NO321226B1 - Process for Stabilizing Ethoxyquin in Aqueous Formic Acid Solution, Aqueous Formic Acid Solution comprising Ethoxyquin as Antioxidant, and Use for Stabilizing Ethoxyquin - Google Patents

Process for Stabilizing Ethoxyquin in Aqueous Formic Acid Solution, Aqueous Formic Acid Solution comprising Ethoxyquin as Antioxidant, and Use for Stabilizing Ethoxyquin Download PDF

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NO321226B1
NO321226B1 NO20041959A NO20041959A NO321226B1 NO 321226 B1 NO321226 B1 NO 321226B1 NO 20041959 A NO20041959 A NO 20041959A NO 20041959 A NO20041959 A NO 20041959A NO 321226 B1 NO321226 B1 NO 321226B1
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ethoxyquin
ascorbic acid
formic acid
weight
stabilizing
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Tom Granli
Mona Galteland
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Yara Int Asa
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Priority to GB0624070A priority patent/GB2429456B/en
Priority to PCT/NO2005/000160 priority patent/WO2005108371A1/en
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Publication of NO321226B1 publication Critical patent/NO321226B1/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463Organic compounds; Microorganisms; Enzymes
    • A23L3/3481Organic compounds containing oxygen
    • A23L3/3508Organic compounds containing oxygen containing carboxyl groups
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463Organic compounds; Microorganisms; Enzymes
    • A23L3/3544Organic compounds containing hetero rings
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/358Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20Oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/62Three oxygen atoms, e.g. ascorbic acid
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

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  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
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  • Anti-Oxidant Or Stabilizer Compositions (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description

Foreliggende oppfinnelse vedrører en fremgangsmåte for å stabilisere etoksyquin i vandig maursyreholdig løsning, vandig maursyreholdig løsning omfattende etoksyquin som antioksidant, og anvendelse av askorbinsyre og/eller sulfitt for å stabilisere etoksyquin i vandig maursyreholdig løsning. The present invention relates to a method for stabilizing ethoxyquin in an aqueous formic acid-containing solution, an aqueous formic acid-containing solution comprising ethoxyquin as an antioxidant, and the use of ascorbic acid and/or sulfite to stabilize ethoxyquin in an aqueous formic acid-containing solution.

Fiskebiprodukter omfatter verdifulle næringsstoffer som fiskeolje og fiskeprotein. For å konservere fiskebiproduktene kan maursyrebaserte konserveringsmidler tilsettes nevnte biprodukter. Et kjent konserveringsmiddel er en vandig maursyreløsning omfattende etoksyquin (6-etoksy-l,2-dihydro-2,2,4-trimetylquinolin) som en antioksidant. Antioksidanten hindrer oksidasjonsdegradering slik som harsknet i fiskelipider. Et hovedproblem i denne forbindelse er at etoksyquin i 85 vekt % maursyreløsninger dekomponerer under lagring, som forårsaker utfelling og en mørkere farge, som kari forårsake problemer under anvendelse. Den kjemiske dekomponeringen kan også føre til en svakere antioksidanteffekt. Det ville således være av stor interesse å utvikle et produkt hvor etoksyquin ikke ville dekomponere under lagring. Fish by-products include valuable nutrients such as fish oil and fish protein. To preserve the fish by-products, formic acid-based preservatives can be added to said by-products. A known preservative is an aqueous formic acid solution comprising ethoxyquin (6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline) as an antioxidant. The antioxidant prevents oxidative degradation such as rancidity in fish lipids. A major problem in this regard is that ethoxyquin in 85% by weight formic acid solutions decomposes during storage, causing precipitation and a darker color, which can cause problems during use. The chemical decomposition can also lead to a weaker antioxidant effect. It would thus be of great interest to develop a product where ethoxyquin would not decompose during storage.

