US20130023609A1 - Use of protected N-hydroxyimide derivates and transition metal as oxygen scavenger system in transparent polyolefin films - Google Patents

Use of protected N-hydroxyimide derivates and transition metal as oxygen scavenger system in transparent polyolefin films Download PDF

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US20130023609A1
US20130023609A1 US13/511,162 US201013511162A US2013023609A1 US 20130023609 A1 US20130023609 A1 US 20130023609A1 US 201013511162 A US201013511162 A US 201013511162A US 2013023609 A1 US2013023609 A1 US 2013023609A1
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alkyl
substituted
unsubstituted
oxygen
phenyl
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Edoardo Menozzi
Massimiliano Sala
Enrico Galfré
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
    • 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
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/012—Additives improving oxygen scavenging properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2207/066—LDPE (radical process)

Definitions

  • oxygen-sensitive products include pharmaceuticals, food products, meats, beverages, etc which are susceptible for degradation due to the presence of oxygen.
  • Limiting the exposure to oxygen provides a means to maintain and enhance the quality and shelf-life of the packaged product.
  • the removal of oxygen from the packaged foods and building barriers against oxygen penetration during storage represents an important objective for the food packaging technologist.
  • packaging a food product in a package capable of minimizing oxygen exposure is a means to maintain the quality of the packaged product over an extended time and to retard spoilage of the product so that it is maintained in inventory longer without wastage and the need of restocking and replacement.
  • Passive gas barrier film that can act as a physical barrier to transmission of oxygen but does not react with oxygen.
  • Films obtained from ethylene vinyl alcohol copolymer (EVOH) or polyvinylidene dichloride (PVDC) are commonly used for this purpose due to their excellent oxygen barrier properties. By physically blocking transmission of oxygen, these barrier films can maintain over time the initial oxygen levels within a package. Because passive barrier films can add cost to a packaging construction and do not reduce levels of oxygen already present in the packaging construction, however, there is a need for effective, lower cost alternatives and improvements.
  • An approach to achieving or maintaining a low oxygen environment inside a package is to use a packet containing an oxygen absorbent material.
  • the packet also sometimes referred to as a pouch or sachet, is placed in the interior of the package along with the product.
  • Sakamoto et al. discloses oxygen absorbent packets in Japan Laid Open Patent Application No. 121634/81 (1981).
  • a typical ingredient used in the oxygen scavenger carried in the packet is reduced iron powder which can react with oxygen to form ferrous oxide or ferric oxide, as disclosed in the U.S. Pat. No. 4,856,650.
  • Japan Laid Open Patent Application No. 82-24634 (1982) discloses an oxygen absorber composition comprising 100 parts by weight (pbw) iron powder, 2 to 7 pbw ammonium chloride, 8 to 15 pbw aqueous acid solution and 20 to 50 pbw of a slightly water soluble filler such as activated clay.
  • Japan Laid Open Patent Application No. 82-24634 (1982) discloses an oxygen absorber composition comprising 100 parts by weight (pbw) iron powder, 2 to 7 pbw ammonium chloride, 8 to 15 pbw aqueous acid solution and 20 to 50 pbw of a slightly water soluble filler such as activated clay.
  • an oxygen arresting composition comprising a metal, such as iron, copper or zinc, and optionally, a metal halide such as sodium chloride or zinc chloride at a level of 0.001 to 100 pbw to 1 pbw of metal and a filler such as clay at a level of 0.01 to 100 pbw to 1 pbw of metal.
  • oxygen absorbent or scavenger materials used in packets can react chemically with oxygen in the package, also sometimes referred to as “headspace oxygen”, they do not prevent external oxygen from penetrating into the package. Therefore, it is common for packaging in which such packets are used to include additional protection such as wrappings or passive barrier films of the type described above. This adds costs to product costs. With many easy-to-prepare foods, another difficulty with oxygen scavenger packets is that consumers may mistakenly open them and consume their contents together with the food. Moreover, the extra manufacturing step of placing a packet into a container can slow production. Further, oxygen absorbent packets are not useful with liquid products.
  • a so-called “active” oxygen absorber i.e., one that reacts with oxygen.
  • active oxygen absorber i.e., one that reacts with oxygen.
  • the packaging is said to provide an “active-barrier” as distinguished from passive barrier films which block transmission of oxygen but do not react with it.
  • Active-barrier packaging is an attractive way to protect oxygen-sensitive products because it not only can prevent oxygen from reaching the product from the outside but also can absorb oxygen present within a container.
  • One approach for obtaining active-barrier packaging is to incorporate a mixture of an oxidizable metal (e.g., iron) and an electrolyte (e.g., sodium chloride) into a suitable resin, melt process the result into monolayer or multilayer sheets or films and form the resulting oxygen scavenger-containing sheets or films into rigid or flexible containers or other packaging articles or components.
