WO2006074521A1 - Compositions pour piegeage d'oxygene - Google Patents

Compositions pour piegeage d'oxygene Download PDF

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Publication number
WO2006074521A1
WO2006074521A1 PCT/AU2006/000041 AU2006000041W WO2006074521A1 WO 2006074521 A1 WO2006074521 A1 WO 2006074521A1 AU 2006000041 W AU2006000041 W AU 2006000041W WO 2006074521 A1 WO2006074521 A1 WO 2006074521A1
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WO
WIPO (PCT)
Prior art keywords
hydrogenated
oxygen
anthraquinone derivative
positions
quinonoid
Prior art date
Application number
PCT/AU2006/000041
Other languages
English (en)
Inventor
Andrew David Scully
Mark Andrew Horsham
James Keith Gerard Murphy
Michael Mcnally
Ross Anthony Santangelo
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2005900118A external-priority patent/AU2005900118A0/en
Application filed by Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Publication of WO2006074521A1 publication Critical patent/WO2006074521A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/16—Quinones the quinoid structure being part of a condensed ring system containing three rings

Definitions

  • This invention relates to a method of scavenging oxygen using polymeric compositions comprising an hydrogenated anthraquinone derivative comprising a quinonoid sub-structure, for use in, for example, food and beverage packaging to scavenge unwanted oxygen, which either remains within the package following the packaging of the food or beverage or otherwise enters the package by permeating through the packaging material.
  • the hydrogenated anthraquinone derivative comprising a quinonoid sub-structure may also be incorporated into packaging materials, to prevent oxygen from permeating through the packaging material to enter the inside of a package.
  • a wide variety of foods, beverages, pharmaceuticals and other materials are susceptible to loss in quality if they are exposed to significant amounts of oxygen during storage.
  • the damage can arise from, for example, chemical oxidation of the product and/or microbial growth.
  • In the field of packaging such damage has been traditionally addressed by generating relatively low-oxygen atmospheres by vacuum packing and/or inert gas flushing.
  • these methods are not generally applicable for various reasons.
  • the fast filling speeds commonly used in the food and beverage industries often prevent effective evacuation of, or thorough inert gas flushing of, food and beverage packages, and neither evacuation or inert gas flushing provides any residual capacity for removal of oxygen which may have desorbed from the package contents or entered the package by leakage or permeation.
  • novel oxygen scavenging compositions comprising a source of labile hydrogen or electrons and a reducible organic compound, which may be readily activated or "triggered” (ie brought to its oxygen scavenging form) as required by exposure to, for example, ultraviolet (UV) light.
  • the oxygen scavenging compositions once activated, are capable of scavenging oxygen from an oxygenated atmosphere or liquid in substantial darkness for periods ranging from up to a few minutes or hours to over 100 days.
  • the substituted anthraquinones of the prior art discussed above tend to be coloured particularly in the reduced states.
  • Compositions and packaging which contain such anthraquinones also tend to be coloured.
  • films made using anthraquinone-based compositions can turn a deep yellow colour when the anthraquinone is reduced to activate the oxygen scavenging capacity.
  • the coloured nature of the anthraquinone-based compositions is undesirable in many forms of packaging, particularly the packaging of foodstuffs. It is therefore desirable, although not essential, that any alternative compounds and compositions for scavenging oxygen have, in general, substantially less colour than the prior art substituted anthraquinones.
  • the present invention provides a method of scavenging oxygen (particularly ground state oxygen) in an atmosphere or liquid comprising the steps of:
  • the present invention provides a method of preventing transmission of oxygen (particularly ground state oxygen) across a film or packaging material, the method comprising forming at least a part of the film or packaging material from a polymeric composition comprising an hydrogenated anthraquinone derivative comprising a quinonoid sub-structure.
  • the present invention provides polymeric compositions suitable for use in the methods of the first and second aspects.
  • Figure 1 shows a graph of oxygen transmission vs time of three polymeric compositions comprising 1,2,3,4-THAQ in MXD6 and of three control compositions of MXD6.
  • Figure 2 shows a graph of oxygen scavenging vs time of polymeric compositions comprising 1,2,3,4-THAQ in MXD6.
  • Figure 3 shows (a) the absorption spectrum of a polymeric film according to the present invention comprising 2%w/w 1,2,3,4-THAQ in MXD6; and (b) a comparative absorption spectrum of a polymeric film comprising 2%w/w AQSO 3 Na in MXD6 following reduction of the AQSO 3 Na by exposure to UV radiation.
  • 1,2,3,4-Tetrahydroanthraquinone is a hydrogenated anthraquinone derivative comprising a quinonoid sub-structure.
  • MXD6 film formed by melt compression of a blend of MXD6 and 1,2,3,4-THAQ absorbs oxygen thereby providing an MXD6 film having a substantially enhanced oxygen barrier as disclosed in Examples 1 and 2.
  • MXD6 is a nylon polymer or polyamide formed from the monomers hexanedioic acid and 1,3-benzenedimethanamine. The film does not require activation (eg through exposure to ultraviolet (UV) light) to scavenge oxygen.
  • the composition is virtually colourless which is beneficial in many packaging applications.
  • the present applicant posits that there are at least two possible mechanisms for the observed oxygen scavenging by the composition - these are, that hydrogenated anthraquinones comprising a quinonoid sub-structure may be oxidised at the hydrogenated carbon positions by oxygen or that hydrogenated anthraquinones comprising a quinonoid sub-structure may activate the MXD6 or other oxidisable polymer so that it is oxidised by oxygen.
  • a combination of the two mechanisms is also possible.
  • the present invention provides a method of scavenging oxygen (particularly ground state oxygen) from an atmosphere or liquid comprising the steps of:
  • the polymeric compositions used in the method of the first aspect would also be useful as barriers to oxygen in, for example, packaging applications.
  • the present invention provides a method of preventing transmission of oxygen (particularly ground state oxygen) across a film or packaging material, the method comprising forming at least a part of the film or packaging material from a polymeric composition comprising an hydrogenated anthraquinone derivative comprising a quinonoid sub-structure.