US 4,772,710 vedrører salter av etoksyquin med en karboksylsyre inneholdende 1 - 5 karbonatomer og med sitronsyre. Karboksylsyren er foretrukket maursyre. Saltene av etoksyquin er anvendelige for oksidasjonsbeskyttelse av bulkmaterialer slik som fiskemel og som midler mot fruktskurv. Etoksyquin i seg selv har ulemper med hensyn til viskositet, løselighet i vann og/eller økende viskositet pga. oksidasjonsforårsaket polymerisasjon. Salter av etoksyquin ser ut til å overkomme eller betydelig redusere de ovennevnte ulempene, men under lagring dekomponerer også salter av etoksyquin fullstendig på 1 - 3 måneder. US 4,772,710 relates to salts of ethoxyquin with a carboxylic acid containing 1-5 carbon atoms and with citric acid. The carboxylic acid is preferably formic acid. The salts of ethoxyquin are useful for oxidation protection of bulk materials such as fishmeal and as agents against fruit scab. Ethoxyquin itself has disadvantages with respect to viscosity, solubility in water and/or increasing viscosity due to oxidation-induced polymerization. Salts of ethoxyquin appear to overcome or significantly reduce the above disadvantages, but during storage, salts of ethoxyquin also decompose completely in 1 - 3 months.

US 3,637,722 vedrører antioksidantsammensetninger inneholdende en antioksidant-synergistblanding. Det er beskrevet at antioksidanter ofte anvendes i kombinasjon med synergister, og eksempler på de mest brukte antioksidanter er gitt, hvor etoksyquin er nevnt. Askorbinsyre er listet opp blant synergistene. Kombinasjonen av antioksidanter med synergister resulterer i noe økning i aktiviteten. Denne synergien er relatert til antioksidanteffekten i bruk, og ikke til en stabilitetseffekt av formuleringen omfattende antioksidantene. US 3,637,722 relates to antioxidant compositions containing an antioxidant synergist mixture. It has been described that antioxidants are often used in combination with synergists, and examples of the most commonly used antioxidants are given, where ethoxyquin is mentioned. Ascorbic acid is listed among the synergists. The combination of antioxidants with synergists results in some increase in activity. This synergy is related to the antioxidant effect in use, and not to a stability effect of the formulation comprising the antioxidants.

PCT/NO03/00349 vedrører et konserveringsmiddel som omfatter karboksylsyrer i blanding med deres salter, en antioksidant som foretrukket er propylgallat og en korrosjonsinhibitor som foretrukket er askorbinsyre. Det er vist at askorbinsyre forhindrer at propylgallat feller ut over tid, og gir således en forlenget lagringstid for produkter behandlet med nevnte konserveringsmiddel. Askorbinsyre er kostbart, så det ville være av interesse å anvende bare begrensede mengder. PCT/NO03/00349 relates to a preservative comprising carboxylic acids in mixture with their salts, an antioxidant which is preferably propyl gallate and a corrosion inhibitor which is preferably ascorbic acid. It has been shown that ascorbic acid prevents propyl gallate from precipitating over time, and thus provides an extended storage time for products treated with the aforementioned preservative. Ascorbic acid is expensive, so it would be of interest to use only limited amounts.

Hovedformålet med foreliggende oppfinnelse var å tilveiebringe en fremgangsmåte for å stabilisere etoksyquin i vandig maursyreholdig løsning. The main purpose of the present invention was to provide a method for stabilizing ethoxyquin in an aqueous solution containing formic acid.

Et annet formål var å oppnå vandig maursyreholdig løsning omfattende etoksyquin som antioksidant, hvor etoksyquin ikke ville dekomponere under lagring. Another purpose was to obtain an aqueous formic acid solution comprising ethoxyquin as an antioxidant, where ethoxyquin would not decompose during storage.

Et ytterligere formål var at produktet og fremgangsmåten skulle gi lave A further purpose was that the product and method should provide low

produksj onskostnader. production costs.

Disse og andre formål med oppfinnelsen ble oppnådd med produktet, fremgangsmåten og anvendelsen som beskrevet nedenfor og som angitt i patentkravene. These and other objects of the invention were achieved with the product, the method and the application as described below and as stated in the patent claims.