  • an oxidizable metal e.g., iron
  • an electrolyte e.g., sodium chloride
  • Component proportions are such that 1 to 500 parts metal halide are present per 100 parts resin and 1 to 200 parts metal halide are present per 100 part metal.
  • the U.S. Pat. No. 5,153,038 discloses plastic multilayer vessels of various layer structures formed from a resin composition formed by incorporating an oxygen scavenger, and optionally a water absorbing agent, in a gas barrier resin.
  • the oxygen scavenger can be a metal powder such as iron, low valence metal oxides or reducing metal compounds.
  • the oxygen scavenger can be used in combination with an assistant compound such as a hydroxide, carbonate, sulfite, thio-sulfite, tertiary phosphate, secondary phosphate, organic acid salt or halide of an alkali metal or alkaline earth metal.
  • the water absorbing agent can be an inorganic salt such as sodium chloride, calcium chloride, zinc chloride, ammonium chloride, ammonium sulfate, sodium sulfate, magnesium sulfate, disodium hydrogenphosphate, sodium dihydrogenphosphate, potassium carbonate or sodium nitrate.
  • the oxygen scavenger can be present at 1 to 1000 weight-% based on weight of the barrier resin.
  • the water absorbing agent can be present at 1 to 300 weight-% based on weight of the barrier resin.
  • scavenger systems incorporating an oxidizable metal (e.g., iron) and a metal halide (e.g., sodium chloride) into a thermoplastic layer is the inefficiency of the oxidation reaction.
  • oxidizable metal e.g., iron
  • metal halide e.g., sodium chloride
  • Another oxygen-scavenging composition disclosed in the U.S. Pat. No. 4,104,192, comprises a dithionite and at least one compound having water of crystallization or water of hydration.
  • Listed among these compounds are various hydrated sodium salts, including carbonate, sulfate, sulfite and phosphates; sodium pyrophosphate decahydrate is specifically mentioned.
  • sodium pyrophosphate decahydrate was the least effective of the compounds tested.
  • use of hydrate containing compounds may not suitable in oxygen-scavenging resins that require high temperature processsing.
  • 6,586,514 describe an oxygen scavenging composition comprising an oxidizable metal component, an electrolyte component, and a non-electrolytic acidifying component that is thermally stable at thermoplastic resin melt fabrication temperatures.
  • WO2006089895 discloses a similar system wherein the electrolytic component participating in the oxidation reaction is obtained by hydrolysis of a Lewis acid salts and/or theirs adducts.
  • a different approach to oxygen scavenger technology employed in synthetic thermoplastics such as polyolefin homo- and copolymers include the use of conventional degradation additives such as transition metal salts based on cobalt, copper or nickel which work well in many applications were oxygen uptake is required.
  • the polymer matrix itself act as oxidizable substrate and the oxygen scavenger process has to proceed via oxidation reactions along the carbon-carbon polyolefin chain catalyzed by the redox cycle of polyvalent metal ions.
  • Many countries have however restrictive regulations on the use of such transition metals for reasons of environmental concern.
  • JP-A-2000-290312 describes a method in which various polymers are denatured with gas containing oxygen atoms using an N-hydroxyimide compound as a catalyst. This method allows a polar group to be introduced efficiently into a polymer without cutting the main chain of the polymer and as a result, a polymer can be obtained that is excellent in antistatic property.
  • An object of the present invention is therefore to provide improved oxygen-scavenging compositions and packagings. Another object is to provide low costs, oxygen-scavenging compositions of improved efficiency. Another object is to provide oxygen scavenging composition that can be used effectively, even at relatively low levels, in a wide range of active-barrier packaging films and sheets, including laminated and coextruded multilayer films and sheets. Another object is ti provide active-barrier packaging containers that can increase the shelf-life of oxygen-sensitive products by slowing the passage of external oxygen into the container, by absorbing oxygen present inside the container or both. Other objects will be apparent to those skilled in the art.
  • the problem which was solved within this invention required the use of thermal stable protected cyclic N-hydroxyimide derivatives, transition metal catalyst in combination with an oxidazable substrate like, but not limited at, polyterpene resin based on alfa and/or beta pinene and/or d-limonene used as organocatalytic oxidation additives for transparent food packaging oxygen scavenger application.
  • polyterpene resin based on alfa and/or beta pinene and/or d-limonene used as organocatalytic oxidation additives for transparent food packaging oxygen scavenger application.
  • suitable catalyst precursors are also given which make use of light, humidity, and/or heat to trigger the initiation of the degradation process.
