DK159307B - Ethoxyquin salts with alkanoic acids, solutions of the ethoxyquin salts, and the use thereof - Google Patents
Ethoxyquin salts with alkanoic acids, solutions of the ethoxyquin salts, and the use thereof Download PDFInfo
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- DK159307B DK159307B DK118085A DK118085A DK159307B DK 159307 B DK159307 B DK 159307B DK 118085 A DK118085 A DK 118085A DK 118085 A DK118085 A DK 118085A DK 159307 B DK159307 B DK 159307B
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Description
DK 159307 BDK 159307 B
Den foreliggende opfindelse angår hidtil ukendte salte af ethoxyquin.The present invention relates to novel salts of ethoxyquin.
Ethoxyquin (6-ethoxy-l,2-dihydro-2,2,4-trimethylquinolin) finder udstrakt anvendelse som antioxidant, især til bulkmaterialer såsom fiskemel eller græsmel for på den ene side at undgå oxidationsned-5 brydning såsom harskning og på den anden side at undgå eksplosioner. Ethoxyquin påføres normalt i koncentrationer i området 100-500 ppm.Ethoxyquin (6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline) is widely used as an antioxidant, especially for bulk materials such as fishmeal or grass meal, to avoid on one hand oxidation degradation such as rancidity and on the other side to avoid explosions. Ethoxyquin is usually applied at concentrations in the range of 100-500 ppm.
Der er imidlertid adskillige ulemper ved ethoxyquin. For det første er rent ethoxyquin en viskos olie ved normale temperaturer (ca. 2000 cps ved 20°C), og viskositeten forøges hurtigt med faldende tempera-10 tur (ca. 6000-7000 cps ved 10°C). Endvidere forøges viskositeten af tekniske kvaliteter af ethoxyquin, der kan indeholde lige fra 90% ethoxyquin og ned til 50-60% eller endnu mindre, væsentligt med stigende indhold af urenheder, og samtidig vil viskositeten af et givet ethoxyquinprodukt også forøges, når det ikke beskyttes af en 15 inert atmosfære såsom N2. Forøgelsen i viskositet skyldes en polymerisationsreaktion, der igen forårsages af tilstedeværelsen af oxygen og accelereres ved påvirkning af lys. Den høje viskositet gør det meget vanskeligt at fordele ethoxyquin jævnt i så lave mængder som de ovennævnte 100-500 ppm i bulkmaterialer såsom fiskemel. Der 20 vil være en tendens til forekomst af lokale, høje koncentrationer af ethoxyquin i bulkmaterialet, hvilket fører til dårlig oxidationsbeskyttelse i andre dele af materialet. For det andet er ethoxyquin kun opløseligt i vand i meget lave koncentrationer, hvilket gør det upraktisk at forsøge at fordele ethoxyquin i et bulkprodukt som en 25 vandig opløsning.However, there are several disadvantages to ethoxyquin. First, pure ethoxyquin is a viscous oil at normal temperatures (about 2000 cps at 20 ° C), and viscosity is rapidly increased with decreasing temperature (about 6000-7000 cps at 10 ° C). Furthermore, the viscosity of technical grades of ethoxyquin, which may range from 90% ethoxyquin to down to 50-60% or even less, is significantly increased with increasing content of impurities, and at the same time the viscosity of a given ethoxyquin product will also increase when not protected. of an inert atmosphere such as N 2. The increase in viscosity is due to a polymerization reaction, which in turn is caused by the presence of oxygen and accelerated by the influence of light. The high viscosity makes it very difficult to distribute ethoxyquin evenly in quantities as low as the above 100-500 ppm in bulk materials such as fishmeal. There will be a tendency for the presence of local, high concentrations of ethoxyquin in the bulk material, leading to poor oxidation protection in other parts of the material. Second, ethoxyquin is only soluble in water at very low concentrations, making it impractical to try to distribute ethoxyquin in a bulk product as an aqueous solution.