For å oppnå formålet med oppfinnelsen begynte oppfinnerne et arbeid for å finne egnede additiver som kunne stabilisere etoksyquin i vandige karboksylsyreholdige løsninger. Det var av interesse å undersøke og finne komponenter som ville stabilisere etoksyquin, og det var av særlig interesse å undersøke askorbinsyre. Det ville også være av interesse å undersøke hvorvidt en kombinasjon av to eller flere komponenter ville stabilisere etoksyquin bedre enn en. Når askorbinsyre er en av komponentene, ville det være mulig å anvende mindre askorbinsyre, som er ganske kostbar, og derved ha en bedre stabilisering og en mer kostnadseffektiv løsning. Det var av særlig interesse å stabilisere etoksyquin i Ensilox® (et ensileringsmiddel fra Hydro Formates AS, omfattende maursyre, vann og etoksyquinformiat). In order to achieve the purpose of the invention, the inventors began work to find suitable additives that could stabilize ethoxyquin in aqueous carboxylic acid-containing solutions. It was of interest to investigate and find components that would stabilize ethoxyquin, and it was of particular interest to investigate ascorbic acid. It would also be of interest to investigate whether a combination of two or more components would stabilize ethoxyquin better than one. When ascorbic acid is one of the components, it would be possible to use less ascorbic acid, which is quite expensive, and thereby have a better stabilization and a more cost-effective solution. It was of particular interest to stabilize ethoxyquin in Ensilox® (an ensiling agent from Hydro Formates AS, comprising formic acid, water and ethoxyquin formate).

Det ble da overraskende funnet at når en kombinasjon av askorbinsyre og sulfitt ble tilsatt, dekomponerte ikke etoksyquin i en vandig maursyreholdig løsning under lagring. Former av sulfitt som kan anvendes er sulfitt, disulfitt (metabisulfitt) og bisulfitt. Kationer kunne være natrium, kalium, magnesium, kalsium eller ammonium. Andre karboksylsyrer, slik som eddiksyre og propionsyre kan anvendes i stedet for eller i tillegg til maursyre. Også små mengder av benzosyre kan anvendes i tillegg til nevnte Ci - C3 karboksylsyrer. It was then surprisingly found that when a combination of ascorbic acid and sulfite was added, ethoxyquin did not decompose in an aqueous formic acid solution during storage. Forms of sulphite that can be used are sulphite, disulphite (metabisulphite) and bisulphite. Cations could be sodium, potassium, magnesium, calcium or ammonium. Other carboxylic acids, such as acetic acid and propionic acid can be used instead of or in addition to formic acid. Small amounts of benzoic acid can also be used in addition to the aforementioned Ci - C3 carboxylic acids.

Den foreliggende oppfinnelse vil i sitt videste omfang omfatte en fremgangsmåte for å stabilisere etoksyquin i vandig maursyreholdig løsning der etoksyquin tilsettes som etoksyquinformiat, som er kjennetegnet ved at 0,1 - 0,5 vekt % askorbinsyre og/eller 0,1-1 vekt % sulfitt tilsettes løsningen. Foretrukket tilsettes 0,3 - 0,4 vekt % askorbinsyre og/eller 0,4 - 0,7 vekt % sulfitt til løsningen. Sulfittet tilsettes foretrukket som natriumdisulfitt. The present invention will in its broadest scope include a method for stabilizing ethoxyquin in an aqueous formic acid-containing solution where ethoxyquin is added as ethoxyquin formate, which is characterized by 0.1-0.5% by weight ascorbic acid and/or 0.1-1% by weight sulfite is added to the solution. Preferably, 0.3 - 0.4% by weight of ascorbic acid and/or 0.4 - 0.7% by weight of sulphite are added to the solution. The sulphite is preferably added as sodium disulphite.