  • the catalytic role of the organic oxidation promoter is summarized in the scheme below considering N-hydroxyphthalimide as example compound:
  • cyclic N-hydroxyimide derivatives By designing cyclic N-hydroxyimide derivatives according to the resin needs, the polarity can be easily adjusted changing the substitution pattern of the basic nucleus.
  • Unpolar resins such as polyolefins will require lipophilic substituents, such as branched and linear alkyl chains, whereas cyclic N-hydroxyimides designed for more polar resins such as polyvinyl alcohol may be modified attaching more hydrophilic groups such as polyethylene glycol or polyhydroxy compounds such as sugars.
  • the formation of the active nitroxyl radical species which is active towards the oxidation of organic substrates, can be triggered by heat, light and/or humidity, wherein the oxidation of the polymer can occur independently both in presence or in absence of a transition metal catalyst, other cocatalysts, radical initiators, photosensitisers or -initiators, primary oxidants or mixture of thereof.
  • the final products can be any type of plastic product for food packaging application, which needs enhanced oxygen scavenger activities.
  • the polymer component may be used to manufacture mono or multilayer plastic films, sheets, laminates, trays, bottles, styrofoam cups, blister packages, boxes, package wrappings.
  • the articles may be manufactured by any process available to those of ordinary skill in the art including, but not limited to, extrusion, extrusion blowing, film casting, film blowing, calendering, injection molding, blow molding, compression molding, thermoforming, spinning, blow extrusion and rotational casting.
  • the cyclic N-hydroxyimide derivatives, transition metal catalyst, oxidazable substrate and optionally other additional components can be admixted with the polymer component either simultaneously or in succession, or also immediately prior to the actual processing step.
  • an oxygen-scavenging composition comprising:
  • thermoplastic polymers preferably a thermoplastic polymers as:
  • Example 1 Example 2
  • Example 3 N-(trityloxy)-phthalimide N-(stearoyloxy)phthalimide N-(toluene-4-sulfonyloxy)-phthalimide
  • Example 4 Example 5
  • Example 6 N-(2-benzoylbenzoyloxy)-phtalimide N,N′-dihydroxypyromellitic diimide N,N′-distearoyloxypyromelitimide
  • the oxidation additive(s) may be present in total in a concentration from 0.001-10 wt %, preferably 0.01-5 wt % and most preferably 0.1-5 wt % based on the polymeric resin;
  • Metal salts based on Co, Ce, Mn, Cu, Ni, Vd Preferably these salts are metal salts of fatty acids with a carbon number raging from C 12 to C 36 . Most preferred are metal carboxylates of palmitic (C 16 ), stearic (C 18 ), oleic (C 18 ), linolic (C 18 ) and linoleic (C 18 ) acids.
  • the transition metal salt is Manganese which may be present in a total concentration from 0.001-10 wt %, preferably 0.01-5 wt % and most preferably 0.1-5 wt % based on the polymeric resin.
  • aromatic acids such as benzoic acid. Examples for the use of these salts are given in U.S. Pat. No. 3,840,512 and U.S. Pat. No. 4,101,720;
  • these oxidizable substrates are present in a total concentration from 0.001-10 wt %, preferably 0.01-5 wt % and most preferably 0.1-5 wt % based on the polymeric resin; and optionally, (V) additional components.
  • the optional additional components includes:
  • R 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-( ⁇ , ⁇ -dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-( ⁇ , ⁇ -dimethylbenzyl)-phenyl]benzotriazole. 21.
  • 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives. 22.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, neopentyl tetra( ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate.
  • Sterically hindered amines for example carbonic acid bis(1-undecyloxy-2,2,6,6-tetra-methyl-4-piperidyl)ester, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,66
  • Oxamides for example 4, 4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted ⁇ -anilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • 2-(2-Hydroxyphenyl)-1,3,5-triazines for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
  • the present invention relates in particular to a polymer article having accelerated oxygen scavenger properties triggered by light and/or heat and/or humidity and made of a composition containing:
  • n 1, 2 or 4;
  • X is >C ⁇ O, >S(O) 2 or >C(X 1 )(X 2 );
  • X 1 and X 2 independently of one another are hydrogen, C 1 -C 20 alkyl, C 3 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 identical or different C 1 -C 20 alkyl; or phenyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl;
  • Y is C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 3 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; C 5 -C 12 cycloalkenyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms, C 7 -C 9 -phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 al
  • the radical Y is preferably different from hydrogen.
  • Z is an organic radical containing one or more aromatic groups.