For at overvinde de ovennævnte problemer har det tidligere været forsøgt at anvende ethoxyquin absorberet i silicagel eller som en emulgatorstabiliseret suspension (stabiliseret med Tween®80 eller andre emulgatorer) med henblik på at opnå en form af ethoxyquin, der 30 lettere lader sig fordele.In order to overcome the aforementioned problems, it has been previously attempted to use ethoxyquin absorbed in silica gel or as an emulsifier stabilized suspension (stabilized with Tween®80 or other emulsifiers) to obtain a form of ethoxyquin that is more easily dispensable.
Selv sådanne former har imidlertid de ulemper, der er forbundet med ethoxyquins generelle opbevaringsegenskaber. Som nævnt ovenfor, vil både oxygen og påvirkningen af lys have tendens til at nedbryde ethoxyquin.However, even such forms have the disadvantages associated with the general storage properties of ethoxyquin. As mentioned above, both oxygen and the influence of light tend to degrade ethoxyquin.
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2 I et yderligere forsøg på at overvinde problemerne omkring ethoxyquin har der tidligere været fremstillet visse salte, nemlig hydrochlo-ridet, sulfatet, phosphatet og succinatet. Uheldigvis er sådanne salte, der i sig selv er krystallinske, ikke særlig opløselige i 5 vand, idet opløseligheden af fx hydrochloridet kun er ca. 5 vægtprocent.2 In a further attempt to overcome the problems surrounding ethoxyquin, certain salts have been previously prepared, namely the hydrochloride, the sulfate, the phosphate and the succinate. Unfortunately, such salts, which in themselves are crystalline, are not very soluble in water, the solubility of, for example, the hydrochloride being only approx. 5% by weight.
Ethoxyquin finder også anvendelse som beskyttelsesmiddel mod æbleskurv, idet æblerne dyppes i en emulgatorstabiliseret opløsning af ethoxyquin i vand, og idet koncentrationen af ethoxyquin er af stør-10 relsesordenen 2 ppm. Fremstillingen af en sådan neddypningsblanding er noget kompliceret og omfatter indblanding af en blanding af ethoxyquin og emulgator (fx Tween®80) i en opløsning af den samme emulgator i vand.Ethoxyquin also finds use as a protective agent against apple scab, the apples being dipped in an emulsifier-stabilized solution of ethoxyquin in water, and the concentration of ethoxyquin of the order of 2 ppm. The preparation of such a immersion mixture is somewhat complicated and involves admixing a mixture of ethoxyquin and emulsifier (e.g. Tween®80) in a solution of the same emulsifier in water.
Opfindelsen angår et salt af ethoxyquin med en alkansyre indeholdende 15 1-5 carbonatomer.The invention relates to a salt of ethoxyquin having an alkanoic acid containing 15 to 5 carbon atoms.
Som eksempler på alkansyrer med 1-5 carbonatomer kan nævnes myresyre, eddikesyre, propionsyre, smørsyre, isosmørsyre og valerianesyre.Examples of alkanoic acids having 1-5 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid and valeric acid.
Blandt disse syrer foretrækkes myresyre.Among these acids, formic acid is preferred.
Ved den foreliggende opfindelse undgås eller reduceres væsentligt de 20 ovenfor beskrevne ulemper ved de tidligere kendte ethoxyquinformer, både hvad angår viskositet, opløselighed i vand og/eller stigende viskositet på grund af oxidationsforårsaget polymerisation.In the present invention, the disadvantages of the above-described ethoxyquine formerly described above are substantially avoided or reduced, both in viscosity, water solubility and / or increasing viscosity due to oxidation-induced polymerization.
Således udmærker saltene ifølge opfindelsen sig ved opløselighed i eller blandbarhed med vand og/eller ved, at de i sig selv er væsker.Thus, the salts of the invention are characterized by solubility in or miscibility with water and / or in that they themselves are liquids.
25 Fx er ethoxyquinformiat opløseligt i vand og er i sig selv en væske, selv ved -18°C.For example, ethoxyquinformiat is soluble in water and is itself a liquid, even at -18 ° C.