Oppfinnelsen vedrører også en vandig maursyreholdig løsning omfattende etoksyquin i form av etoksyquinformiat som antioksidant, som er kjennetegnet ved at løsningen videre omfatter 0,1 - 0,5 vekt % askorbinsyre og/eller 0,1-1 vekt % sulfitt. Foretrukket omfatter løsningen 0,3 - 0,4 vekt % askorbinsyre og/eller 0,4 - 0,7 vekt % sulfitt. Sulfittet er foretrukket natriumdisulfitt. Konsentrasjonen av maursyre er 60 - 95 vekt %. The invention also relates to an aqueous solution containing formic acid comprising ethoxyquin in the form of ethoxyquin formate as an antioxidant, which is characterized in that the solution further comprises 0.1-0.5% by weight ascorbic acid and/or 0.1-1% by weight of sulphite. The solution preferably comprises 0.3 - 0.4% by weight of ascorbic acid and/or 0.4 - 0.7% by weight of sulphite. The sulphite is preferably sodium disulphite. The concentration of formic acid is 60 - 95% by weight.

Oppfinnelsen vedrører også anvendelse av 0,1 - 0,5 vekt % askorbinsyre og/eller 0,1-1 vekt % sulfitt for å stabilisere etoksyquin i form av etoksyquinformiat i vandig maursyreholdig løsning. Mengden av askorbinsyre er foretrukket 0,3 - 0,4 vekt % og/eller mengden av sulfitt er foretrukket 0,4 - 0,7 vekt %. Sulfittet er foretrukket natriumdisulfitt. The invention also relates to the use of 0.1-0.5% by weight of ascorbic acid and/or 0.1-1% by weight of sulphite to stabilize ethoxyquin in the form of ethoxyquin formate in aqueous formic acid-containing solution. The amount of ascorbic acid is preferably 0.3 - 0.4% by weight and/or the amount of sulfite is preferably 0.4 - 0.7% by weight. The sulphite is preferably sodium disulphite.

Oppfinnelsen er ytterligere beskrevet og forklart i de følgende eksempler og figurer. Figur 1 viser dekomponering av etoksyquin i vandige maursyreholdige løsninger under forskjellige lagringsbetingelser. Figur 2 viser stabilisering av etoksyquin i vandige maursyreholdige løsninger med tilsats av askorbinsyre eller sulfitt. Figur 3 viser innhold av etoksyquin i et antall lagrede prøver av vandige maursyreholdige løsninger med tilsats av askorbinsyre og/eller natriumdisulfitt. The invention is further described and explained in the following examples and figures. Figure 1 shows the decomposition of ethoxyquin in aqueous solutions containing formic acid under different storage conditions. Figure 2 shows the stabilization of ethoxyquin in aqueous solutions containing formic acid with the addition of ascorbic acid or sulphite. Figure 3 shows the content of ethoxyquin in a number of stored samples of aqueous solutions containing formic acid with the addition of ascorbic acid and/or sodium disulfite.

I alle eksemplene ble Ensilox® fremstilt ved å tilsette 0,75 vekt % FEQ 500 (ekvimolart forhold av etoksyquin og maursyre, LL Chemie) til 85 vekt % maursyre. I teorien skulle dette gi 0,375 vekt % etoksyquinekvivalenter i den blandede formuleringen. In all examples, Ensilox® was prepared by adding 0.75 wt% FEQ 500 (equimolar ratio of ethoxyquin and formic acid, LL Chemie) to 85 wt% formic acid. In theory, this should give 0.375 wt% ethoxyquin equivalents in the mixed formulation.

Eksempel 1 Example 1

Eksempel 1 ble utført for å finne den relative betydningen av spesifiserte forhold, som luft, temperatur, lys, jern og kobber, på dekomponeringen av etoksyquin i Ensilox®. Example 1 was carried out to find the relative importance of specified conditions, such as air, temperature, light, iron and copper, on the decomposition of ethoxyquin in Ensilox®.