  • Z is in particular a group of the formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i), (I-j), (I-k), (I-l), (I-m) or (I-n)
  • the aromatic rings of the formulae (I-a) to (I-d) and (I-k) to (I-n) and the residues of the formulae (I-e) to (I-j) are optionally substituted by one or more radicals selected from the group consisting of hydroxy, C 1 -C 30 alkyl, C 1 -C 30 alkyloxy, C 2 -C 30 alkenyl, C 2 -C 30 alkenyloxy, C 3 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 C 1-30 alkyl; C 3 -C 12 cycloalkyloxy unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; C 6 -C 18 aryl, C 6 -C 18 aryloxy, C 2 -C 30 carboxylate, C 2 -C 30 carboxamide, C 2 -C 30 acyloxy, C 1 -C 30 acyl, C 1 -C 30 s
  • the aromatic rings of the formulae (II-a) to (II-c) are optionally substituted by one or more radicals selected from the group consisting of hydroxy, C 1 -C 30 alkyl, C 1 -C 30 alkyloxy, C 2 -C 30 alkenyl, C 2 -C 30 alkenyloxy, C 3 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; C 3 -C 12 cycloalkyloxy unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; C 6 -C 18 aryl, C 6 -C 18 aryloxy, C 2 -C 30 carboxylate, C 2 -C 30 carboxamide, C 2 -C 30 acyloxy, C 1 -C 30 acyl, C 1 -C 30 sulfonyl, —S—Z 100 , —S(O) 2 (N(Z 101
  • alkyl having up to 30 carbon atoms examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetrade
  • C 1 -C 20 alkyl in particular C 4 -C 20 alkyl or C 6 -C 20 alkyl is preferred.
  • Z 1 , R 1 and R 2 independently of one another are e.g. C 1 -C 4 alkyl.
  • C 1 -C 30 alkyloxy examples are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, 2-ethylbutoxy, n-pentyloxy, isopentyloxy, 1-methylpentyloxy, 1,3-dimethylbutyloxy, n-hexyloxy, 1-methylhexyloxy, n-heptyloxy, isoheptyloxy, 1,1,3,3-tetramethylbutyloxy, 1-methylheptyloxy, 3-methylheptyloxy, n-octyloxy, 2-ethylhexyloxy, 1,1,3-trimethylhexyloxy, 1,1,3,3-tetramethylpentyloxy, nonyloxy, decyloxy, undecyloxy, 1-methylundecyloxy, do-decyloxy, 1,1,3,3,5,5-hexamethylhex
  • alkenyl having up to 30 carbon atoms examples include allyl, 2-methallyl, butenyl, pentenyl, hexenyl and oleyl.
  • the carbon atom in position 1 is preferably saturated.
  • C 3 -C 18 alkenyl is particularly preferred.
  • C 2 -C 30 alkenyloxy examples are allyloxy, 2-methallyloxy, butenyloxy, pentenyloxy, hexenyloxy and oleyloxy.
  • C 3 -C 18 alkenyloxy is particularly preferred.
  • C 3 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl are cyclo-pentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and 2-methylcyclohexyl.
  • C 5 -C 6 cycloalkyl unsubstituted or substituted by methyl are preferred.
  • C 3 -C 12 cycloalkyloxy unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl are cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclododecyloxy and 2-methylcyclohexyloxy.
  • C 5 -C 6 cycloalkyloxy unsubstituted or substituted by methyl are preferred.
  • Examples of C 5 -C 12 cycloalkenyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl are cyclo-hexenyl and methylcyclohexenyl.
  • C 6 -C 12 aryl examples include phenyl and naphthyl which may optionally be substituted. Unsubstituted or substituted phenyl is preferred.
  • phenyl substituted by 1, 2 or 3 C 1 -C 4 alkyl are 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-sec-butylphenyl, 4-isobutylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,4-dimethylphenyl, 2,6-diethylphenyl, 2-ethyl-6-methylphenyl and 2,6-diisopropylphenyl.
  • C 6 -C 18 aryloxy examples are phenyloxy and naphthyloxy which may optionally be substituted. Phenyloxy unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl is preferred.
  • diphenylmethyl substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl is di[methyl-phenyl]methyl.
  • triphenylmethyl substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl is tris[methyl-phenyl]methyl.
  • C 7 -C 9 -phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl are benzyl, 2-phenylethyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl and tert-butylbenzyl.
  • acyl having up to 30 carbon atoms are C 2 -C 30 alkanoyl, C 3 -C 30 alkenoyl and unsubstituted or substituted benzoyl.
  • C 2 -C 20 alkanoyl, C 3 -C 20 alkenoyl and substituted benzoyl are preferred.
  • Acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, acryloyl and crotonoyl are more specific examples.
  • C 2 -C 20 alkanoyl and C 3 -C 20 alkenoyl are particularly preferred.
  • C 1 -C 30 sulfonyl is the group
  • a 1 is C 1 -C 30 alkyl, C 3 -C 30 alkenyl, C 3 -C 12 cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; phenyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 20 alkyl; or C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl.
