100 % in at least one direction.
  • compositions of the present invention are useful in production article such as gas barriers wherein the gas is oxygen, carbon oxides or both.
  • the article is in the form of a film. In other embodiments, the article is a multilayer film. In other embodiments, the article is rigid or semi-rigid structure.
  • article means a particular form or physical object that comprises the barrier composition of the present invention.
  • articles are injection- molded, stretch-molded, blow-molded, extruded physical objects of defined shapes, sizes and forms. These may include, but are not limited to, bottles, containers, hollow blocks or shapes, planar or non-planar trays, film, sheet, tubing, pipe, fiber, container preforms, blow molded articles such as rigid containers, thermoformed articles, flexible bags and the like and combinations thereof.
  • rigid or semi-rigid articles can be formed from plastic, paper or cardboard cartons or bottles such as juice, milk, soft drink, beer and soup containers, thermoformed trays or cups.
  • Ethanox ® 330 (CAS No. 1709-70-2), is used in examples of the present disclosure, such as that manufactured by SI Group. Typical commercial purity of Ethanox ® 330 is greater than 99 % by weight. Amounts of the Ethanox ® 330 useful in the masterbatch preparations of Example 1 and Example 4 range from 0 to about 1 kg.
  • An industrial sterically hindered amine light stabilizer Chimassorb ® 944 FDL (CAS No. 70624-18-9), as used in examples of the present disclosure, is manufactured by BASF. Amounts of Chimassorb ® 944 FDL useful in the masterbatch preparations of Example 1 and Example 4 range from 0 to about 1 kg.
  • Cobalt stearate (CAS No. 13586-84-0), as used in Examples 1 and Example 4 of the present disclosure, is manufactured and supplied by Umicore under the“Ecos S 9.5: cobalt stearate 9.5 %” product name. Amounts of the cobalt stearate useful in the masterbatch preparations of Example 1 and 4 range from about 20 to about 130 kg.
  • Zinc stearate (CAS No. 557-05-1), used in examples of the present disclosure, is supplied by Sigma-Aldrich® as zinc stearate purum. The zinc content is 10-12% by weight. Amounts of the zinc stearate useful in the masterbatch preparations of Example 1 and 4 range from about 0 to about 45 kg.
  • Sodium stearate (CAS No. 68424-38-4), as used in examples of the present disclosure, is supplied by Peter Greven GmbH & Co. KG, Germany, under the“Ligastar NA R/D” product trade name.
  • the sodium content in Ligastar NA R/D is about 6 % by weight.
  • Amounts of the sodium stearate useful in the masterbatch preparations of Example 1 range from about 0 to about 30 kg.
  • Aromatic polyamide (poly (m-xylene adipamide)) MXD6 used in examples is commercially available from Mitsubishi Gas Chemical Company, MXD6 S6007 (CAS: 25718-70-1). Amounts of the aromatic polyamide useful in the MXD6 additive preparation in Example 2 and 4 range from about 300 to about 800 kg.
  • 5-Sulfoisophthabc acid dimethyl ester sodium salt (SIM ester; CAS No. 3965- 55-7), is commercially available from Sigma-Aldrich® under the“Dimethyl 5- sulfoisophthalate sodium salt” name with a molecular weight of 296.3g/mol. Amounts of SIM ester used in the masterbatch preparations of Example 1,2, and 4 range from 0 to about 45 kg.
  • Polyethylene (PE) as used in examples of the present disclosure is supplied by Total as Polyethylene HDPE SB 1359 (CAS No. 9002-88-4; 25213-02-9). Amounts of the polyethylene useful in the masterbatch preparations of Example 1 range from about 600 to about 980 kg. Amounts of the polyethylene useful in the MXD6 additive preparation in Example 2 range from about 0 to about 500 kg. Amounts of the polyethylene useful in the masterbatch preparations of Example 4 range from about 100 to about 500 kg.
  • PE-g-MA Maleic anhydride grafted PE
  • Amounts of the PE-g-MA useful in the masterbatch preparation of Example 1 range from 0 to about 400 kg.
  • Amounts of the PE-g-MA useful in the masterbatch preparation of Example 2 and 4 range from about 0 to about 500 kg.
  • a commercially available antioxidant DL-a-Tocopherol (CAS No. 10191-41- 0), is used in examples of the present disclosure, such as that distributed by Alfa Aesar. Typical commercial purity of DL-a-Tocopherol is greater than 96 % by weight. Amounts of the DL-a-Tocopherol useful in the masterbatch preparations of Example 1 and Example 5 range from 0 to about 2 kg.
  • PE-g-MA is used as received pure or in a premix with PE to provide the matrix material/source material for the extrusion step.
  • Cobalt stearate, sodium stearate, 5-Sulfoisophthalic acid dimethyl ester sodium salt (SIM ester), Ethanox® 330, zinc stearate, Chimassorb® 944, and DL-a- tocopherol are added directly in the melt extrusion step, respectively.