Fig. 1 viser dekomponering av etoksyquin i Ensilox® under forskjellige lagringsbetingelser. Forklaring av forkortelsene anvendt i Fig. 1: Kontroll (4 °C og fravær av luft, lys, jern og kobber), Temp (romtemperatur, men fravær av luft, lys, jern og kobber), Luft (4 °C i nærvær av luft, fravær av lys, jern og kobber), T + Lu (romtemperatur og nærvær av luft, fravær av lys, jern og kobber), Ly + Fe + Cu (Nærvær av lys, kobber og jern, men fravær av luft og ved 4 °C). Fig. 1 shows the decomposition of ethoxyquin in Ensilox® under different storage conditions. Explanation of the abbreviations used in Fig. 1: Control (4 °C and absence of air, light, iron and copper), Temp (room temperature but absence of air, light, iron and copper), Air (4 °C in the presence of air, absence of light, iron and copper), T + Lu (room temperature and presence of air, absence of light, iron and copper), Ly + Fe + Cu (Presence of light, copper and iron, but absence of air and wood 4 °C).

Fra Fig. 1 kan det ses at luft var den viktigste faktoren og temperatur den nest viktigste faktoren for dekomponering av etoksyquin i vandige maursyreløsninger. I tillegg økte disse faktorene effekten av hverandre. Under ufordelaktige forhold (høy temperatur og luft) dekomponerte etoksyquin fullstendig på 1 - 3 måneder. Under optimale forhold (fravær av luft, lav temperatur) var dekomponeringen langsom, og etter 6 måneder hadde bare opptil 10 - 15 % dekomponert (avhengig av nærvær av jern, kobber og lys). Med tilgang til luft, men ved lav temperatur (og ikke jern, kobber og lys), var dekomponeringen ca. 25 % og 65 % etter henholdsvis 3 og 6 måneder. Med fravær av luft, men ved høy temperatur (og ikke jern, kobber og lys), var dekomponeringen ca. 25 % etter 6 måneder. From Fig. 1 it can be seen that air was the most important factor and temperature the second most important factor for the decomposition of ethoxyquin in aqueous formic acid solutions. In addition, these factors increased the effect of each other. Under unfavorable conditions (high temperature and air) ethoxyquin completely decomposed in 1 - 3 months. Under optimal conditions (absence of air, low temperature) decomposition was slow, and after 6 months only up to 10 - 15% had decomposed (depending on the presence of iron, copper and light). With access to air, but at a low temperature (and not iron, copper and light), the decomposition was approx. 25% and 65% after 3 and 6 months respectively. With the absence of air, but at high temperature (and not iron, copper and light), the decomposition was approx. 25% after 6 months.

Både nærvær av lys og jern så ut til å ha mindre, men signifikant effekt. I tillegg økte disse faktorene effekten av hverandre. Effekten av kobber var ikke signifikant. Med lys, jern og kobber til stede, i fravær av luft og med lav temperatur, dekomponerte ca. 35 % av etoksyquin på 6 måneder. Nærvær av kobber reduserte effekten av temperatur, mens lys og luft også til en viss grad reduserte effekten av hverandre. Both the presence of light and iron appeared to have a smaller but significant effect. In addition, these factors increased the effect of each other. The effect of copper was not significant. With light, iron and copper present, in the absence of air and at a low temperature, approx. 35% of ethoxyquin in 6 months. The presence of copper reduced the effect of temperature, while light and air also reduced the effect of each other to some extent.

Eksempel 2 Example 2

Dette eksemplet ble utført for å undersøke den stabiliserende effekten av askorbinsyre og natriumdisulfitt på etoksyquin i Ensilox®. This example was carried out to investigate the stabilizing effect of ascorbic acid and sodium disulfite on ethoxyquin in Ensilox®.