  • the hydrogenated anthraquinone derivative comprising a quinonoid sub-structure of the first and second aspects is selected from the group of compounds represented by the following formula and substituted derivatives thereof:
  • Preferred hydrogenated anthraquinone derivatives with a quinonoid sub-structure include compounds represented by the following formulae and substituted derivatives thereof:
  • a particularly preferred hydrogenated anthraquinone derivative is 1,2,3,4-Tetrahydroanthraquinone (1,2,3,4-THAQ) and substituted derivatives thereof.
  • Preferred substituents are selected from alkyl, alkenyl, ether, halo, carboxylic acid, ester, anhydride, epoxy, hydroxy, and amine substituents.
  • a substituent comprises an alkyl group, the group may be branched or unbranched, substituted or unsubstituted, and is preferably Q-C ⁇ alkyl, more preferably Q-Qoalkyl, even more preferably Q-C ⁇ alkyl and yet more preferably C; ⁇ -C 3 alkyl.
  • a substituent includes an alkenyl group
  • the group may be branched or unbranched, substituted or unsubstituted, mono- or poly-unsaturated, and is preferably C 2 -C 2 oalkenyl, more preferably C 2 -C 1 oalkenyl, even more preferably C 2 -C 6 alkenyl and yet more preferably C 2 -C 3 alkenyl.
  • the hydrogenated anthraquinone derivative comprising a quinonoid sub-structure is substantially colourless or shows less colour relative to reduced anthraquinones
  • the hydrogenated anthraquinone derivative comprising a quinonoid sub-structure is selected such that it has a maximum absorbance in the visible region (400nm-700nm) that is no more than half that of the reduced form of AQSO 3 Na in MXD6 under the same conditions.
  • the polymeric compositions of the present invention are able to scavenge oxygen independently of the presence of a transition metal catalyst. Accordingly, in a preferred embodiment, the polymeric compositions do not comprise a transition metal catalyst.
  • Polymeric compositions used in the methods of the first to fourth aspects of the present invention may be in a solid, semi-solid (eg a gel) or liquid (eg a polymeric liquid such as an ink) form. They may therefore be applied as, or incorporated in, for example, bottle closure liners, inks, coatings, adhesives (eg polyurethanes), films, sheets or layers in containers such as trays, bottles or blister packaging either alone or as laminations or co-extrusions. When used in films or layers, they may be blended with typical polymers or copolymers used for construction of films or layers such as those approved for food or pharmaceutical contact. Such films or layers may be produced by extrusion at temperatures between 50 0 C and 350 0 C depending upon chemical composition and molecular weight distribution.
  • the hydrogenated anthraquinone derivative may be blended into the polymeric composition.
  • the polymeric composition of the first and second aspects may be formed from any suitable polymer or blend of polymers including nylons, polyesters, polyolefins and ethylene- vinyl alcohol copolymers.
  • the polymer is nylon and more preferably MXD6.
  • the hydrogenated anthraquinone derivative itself may be in a polymerised form either as a homopolymer or as a copolymer. Oligomer forms may also be suitable.
  • Hydrogenated anthraquinone derivative-based monomers can be made, for example, by covalently bonding an ethylenically unsaturated group to a phenyl ring of the hydrogenated anthraquinone derivative.
  • a polymerised form of the hydrogenated anthraquinone derivative may also be prepared by using an hydrogenated anthraquinone derivative carrying groups, such as carboxylic acid, ester, anhydride, epoxy, hydroxy, and amine groups, that enable the derivative to react with polymerisable molecules and preformed polymers.
  • an hydrogenated anthraquinone derivative carrying groups such as carboxylic acid, ester, anhydride, epoxy, hydroxy, and amine groups
  • the present invention provides polymeric compositions suitable for use in the methods of the present invention comprising an hydrogenated anthraquinone derivative comprising a quinonoid sub-structure.
  • Example 1 Oxygen barrier performance of a composition comprising 1,2,3,4-THAQ in MXD6
  • Amorphous MXD6 films containing 2% w/w 1,2,3,4-THAQ having film thicknesses in the range 71-74 ⁇ m were prepared by melt-mixing, followed by melt-compression at 250 0 C.
  • Amorphous MXD6 films without 1,2,3,4-THAQ, and having film thicknesses of approximately 45 ⁇ m were prepared by melt-compression at 25O 0 C and used as controls.
  • the oxygen transmission measurements were conducted using a technique (R.V. Holland, M. L. Rooney, R. A.
  • test films both test films are either MXD6-THAQ, or MXD6
  • MXD6-THAQ both test films are either MXD6-THAQ, or MXD6
  • the test cell is then placed in an illuminated controlled temperature/humidity cabinet.
  • the tests in this work were performed in air at 23 0 C and 57% RH.
  • the colour of the rubrene film decreases in the presence of oxygen and light, and this change is used to determine the permeation rate of oxygen through the test films.
  • the light in the storage cabinet was filtered to prevent any absorption of light by the THAQ during the course of experiments.
  • the results for three MXD6-THAQ and three control MXD6 film samples are shown in Figure 1.
  • the amount of oxygen transmitted by the MXD6 films containing 2%w/w 1,2,3,4-THAQ is at least 2 orders of magnitude lower than for the films of MXD6 alone.
  • the MXD6 films containing 2%w/w 1,2,3,4-THAQ were substantially colourless and remained that way after exposure to oxygen.
  • Example 2 Oxygen scavenging performance of a composition comprising 1,2,3,4-THAQ in MXD6
  • MXD6-THAQ films Two amorphous MXD6 films containing 2% w/w 1,2,3,4-THAQ, and having a thickness of approximately 50 ⁇ m were used for oxygen scavenging experiments.
  • the MXD6-THAQ films were vacuum-sealed in foil-laminate pouches and then injected with 10ml of air. The pouches were then placed in a 12O 0 C oven to simulate the temperature of retort processing.
  • the oxygen concentration of the headspace was measured by Gas Chromatography after 30 minutes, and then again after 60 minutes in the oven.
  • the results of oxygen scavenging measurements for the MXD6-THAQ films are shown in Figure 2.
  • the scavenging efficiency is the ratio of the actual volume of oxygen scavenged by the film to the theoretical volume of oxygen that could be removed by the film if each molecule of the 1,2,3,4-THAQ was capable of scavenging a molecule of oxygen.
  • the films were substantially colourless and remained that way after exposure to oxygen.
  • Example 3 Comparison of the absorption spectra of a polymeric composition comprising 1,2,3,4-THAQ in MXD6 with a polymeric composition comprising the reduced form of AQSOsNa in MXD6