Endvidere undergår de salte ifølge opfindelsen, der er væsker, ikke i nogen signifikant grad forøgelse i viskositet, når de udsættes for påvirkning af oxygen og lys. Det antages, at dette skyldes, at 30 dannelsen af ethoxyquin-ioner inhiberer de omlejrings- og radikal-reaktioner, der udgør en del af polymerisationsprocessen. Saltene 3Furthermore, the salts of the invention which are liquids do not undergo any significant increase in viscosity when exposed to the influence of oxygen and light. This is believed to be due to the formation of ethoxyquin ions inhibiting the rearrangement and radical reactions that form part of the polymerization process. The salts 3
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ifølge opfindelsen udviser længere holdbarhed end ethoxyquin, når de udsættes for oxygen og lys.according to the invention exhibit longer shelf life than ethoxyquin when exposed to oxygen and light.
Selv hvis viskositeten af saltene ifølge opfindelsen skulle være for høj til visse anvendelser, kan tilsætning af små mængder vand til 5 saltet, såsom mængder mellem 0,1 og 20 vægtprocent, i det væsentlige reducere viskositeten og derved muliggøre tilpasning til den pågældende anvendelse uden at forøge den til det specielle formål nødvendige mængde ethoxyquinsalt væsentligt.Even if the viscosity of the salts of the invention were to be too high for certain applications, adding small amounts of water to the salt, such as amounts between 0.1 and 20% by weight, can substantially reduce the viscosity and thereby enable adaptation to the particular application without significantly increase the amount of ethoxyquin salt needed for the particular purpose.
Saltene ifølge opfindelsen er også godt opløselige i/ blandbare med 10 lavere alkansyrer. Dette er overraskende, især i lyset af den lave opløselighed af andre ethoxyquinsalte i vandige medier, fx den ovenfor beskrevne lave opløselighed af ethoxyquinhydrochlorid i vand. Opfindelsen angår derfor også en opløsning af et ethoxyquinsalt af en alkansyre indeholdende 1-5 carbonatomer i en alkansyre indeholdende 15 1-5 carbonatomer eller i en blanding af sådanne alkansyrer, idet vægtforholdet mellem ethoxyquinbase og alkansyren eller blandingen deraf er fra 1:100 til 5:1, især fra 1:10 til 5:1.The salts of the invention are also well soluble in / miscible with 10 lower alkanoic acids. This is surprising, especially in view of the low solubility of other ethoxyquin salts in aqueous media, for example the low solubility of ethoxyquin hydrochloride in water described above. The invention therefore also relates to a solution of an ethoxyquin salt of an alkanoic acid containing 1-5 carbon atoms in an alkanoic acid containing 15-5 carbon atoms or in a mixture of such alkanoic acids, the weight ratio of ethoxyquin base to the alkanoic acid or mixture thereof being from 1: 100 to 5 : 1, especially from 1:10 to 5: 1.
Fordelen ved de ovenfor beskrevne opløsninger af ethoxyquinsalte i lavere alkansyrer er, at sådanne syrer, fx myresyre, propionsyre og 20 isosmørsyre, også anvendes som ensileringsmidler, og opløsningerne af ethoxyquinsaltene i de lavere alkansyrer tilvejebringer derved en let fordelbar kombination af ensileringsmiddel og antioxidant til fremstillingen af ensilage.The advantage of the above-described solutions of ethoxyquin salts in lower alkanoic acids is that such acids, for example formic acid, propionic acid and isobutyric acid, are also used as silicating agents, and the solutions of the ethoxyquin salts of the lower alkanoic acids thus provide an easily distributable combination of silicating agent and antioxidant for the preparation. of silage.
Salte af ethoxyquin med en alkansyre indeholdende 1-5 carbonatomer 25 kan fremstilles ved en fremgangsmåde, der omfatter blanding af ethoxyquin med alkansyren, idet ethoxyquinet eventuelt er opløst i et opløsningsmiddel såsom et aliphatisk carbonhydrid, et aromatisk car-bonhydrid eller et halogeneret carbonhydrid. Det foretrækkes, at den anvendte syre er myresyre.Salts of ethoxyquin with an alkanoic acid containing 1 to 5 carbon atoms can be prepared by a process comprising mixing ethoxyquin with the alkanoic acid, the ethoxyquin being optionally dissolved in a solvent such as an aliphatic hydrocarbon, an aromatic hydrocarbon or a halogenated hydrocarbon. It is preferred that the acid used is formic acid.