Undersøkelsene med disse komponentene ble utført under ufordelaktige, men realistiske forhold, med nærvær av luft og lys og ved romtemperatur. Selv under disse forholdene dekomponerte bare 10 % og 25 % av etoksyquin, med tilsats av henholdsvis 1 vekt % askorbinsyre og 1 vekt % natriumdisulfitt. Fig. 3 viser stabilisering av etoksyquin i Ensilox® med askorbinsyre og natriumdisulfitt. Forklaring av forkortelsene anvendt i Fig. 2: Kontroll (4 °C og fravær av luft, lys, jern og kobber), T + Lu + Ly (romtemperatur og nærvær av luft og lys), 1,0 % AS (1,0 vekt % askorbinsyre), 0,1 % AS (0,1 vekt % askorbinsyre), 1,0 % Sul (1.0 vekt % natriumdisulfitt), 0,1 % Sul (0,1 vekt % natriumdisulfitt). Fig. 2 viser at askorbinsyre og natriumdisulfitt hadde en meget høy stabiliserende effekt på etoksyquin i vandige maursyreholdige løsninger. The investigations with these components were carried out under unfavorable but realistic conditions, with the presence of air and light and at room temperature. Even under these conditions, only 10% and 25% of ethoxyquin decomposed with the addition of 1 wt% ascorbic acid and 1 wt% sodium disulfite, respectively. Fig. 3 shows stabilization of ethoxyquin in Ensilox® with ascorbic acid and sodium disulfite. Explanation of the abbreviations used in Fig. 2: Control (4 °C and absence of air, light, iron and copper), T + Lu + Ly (room temperature and presence of air and light), 1.0% AS (1.0 wt% ascorbic acid), 0.1% AS (0.1 wt% ascorbic acid), 1.0% Sul (1.0 wt% sodium disulfite), 0.1% Sul (0.1 wt% sodium disulfite). Fig. 2 shows that ascorbic acid and sodium disulfite had a very high stabilizing effect on ethoxyquin in aqueous solutions containing formic acid.

Både askorbinsyre og natriumdisulfitt er oksygen "scavengers". Det ville være sannsynlig å anta at disse komponentene virker ved å fjerne oksygen eller reaktive oksygenkomponenter (for eksempel de svært ustabile peroksider). Med en slik mekanisme forbrukes askorbinsyre og sulfitt, og dette er i samsvar med resultatene, som viste at de laveste konsentrasjonene av både askorbinsyre og sulfitt ga beskyttelse i 3 måneder, mens dekomponeringen etter dette så ut til å være raskere. Both ascorbic acid and sodium disulphite are oxygen scavengers. It would be plausible to assume that these components act by removing oxygen or reactive oxygen components (for example, the highly unstable peroxides). By such a mechanism, ascorbic acid and sulfite are consumed, and this is consistent with the results, which showed that the lowest concentrations of both ascorbic acid and sulfite provided protection for 3 months, while decomposition after this appeared to be more rapid.

Eksempel 3 Example 3

Dette eksemplet ble utført for å undersøke effekten av en kombinasjon av askorbinsyre og natriumdisulfitt på dekomponeringen av etoksyquin i Ensilox®, og for å finne den mest optimale doseringen av disse tilsetningsstoffene. This example was carried out to investigate the effect of a combination of ascorbic acid and sodium disulfite on the decomposition of ethoxyquin in Ensilox®, and to find the most optimal dosage of these additives.

Forskjellige kombinasjoner av 0 - 0,5 vekt % askorbinsyre og 0 - 1,0 vekt % natriumdisulfitt i Ensilox® ble lagret under to forskjellige betingelser: Different combinations of 0 - 0.5 wt % ascorbic acid and 0 - 1.0 wt % sodium disulfite in Ensilox® were stored under two different conditions:

Ved romtemperatur og med nærvær av lys. At room temperature and in the presence of light.

I et kjøleskap uten lys. In a refrigerator without light.