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Packages (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne un procédé de piégeage de l'oxygène ( en particulier, de l'oxygène à l'état fondamental) dans une atmosphère ou un liquide, procédé comprenant les étapes suivantes : (i) préparation d'une composition polymère comprenant un dérivé anthraquinonique hydrogéné ayant une sous-structure quinonoïde, composition dans laquelle le dérivé anthraquinonique est sélectionné à partir de composés répondant à la formule présentement définie, et de dérivés substitués de celui-ci, ; au moins deux des atomes de carbone en positions 1 à 8 étant hydrogénés, et chaque atome de carbone restant non hydrogéné en positions 1 à 8 étant compris dans une liaison insaturée à un atome de carbone adjacent non hydrogéné en positions 1 à 8 ; et (ii) exposition de l'atmosphère ou du liquide à ladite composition, de façon qu'au moins une portion de l'oxygène dans l'atmosphère ou le liquide soit éliminée par réaction avec la composition. L'invention concerne également des procédés de prévention de la transmission de l'oxygène à travers un film ou un matériau d'emballage au moyen de la composition polymère de l'invention. L'invention concerne en outre une composition polymère comprenant un dérivé anthraquinonique hydrogéné présentant une sous-structure quinonoïde.
PCT/AU2006/000041 2005-01-13 2006-01-13 Compositions pour piegeage d'oxygene WO2006074521A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2005900118A AU2005900118A0 (en) 2005-01-13 Compositions for scavenging oxygen
AU2005900118 2005-01-13