30 Som eksempler på aliphatiske carbonhydridopløsningsmidler kan nævnes pentan, hexan, heptan, octan eller nonan, eller blandinger deraf såsom blandinger, der er defineret ved hjælp af kogepunktsinterval-ler, nemlig petroleumsethere med kogepunktsintervaller såsom 40-60°C,Examples of aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane or nonane, or mixtures thereof such as mixtures defined by boiling intervals, namely petroleum ethers at boiling intervals such as 40-60 ° C.
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4 60-80eC, 80-100°C, 100-120°C eller lignende. Som eksempler på aromatiske carbonhydrider kan nævnes benzen eller aliphatisk substitueret benzen såsom toluen eller xylen, eller andre substituerede benzener såsom nitrobenzener. Halogenerede carbonhydrider kan omfatte 5 både halogenerede aliphatiske carbonhydrider såsom methylenchlorid, chloroform, carbontetrachlorid, trichlorethylen, eller perchlorethy-len, eller halogenerede aromatiske carbonhydrider såsom chlorbenzen, dichlorbenzen eller lignende.4 60-80 ° C, 80-100 ° C, 100-120 ° C or the like. Examples of aromatic hydrocarbons include benzene or aliphatic substituted benzene such as toluene or xylene, or other substituted benzenes such as nitrobenzenes. Halogenated hydrocarbons may include both halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, trichlorethylene, or perchlorethylene, or halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene or the like.
Blandingen af ethoxyquin og alkansyren, uanset om ethoxyquinet er 10 opløst i et opløsningsmiddel af den ovenfor beskrevne type eller ikke, kan udføres inden for et bredt temperaturinterval såsom mellem 0°C og 100°C, fx ved stuetemperatur.The mixture of ethoxyquin and alkanoic acid, whether or not the ethoxyquin is dissolved in a solvent of the type described above, can be carried out within a wide temperature range such as between 0 ° C and 100 ° C, for example at room temperature.
Den foreliggende opfindelse angår også anvendelsen af et salt af ethoxyquin med en alkansyre indeholdende 1-5 carbonatomer som 15 antioxidant eller som et antifrugtskurvmiddel. Opfindelsen angår endvidere de samme anvendelser af en opløsning af et salt i en alkansyre indeholdende 1-5 carbonatomer eller i en blanding af sådanne alkansyrer.The present invention also relates to the use of a salt of ethoxyquin with an alkanoic acid containing from 1 to 5 carbon atoms as an antioxidant or as an antifungal scouring agent. The invention further relates to the same uses of a solution of a salt in an alkanoic acid containing from 1 to 5 carbon atoms or in a mixture of such alkanoic acids.
Ved den ovenfor beskrevne anvendelse kan alkansyresaltet af ethoxy-20 quin eller opløsningen deraf i en alkansyre anvendes i vandige opløsninger i koncentrationer, der ligger fra 0,1 ppm til 10%, især fra 0,5 ppm til 1%, specielt 1-100 ppm såsom 1-10 ppm beregnet ud fra ethoxyquinsalt.In the application described above, the alkanoic acid salt of ethoxyquin or the solution thereof in an alkanoic acid can be used in aqueous solutions at concentrations ranging from 0.1 ppm to 10%, especially from 0.5 ppm to 1%, especially 1-100 ppm such as 1-10 ppm calculated from ethoxyquin salt.