Fig. 3 viser innholdet av etoksyquin i et representativt utvalg av lagrede prøver av Ensilox®, med tilsetning av askorbinsyre (AS) og/eller natriumdisulfitt (Sul). Prøvene ble lagret i 3 måneder, enten kjølig (4 °C) og mørkt, eller i romtemperatur og lys. Referansen var en prøve Ensilox® fremstilt i det analysene ble foretatt. Forklaring av forkortelsene anvendt i Fig. 3: Referanse (se ovenfor), Kontroll (uten tilsetninger av askorbinsyre eller natriumdisulfitt), Med Sul (0,3 vekt % natriumdisulfitt), Høy Sul (1,0 vekt % natriumdisulfitt), Med AS (0,3 vekt % askorbinsyre), Høy AS (0,5 vekt % askorbinsyre), Kombi (0,3 vekt % natriumdisulfitt og 0,3 vekt % askorbinsyre). Fig. 3 shows the content of ethoxyquin in a representative selection of stored samples of Ensilox®, with the addition of ascorbic acid (AS) and/or sodium disulphite (Sul). The samples were stored for 3 months, either cool (4 °C) and dark, or at room temperature and light. The reference was a sample of Ensilox® produced at the time the analyzes were carried out. Explanation of the abbreviations used in Fig. 3: Reference (see above), Control (without additions of ascorbic acid or sodium disulfite), Med Sul (0.3 wt% sodium disulfite), High Sul (1.0 wt% sodium disulfite), Med AS ( 0.3 wt% ascorbic acid), Høy AS (0.5 wt% ascorbic acid), Kombi (0.3 wt% sodium disulfite and 0.3 wt% ascorbic acid).

Forsøkene viste at en tilfredstillende stabilisering av etoksyquin i vandige maursyreholdige løsninger ble oppnådd ved tilsetning av 0,3 - 0,5 vekt % askorbinsyre. Ytterligere stabilisering ble oppnådd ved i tillegg til askorbinsyre å tilsette mer enn 0,4 vekt % natriumdisulfitt. Tilsetningen av natriumdisulfitt kunne kompensere for en reduksjon av mengden askorbinsyre. Den optimale kombinasjonen av askorbinsyre og natriumdisulfitt ble funnet å være 0,3 - 0,4 vekt % askorbinsyre og 0,4 - 0,7 vekt % natriumdisulfitt. Konsentrasjonen av maursyren skulle være 60 - 95 vekt %. The experiments showed that a satisfactory stabilization of ethoxyquin in aqueous solutions containing formic acid was achieved by the addition of 0.3 - 0.5% by weight ascorbic acid. Further stabilization was achieved by adding more than 0.4% by weight sodium disulfite in addition to ascorbic acid. The addition of sodium disulfite could compensate for a reduction in the amount of ascorbic acid. The optimum combination of ascorbic acid and sodium disulfite was found to be 0.3 - 0.4 wt % ascorbic acid and 0.4 - 0.7 wt % sodium disulfite. The concentration of the formic acid should be 60 - 95% by weight.

Ved romtemperatur og utsatt for luft ble etoksyquin fullstendig dekomponert på 1 - 3 måneder. Generelt så det ut til å være umulig å unngå at 10-20 % av etoksyquin dekomponerte på 3 måneder selv med de høyeste mengdene askorbinsyre og sulfitt. Dette kan imidlertid skyldes en systematisk eksperimentell feil. Sulfitt alene syntes ikke å gi nok beskyttelse under lagring over en lengre tidsperiode. Askorbinsyre så ut til å gi tilfredsstillende beskyttelse av etoksyquin i minst 3 måneder, selv ved romtemperatur og utsatt for luft. Kombinasjonen av askorbinsyre og sulfitt så ut til å gi en forbedret beskyttelse i forhold til askorbinsyre eller sulfitt alene. En kombinasjon er av stor interesse siden den rimeligere sulfitt da kunne erstatte deler av den mer kostbare askorbinsyren. At room temperature and exposed to air, ethoxyquin was completely decomposed in 1 - 3 months. In general, it seemed impossible to avoid 10-20% of ethoxyquin decomposing in 3 months even with the highest amounts of ascorbic acid and sulfite. However, this may be due to a systematic experimental error. Sulfite alone did not appear to provide enough protection during storage over a longer period of time. Ascorbic acid appeared to provide satisfactory protection from ethoxyquin for at least 3 months, even at room temperature and exposed to air. The combination of ascorbic acid and sulfite appeared to provide improved protection compared to ascorbic acid or sulfite alone. A combination is of great interest since the cheaper sulphite could then replace parts of the more expensive ascorbic acid.