  • a particularly preferred radical is
  • Examples of a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms are:
  • C 2 -C 30 carboxylate is the group
  • a 2 is C 1 -C 29 alkyl, C 3 -C 18 alkenyl, C 3 -C 12 cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; phenyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; or C 7 -C 9 -phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl.
  • C 2 -C 30 carboxamide is the group
  • A′ 2 has one of the definitions of A 2
  • C 2 -C 30 acyloxy are C 2 -C 20 alkanoyloxy, C 3 -C 20 alkenoyloxy and substituted benzoyloxy are preferred.
  • Acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, octanoyloxy, benzoyloxy, acryloyloxy and crotonoyloxy are more specific examples.
  • C 2 -C 20 alkanoyloxy, C 3 -C 20 alkenoyloxy and benzoyloxy are particularly preferred.
  • C 3 -C 30 diacyl is the group
  • a 3 is C 2 -C 20 alkylene, C 2 -C 20 alkylene interrupted by oxygen, sulphur or >N—R 3 with R 3 having one of the meanings of R 1 ; C 2 -C 12 alkenylene, C 2 -C 12 alkynylene, C 5 -C 12 cycloalkylene, C 5 -C 12 cycloalkylene-(C 1 -C 4 alkylene)-C 5 -C 12 cycloalkylene, C 1 -C 4 alkylene-(C 5 -C 12 cycloalkylene)-C 1 -C 4 alkylene, phenylene, phenylene-(C 1 -C 4 alkylene)-phenylene or C 1 -C 4 alkylene-phenylene-C 1 -C 4 alkylene.
  • C 3 -C 30 di(acyloxy) is the group
  • a 4 has one of the definitions of A 3 .
  • C 3 -C 45 dicarboxylate is the group
  • a 5 has one of the definitions of A 3 .
  • a further preferred example is
  • C 3 -C 45 di(carboxamide) is the group
  • A′ 5 has one of the definitions of A 3 .
  • a preferred example of diamine is the group consisting of:
  • R 4 and R 5 independently of one another have one of the meanings of R 1 and A 6 has one of the meanings of A 3 .
  • diamide is the group consisting of:
  • R 6 and R 7 independently of one another have one of the definitions of R 1 and A 7 has one of the definitions of A 3 .
  • alkylene having up to 20 carbon atoms examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene.
  • alkylene having up to 20 carbon atoms and being interrupted by oxygen, sulphur or >N—R 3 are 3-oxapentane-1,5-diyl, 4-oxaheptane-1,7-diyl, 3,6-dioxaoctane-1,8-diyl, 4,7-dioxadecane-1,10-diyl, 4,9-dioxadodecane-1,12-diyl, 3,6,9-trioxaundecane-1,1′-diyl, 4,7,10-trioxamidecane-1,13-diyl, 3-thiapentane-1,5-diyl, 4-thiaheptane-1,7-diyl, 3,6-dithiaoctane-1,8-diyl, 4,7-dithiadecane-1,10-diyl, 4,9-dithiadodecane-1,
  • C 2 -C 12 alkenylene is 3-hexenylene.
  • C 6 -C 12 alkynylene is preferred.
  • C 5 -C 12 cycloalkylene is cyclohexylene.
  • Examples of C 5 -C 12 cycloalkylene-(C 1 -C 4 alkylene)-C 5 -C 12 cycloalkylene are methylenedicyclohexylene and isopropylidenedicyclohexylene.
  • C 1 -C 4 alkylene-(C 5 -C 12 cycloalkylene)-C 1 -C 4 alkylene is cyclohexylenedimethylene.
  • phenylene-(C 1 -C 4 alkylene)-phenylene is methylenediphenylene.
  • C 1 -C 4 alkylene-phenylene-C 1 -C 4 alkylene is phenylenedimethylene.
  • radical X are >C ⁇ O, >S(O) 2 , >CH 2 , >C(CH 3 ) 2 and >C(phenyl) 2 .
  • n is preferably 1 or 2
  • a preferred example of the group (I-a) is the residue of the formula (I-a-1).
  • Y is C 1 -C 30 alkyl, C 7 -C 9 -phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; triphenylmethyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; C 2 -C 30 acyl, —COOY 0 , C 1 -C 30 sulfonyl or —Si(Y 1 ) 3 ; and Y 0 and Y 1 are C 1 -C 18 alkyl or phenyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl.
  • Z 0 is COOH or —COO—(C 1 -C 20 alkyl); when n is 2, Z is a group of the formula
  • component (B) is a compound of the formula
  • Incorporation of the various additives is best performed in a thermal compounding step, mixing thoroughly the oxidation additives and optional additives, followed by an extrusion of the physical blend at elevated temperature. Typically an extruder with suitable screw configuration is used for this step.