Publications (1)

Publication Number Publication Date
WO2006074521A1 true WO2006074521A1 (fr) 2006-07-20

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6214940A (ja) * 1985-07-12 1987-01-23 Kawasaki Kasei Chem Ltd 脱酸素剤の製造法
RU1838264C (ru) * 1991-06-03 1993-08-30 Гомельский Филиал Нпо@ Электроники Органических Материалов Материал дл защитного покрыти
WO1994012590A1 (fr) * 1992-11-24 1994-06-09 Commonwealth Scientific And Industrial Research Organisation Desoxygenants independants de catalyseurs a base de metaux de transition
WO2002076916A1 (fr) * 2001-03-23 2002-10-03 Commonwealth Scientific And Industrial Research Organisation Composes auto-reducteurs d'anthraquinone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6214940A (ja) * 1985-07-12 1987-01-23 Kawasaki Kasei Chem Ltd 脱酸素剤の製造法
RU1838264C (ru) * 1991-06-03 1993-08-30 Гомельский Филиал Нпо@ Электроники Органических Материалов Материал дл защитного покрыти
WO1994012590A1 (fr) * 1992-11-24 1994-06-09 Commonwealth Scientific And Industrial Research Organisation Desoxygenants independants de catalyseurs a base de metaux de transition
WO2002076916A1 (fr) * 2001-03-23 2002-10-03 Commonwealth Scientific And Industrial Research Organisation Composes auto-reducteurs d'anthraquinone

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199519, Derwent World Patents Index; Class A82, AN 1995-146068 *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 192 *

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