Claims (10)

1. Fremgangsmåte for å stabilisere etoksyquin i vandig maursyreholdig løsning der etoksyquin tilsettes som etoksyquinformiat, karakterisert ved at 0,1-0,5 vekt % askorbinsyre og/eller 0,1-1 vekt % sulfitt tilsettes løsningen.1. Method for stabilizing ethoxyquin in an aqueous solution containing formic acid where ethoxyquin is added as ethoxyquin formate, characterized in that 0.1-0.5% by weight of ascorbic acid and/or 0.1-1% by weight of sulphite is added to the solution. 2. Fremgangsmåte ifølge krav 1, karakterisert ved at 0,3-0,4 vekt % askorbinsyre og/eller 0,4 - 0,7 vekt % sulfitt tilsettes løsningen.2. Method according to claim 1, characterized in that 0.3-0.4% by weight of ascorbic acid and/or 0.4-0.7% by weight of sulphite is added to the solution. 3. Fremgangsmåte ifølge krav 1, karakterisert ved at sulfitt tilsettes som natriumdisulfitt.3. Method according to claim 1, characterized in that sulphite is added as sodium disulphite. 4. Vandig maursyreholdig løsning omfattende etoksyquin i form av etoksyquinformiat som antioksidant, karakterisert ved at løsningen videre omfatter 0,1 - 0,5 vekt % askorbinsyre og/eller 0,1-1 vekt % sulfitt.4. Aqueous solution containing formic acid comprising ethoxyquin in the form of ethoxyquin formate as antioxidant, characterized in that the solution further comprises 0.1-0.5% by weight of ascorbic acid and/or 0.1-1% by weight of sulphite. 5. Løsning ifølge krav 4, karakterisert ved at løsningen omfatter 0,3 - 0,4 vekt % askorbinsyre og/eller 0,4 - 0,7 vekt % sulfitt.5. Solution according to claim 4, characterized in that the solution comprises 0.3 - 0.4% by weight of ascorbic acid and/or 0.4 - 0.7% by weight of sulfite. 6. Løsning ifølge krav 4, karakterisert ved at sulfitt er natriumdisulfitt.6. Solution according to claim 4, characterized in that sulfite is sodium disulfite. 7. Løsning ifølge krav 4, karakterisert ved at konsentrasjonen av maursyre er 60 - 95 vekt %.7. Solution according to claim 4, characterized in that the concentration of formic acid is 60 - 95% by weight. 8. Anvendelse av 0,1 - 0,5 vekt % askorbinsyre og/eller 0,1-1 vekt % sulfitt for å stabilisere etoksyquin i form av etoksyquinformiat i vandig maursyreholdig løsning.8. Use of 0.1 - 0.5% by weight of ascorbic acid and/or 0.1-1% by weight of sulphite to stabilize ethoxyquin in the form of ethoxyquin formate in aqueous formic acid-containing solution. 9. Anvendelse ifølge krav 8, hvor mengden askorbinsyre er 0,3 - 0,4 vekt % og/eller mengden sulfitt er 0,4 - 0,7 vekt %.9. Use according to claim 8, where the amount of ascorbic acid is 0.3 - 0.4% by weight and/or the amount of sulphite is 0.4 - 0.7% by weight. 10. Anvendelse ifølge krav 8, hvor sulfitt er natriumdisulfitt.10. Use according to claim 8, where sulfite is sodium disulfite.
NO20041959A 2004-05-12 2004-05-12 Process for Stabilizing Ethoxyquin in Aqueous Formic Acid Solution, Aqueous Formic Acid Solution comprising Ethoxyquin as Antioxidant, and Use for Stabilizing Ethoxyquin NO321226B1 (en)

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GB0624070A GB2429456B (en) 2004-05-12 2005-05-12 Method for stabilization of ethoxyquin in aqueous C1-C3 carboxylic acid containing solutions by adding ascorbic acid and sulphite
PCT/NO2005/000160 WO2005108371A1 (en) 2004-05-12 2005-05-12 Method for stabilization of ethoxyquin, and aqueous c1-c3 carboxylic acid - containing solutions comprising ethoxyquin as antioxidant

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