  • the additives can also be added in the form of a preconfectioned master-batch produced in a different manner.
  • any appropriate machine can be used, depending on the final form of the article, for example a blow extruder in the case of films, a cast extrusion machine in the case of sheets or an injection-molding ma-chine.
  • Oxidant Additives Accessibility of the starting materials: Starting materials for the cited examples 1-6 are commercially available compounds, for example N-hydroxy phthalimide Pyromellitic dianhydride Phthalic anhydride
  • Poly limonene Other base nuclei that can be used are: Trimellitic anhydride anhydride N-hydroxyl 1,8-phthalimide Perylene tetracarboxylic acid
  • Example 1 2 Structure Melting point 285-288° C. 209-216° C. MW (g/mol) 213.19 379.42 Data of 210° C.: 0.34% 210° C.: 0.23% thermogra- 260° C.: 2.92% 260° C.: 1.35% vimetric 300° C.: 21.41% 300° C.: 11.11% analysis/ weight loss
  • Example 3 4 Structure Melting point 157-164° C. 232-239° C.
  • a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 200 ml of DMA, 17.8 g of triethylamine and 24.9 g of diphenylchloromethane and 25 g of N-hydroxy-1,8-naphthalimide.
  • the stirred mixture is then heated up at 90° C. for 8 hours.
  • the reaction mixture is then cooled down at room temperature and the precipitate is separated by filtering off the solution, washed with water several times and dried in oven under vacuum at 100° C.
  • the product is obtained as a white solid.
  • a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 200 ml of THF, 17.8 g of triethylamine and 25 g of N-hydroxy-1,8-naphthalimide.
  • THF tetrahydrofuran
  • 23.5 g of p-toluenesulfonyl chloride is then slowly added, at room temperature, 23.5 g of p-toluenesulfonyl chloride; the reaction is then heated at reflux for 4 hours.
  • the reaction mixture is then cooled down at room temperature; the precipitate is separated by filtering off the solution, washed with water several times and dried in oven under vacuum at 100° C.
  • the product is obtained as a white solid.
  • a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 500 ml of THF, 11.44 g of triethylamine and 20 g of N-hydroxy-1,8-naphthalimide. 9.34 g of Acryloyl chloride are slowly added to the mixture and the reaction is stirred at room temperature for 16 hours. The white precipitate is filtered off and the solvent removed under reduce pressure to give an orange solid which is crystallized from 200 mL of isopropanol as a white solid and dried in oven under vacuum at 100° C.
  • a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 25.0 g N-hydroxy-1,8-naphthalimide, 17.76 g of triethylamine in 200 ml of DMF. 32.69 g of Trityl chloride are slowly added to the mixture and the reaction is stirred at room temperature for 16 hours. The white precipitate is filtered and washed with H 2 O, hexane, THF and finally dried in oven under vacuum at 100° C.
  • a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 20.0 g of compound 6, 63.86 g of butyl methacrylate and 4.0 g of AlBN in 400 ml of THF.
  • the mixture is heated at reflux for 4 hours.
  • the solvent is then removed and the solid dissolved in 400 ml of CH 2 Cl 2 , washed with H 2 O and the organic phase dried over Na 2 SO 4 .
  • the solvent is removed to give a light yellow solid which is washed with 100 ml of cold MeOH and finally dried in oven under vacuum at 90° C.
  • Riblene GP20® low density polyethylene has been obtained from Polimeri Europa; Dercolyte is a poly terpene product obtain from Les Dérivés Résiniques & Tercherniques; Manganese Stearate, Mn(C 18 H 35 O 2 ) x , has been purchased from Shepherd Chemical Company and Shelf-plus O 2 2400® has been obtain from ALBIS.
  • shelfplus O 2 2400® was mixed in a 1:1 ratio with low density polyethylene, Riblene® so that the final Iron concentration was 5.0% by weight.
  • Compounds were prepared with an OMC pilot double screw extruder (model EBV 19/25, with a 19 mm screw diameter and 1:25 ratio), and 50 micron-thick films were prepared using Collin Cast Flat-die Extruder model 30 ⁇ 25 L/D (30 mm screw diameter, 1:25 diameter/length ratio).
  • Film thickness is measured and 4.0 grams of film are weighted.
  • the extruded film is folded and placed in a clean 500 ml sealed glass container.
  • a vial containing 15 ml of deionized water is added to produce 100% relative humidity inside the glass container (only for Comparative Sample 1).
  • the oxygen content in the ambient air on day 0 (i.e. equal to the initial oxygen content in the sealed glass container) is tested and recorded using a Mocon Oxygen Analyzer.
  • the glass containers with test films and water vials are stored at 22° C. (generally, room temperature) for 28 days.