  • the melt extruder used is a co-rotating, 27 mm extruder screw diameter and screw length to diameter (L:D) ratio of 36: 1, for example, Leistritz Micro 27 36D model melt extruder.
  • the polymer processing rate is about 4 kg/hr.
  • Stage-wise operating temperatures are: water at room temperature (To), 200 °C (T1-T4), 205 °C (T5-T7), 210 °C (Tx) and 220 °C (T9).
  • the desired molten material is extruded into a deionized water cooling bath.
  • the cooled polymer strands are pelletized with a Pell-tec pelletizer into typical cylindrical granules of about 2 mm diameter and about 3 mm length.
  • Either of the additives (stearates, SIM ester, antioxidants, stabilizers), and/or PE-g-MA in the final Cobalt stearate Masterbatch (Catalyst-MB) composition may be varied by adjusting the amounts of additives and/or PE-g-MA, respectively.
  • PE-g-MA is used as received in a premix with PE and/or MXD6 to provide the source material for the extrusion step.
  • the melt extruder used is a co-rotating, 27 mm extruder screw diameter and screw length to diameter (L:D) ratio of 36: 1, for example, Leistritz Micro 27 36D model melt extruder.
  • the polymer processing rate is about 4 kg/hr.
  • Stage-wise operating temperatures are: water at room temperature (To), 240 °C (Ti), 250 °C (T2-T8), and 255 °C (T9).
  • the desired molten material is extruded into a deionized water cooling bath.
  • the cooled polymer strands are pelletized with a Pell-tec pelletizer into typical cylindrical granules of about 2 mm diameter and about 3 mm length.
  • Either of the polyamide and/or PE-g-MA in the final MXD6 additive composition may be varied by adjusting the amounts of polyamide and/or PE-g-MA, respectively.
  • 1000 kg of MXD6 additive product is prepared using the following component quantities as listed in Table 2. TABLE 2
  • Catalyst Masterbatch and MXD6 (pure or as additive shown in Table 2) may be mixed prior to use for injection molding with any polyolefin base resin.
  • Catalyst Masterbatch as shown in Examples la-j is used in concentrations of 1-15 wt % for injection molding into preforms and/or test bars. Preforms are further stretch blow molded into bottles.
  • MXD6 may be used pure or as an additive (cf. example 2) in a premix with the base resin or premixed with catalyst masterbatch to obtain 1- 10 wt % MXD6 in the final application.
  • the MXD6 amount may be varied further by adjusting the amounts of MXD6/MXD6 additive.
  • PE and/or PE-g-MA are used in a premix with MXD6 to provide the source material for the extrusion step
  • the melt extruder used is a co-rotating, 27 mm extruder screw diameter and screw length to diameter (L:D) ratio of 36: 1, for example, Leistritz Micro 27 36D model melt extruder.
  • the polymer processing rate is about 4 kg/hr.
  • Stage-wise operating temperatures are: water at room temperature (To), 240 °C (Ti), 250 °C (Ti-Tx). and 255 °C (T9).
  • the desired molten material is extruded into a deionized water cooling bath.
  • the cooled polymer strands are pelletized with a Pell-tec pelletizer into typical cylindrical granules of about 2 mm diameter and about 3 mm length.
  • Either of the MXD6 and/or PE-g-MA in the final“all in one” additive composition may be varied by adjusting the amounts of polyamide and/or PE-g-MA, respectively.
  • Either of the additives (stearates, SIM ester, antioxidants, stabilizers) in the final“all in one” additive composition may be varied by adjusting the amounts of additives, respectively.
  • 1000 kg of“all in one” additive product may be prepared using the following component quantities as listed in Table 3.
  • All in one” masterbatch may be mixed prior to use for injection molding with any polyolefin base resin.
  • Example 4a and 4b “all in one” masterbatch as shown in Example 4a and 4b is used in concentrations of 1-10 wt % for injection molding into preforms and/or test bars. Preforms are further stretch blow molded into bottles. Approximately 1-10 wt % MXD6 is obtained in the final application. MXD6 amount may be varied by using different amounts of “all in one” masterbatch.

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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne de nouvelles compositions de polymère et leur utilisation dans des résines de polyoléfine comprenant une polyoléfine, un polymère contenant un composant oxydable, un composé de métal de transition ou un mélange de composés de métal de transition, et un ou plusieurs additifs. Des films et des articles rigides ou semi-rigides fabriqués à partir de ces nouvelles compositions polymères fournissent des protections de barrière aux gaz, une capacité d'absorption d'oxygène, un aspect optique et/ou des propriétés mécaniques améliorés.
PCT/IB2019/000560 2018-06-08 2019-05-31 Mélanges de polymères ayant une capacité d'absorption d'oxygène améliorée WO2019234492A1 (fr)

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