  • Oxygen absorbed (ml/g) ⁇ (% O 2 ) i ⁇ (% O 2 ) f ⁇ *0.01 *V j /( W F *W S /W B )
  • the invention can be applied in all areas of packaging where oxygen scavenger activity is de-sired.
  • the polymer article may be used to manufacture plastic films, sheets, laminates, bags, bottles, styrofoam cups, utensils, blister packages, boxes, package wrappings,.
  • the articles may be manufactured by any process available to those of ordinary skill in the art including, but not limited to, extrusion, extrusion blowing, film casting, film blowing, calendering, injection molding, blow molding, compression molding, thermoforming, spinning, blow extrusion and rotational casting. In particular, this is of interest in the area of modify atmosphere (CO 2 , N2) food packaging.
  • the rate of the oxygen uptake can simply be adjusted by changing the concentration of the additives i.e. if higher oxygen scavenger performance is desired, then higher amount of additives is added.

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160093272A1 (en) * 2014-09-29 2016-03-31 Brother Kogyo Kabushiki Kaisha Information processing device and non-transitory storage medium storing instructions executable by the information processing device
US9670408B2 (en) 2013-03-06 2017-06-06 Mitsubishi Gas Chemical Company, Inc. Oxygen absorbent composition and molded body and package using the same
EP3149059B1 (de) * 2014-05-28 2018-09-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von oxyimid-enthaltenden copolymeren oder polymeren als flammschutzmittel, stabilisatoren, rheologiemodifikatoren für kunststoffe, initiatoren für polymerisations- und pfropfprozesse, vernetzungs- oder kopplungsmittel sowie solche copolymere oder polymere enthaltende kunststoffformmassen
US10544284B2 (en) 2014-09-18 2020-01-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of phosphorous-containing organic oxyimides as flame retardants and/or as stabilizers for plastics, flame-retardant and/or stabilized plastic compositions, method for the production thereof, moulded part, paint and coatings
WO2020212377A1 (en) * 2019-04-16 2020-10-22 Byk-Chemie Gmbh Silyl functional compound for improving flame retardant properties
US11680155B2 (en) 2019-04-16 2023-06-20 Byk-Chemie Gmbh Silyl functional compound for improving flame retardant properties

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2507307B1 (en) * 2009-12-02 2014-02-12 Basf Se Use of protected n-hydroxyimide derivates and transition metal as oxygen scavenger system in transparent polyolefin films
AU2012308752B2 (en) 2011-09-12 2015-09-24 Plastipak Packaging, Inc. Monolayer carbon dioxide barrier PET bottles
DE102013005307A1 (de) * 2013-03-25 2014-09-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von organischen Oxyimiden als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffzusammensetzung und hieraus hergestelltem Formteil
JP6255745B2 (ja) * 2013-06-28 2018-01-10 東洋製罐グループホールディングス株式会社 酸素吸収剤
CA3217615A1 (en) 2016-01-07 2017-07-07 Camso Inc. Track system for traction of a vehicle
USD870594S1 (en) 2016-06-28 2019-12-24 Camso Inc. Track for traction of a vehicle
DE102017212772B3 (de) 2017-07-25 2018-01-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Halogenfreie Sulfonsäureester und/oder Sulfinsäureester als Flammschutzmittel in Kunststoffen, diese enthaltende Kunststoffzusammensetzungen und deren Verwendung
EP3684858A1 (en) * 2017-09-18 2020-07-29 Basf Se Additive mixture

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090286060A1 (en) * 2005-09-07 2009-11-19 Massimiliano Sala Degradable polymer article

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101720A (en) 1972-03-01 1978-07-18 Owens-Illinois, Inc. Degradable plastic
US3840512A (en) 1972-11-09 1974-10-08 Ici Ltd Degradable plastics composition
JPS5290485A (en) 1976-01-26 1977-07-29 Mitsubishi Gas Chem Co Inc Oxygen absorbent
JPS54158386A (en) 1978-06-06 1979-12-14 Teijin Ltd Oxygen capturing composition
JPS5660642A (en) 1979-10-25 1981-05-25 Teijin Ltd Oxygen absorptive sheet structure
JPS56121634A (en) 1980-02-29 1981-09-24 Nitto Kasei Kk Oxygen absorbent composition
JPS5724634A (en) 1980-07-22 1982-02-09 Kureha Chem Ind Co Ltd Deoxydizer composition
EP0268848B1 (en) 1986-10-27 1992-05-20 Mitsubishi Gas Chemical Company, Inc. An oxygen absorbent package
EP0367835B1 (en) 1988-04-30 1996-07-31 Toyo Seikan Kaisha, Ltd. Multilayered plastic container
US4992410A (en) 1989-02-17 1991-02-12 Multiform Desiccants, Inc. Oxygen-absorbing package, composition and method of formulation thereof
US5744056A (en) 1993-07-16 1998-04-28 Amoco Corporation Oxygen-scavenging compositions and articles
US6369148B2 (en) 1993-07-16 2002-04-09 Ciba Specialty Chemicals Corporation Oxygen-scavenging compositions and articles
US5776361A (en) * 1995-02-15 1998-07-07 Chevron Chemical Company Multi-component oxygen scavenging composition
BR9909074A (pt) * 1998-03-25 2000-12-05 Chevron Phillips Chemical Co Composição e camada apropriada para remover oxigênio, artigo de fabricação apropriado como um recipiente, pelìcula de múltiplas camadas, artigo para embalagem, processo para fabricar um material polimérico, composição de polìmero removedor de oxigênio não odoroso, e, recipiente rìgido para alimentos ou bebidas
JP4592128B2 (ja) 1999-04-12 2010-12-01 ダイセル化学工業株式会社 ポリマーの変性方法及び変性ポリマー
JP3777888B2 (ja) * 1999-07-27 2006-05-24 東洋製罐株式会社 樹脂組成物、積層体、容器及び容器蓋
US7740926B2 (en) 2001-07-26 2010-06-22 M&G Usa Corporation Oxygen-scavenging containers
JP4590823B2 (ja) * 2002-02-19 2010-12-01 凸版印刷株式会社 酸素吸収能樹脂組成物及びそれを用いた積層体及び包装体
WO2005010101A1 (ja) 2003-07-24 2005-02-03 Kuraray Co., Ltd. 酸素吸収体およびその製造方法ならびにそれを用いた包装材
JP5193606B2 (ja) 2005-02-28 2013-05-08 マルチソーブ テクノロジーズ インク 水活性化酸素掃去組成物
JP2009031444A (ja) * 2007-07-25 2009-02-12 Ricoh Co Ltd プロセスカートリッジ、画像形成装置
JP2011509166A (ja) 2007-12-21 2011-03-24 ビーエーエスエフ ソシエタス・ヨーロピア 酸素捕捉混合物
US8609744B2 (en) 2008-05-06 2013-12-17 Basf Se Oxygen-scavenging mixtures
ES2605619T3 (es) 2009-08-17 2017-03-15 Albis Plastic Gmbh Uso de tensioactivos no iónicos para aumentar la actividad de desoxigenación de películas de poliolefina funcionalizadas
CA2770165A1 (en) 2009-08-17 2011-02-24 Basf Se Use of thermoplastic elastomer to increase oxygen scavenger activity of functionalized polyolefin films
EP2507307B1 (en) * 2009-12-02 2014-02-12 Basf Se Use of protected n-hydroxyimide derivates and transition metal as oxygen scavenger system in transparent polyolefin films

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090286060A1 (en) * 2005-09-07 2009-11-19 Massimiliano Sala Degradable polymer article

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9670408B2 (en) 2013-03-06 2017-06-06 Mitsubishi Gas Chemical Company, Inc. Oxygen absorbent composition and molded body and package using the same
EP3149059B1 (de) * 2014-05-28 2018-09-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von oxyimid-enthaltenden copolymeren oder polymeren als flammschutzmittel, stabilisatoren, rheologiemodifikatoren für kunststoffe, initiatoren für polymerisations- und pfropfprozesse, vernetzungs- oder kopplungsmittel sowie solche copolymere oder polymere enthaltende kunststoffformmassen
US10370537B2 (en) 2014-05-28 2019-08-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of oxyimide-comprising copolymers or polymers as flame retardants, stabilisers, rheology modifiers for plastic materials, initiators for polymerisation- and grafting processes, crosslinking- or coupling agents and also plastic moulding compounds comprising such copolymers or polymers
US10544284B2 (en) 2014-09-18 2020-01-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of phosphorous-containing organic oxyimides as flame retardants and/or as stabilizers for plastics, flame-retardant and/or stabilized plastic compositions, method for the production thereof, moulded part, paint and coatings
US20160093272A1 (en) * 2014-09-29 2016-03-31 Brother Kogyo Kabushiki Kaisha Information processing device and non-transitory storage medium storing instructions executable by the information processing device
WO2020212377A1 (en) * 2019-04-16 2020-10-22 Byk-Chemie Gmbh Silyl functional compound for improving flame retardant properties
US11680155B2 (en) 2019-04-16 2023-06-20 Byk-Chemie Gmbh Silyl functional compound for improving flame retardant properties
US11680154B2 (en) 2019-04-16 2023-06-20 Byk-Chemie Gmbh Silyl functional compound for improving flame retardant properties

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JP2013512977A (ja) 2013-04-18

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