Der er i litteraturen (Preben Møller Jensen, Gunnar Jørgensen (Dan-25 mark) Beret. Statens Husdyrbrugsfors. 1975, 427. s. 79) beskrevet eksperimenter, hvor sildeensilage til minkfoder blev behandlet med en blanding af myresyre og ethoxyquin. Der er i artiklen ingen antydning af nogen mulighed for, at denne behandling forårsager dannelse af ethoxyquinformiat i ensilagen, og det er desuden klart, at pro-30 blemerne omkring anvendelse af ethoxyquin selv, dvs. høj viskositet og lav opløselighed i vand, stadigvæk er relevante i denne forbindelse .Experiments have been described in the literature (Preben Møller Jensen, Gunnar Jørgensen (Dan-25 mark) Beret. Statens Livdyrbrugsfors. 1975, 427. p. 79) where herring silage for mink feed was treated with a mixture of formic acid and ethoxyquin. There is no indication in the article that this treatment causes the formation of ethoxyquinformiate in the silage, and it is further clear that the problems of using ethoxyquin itself, ie. high viscosity and low solubility in water are still relevant in this regard.
Opfindelsen illustreres yderligere ved følgende eksempler.The invention is further illustrated by the following examples.
55
DK 159307 BDK 159307 B
EKSEMPEL 1 EthoxyquinformiatEXAMPLE 1 Ethoxyquinformiat
Formiatet af ethoxyquin blev fremstillet ved at blande ækvimolære mængder af ethoxyquin (100 g, renhed ca. 99,9%) og myresyre (21,1 g, 5 renhed 99-100%) i en kolbe under omrøring ved stuetemperatur. Det resulterende salt var flydende og kunne ikke bringes til at krystallisere selv efter afkøling til -18°C. Saltet var opløseligt i vand ved en pH-værdi under 3, i myresyre, eddikesyre og propionsyre, samt i isopropanol, acetone og ethylacetat. Saltet var, i modsætning til 10 ethoxyquin selv, uopløseligt i petroleumsether, chloroform og carbontetrachlorid.The formate of ethoxyquin was prepared by mixing equimolar amounts of ethoxyquin (100 g, purity approximately 99.9%) and formic acid (21.1 g, purity 99-100%) in a flask with stirring at room temperature. The resulting salt was liquid and could not be crystallized even after cooling to -18 ° C. The salt was soluble in water at a pH below 3, in formic acid, acetic acid and propionic acid, as well as in isopropanol, acetone and ethyl acetate. The salt, unlike 10 ethoxyquin itself, was insoluble in petroleum ether, chloroform and carbon tetrachloride.
Det rene ethoxyquinformiat, ethoxyquinformiat med 3 vægtprocent vand tilsat og med 15% vand tilsat havde viskositeter på henholdsvis 600 cps, 330 cps og 80 cps målt ved 20eC på et Brookfield LVT-viskosime-15 ter. Ethoxyquinformiat med 15 vægtprocent vand tilsat havde endvidere en viskositet på 100 cps ved 5°C og 280 cps ved ca. 0°C.The pure ethoxyquinformiat, ethoxyquinformiat with 3 wt% water added and with 15% water added had viscosities of 600 cps, 330 cps and 80 cps, respectively, measured at 20 ° C on a Brookfield LVT viscometer. Furthermore, ethoxyquinformiat with 15% by weight of water added had a viscosity of 100 cps at 5 ° C and 280 cps at ca. 0 ° C.
EKSEMPEL 2EXAMPLE 2
Ethoxyquinacetat opløst i eddikesyre 100 g ethoxyquin og 153,4 g iseddikesyre blev blandet under omrøring 20 ved stuetemperatur. Herved blev der vundet en 50 vægtprocent opløsning af ethoxyquinacetat i iseddikesyre. Opløsningen havde en viskositet på 60 cps ved 20°C.Ethoxyquin acetate dissolved in acetic acid 100 g of ethoxyquine and 153.4 g of glacial acetic acid were mixed with stirring 20 at room temperature. A 50% by weight solution of ethoxyquin acetate in glacial acetic acid was thus obtained. The solution had a viscosity of 60 cps at 20 ° C.
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DK118085A DK159307C (en) | 1983-07-15 | 1985-03-14 | ETHOXYQUIN SALTS WITH ALKANIC ACIDS, SOLUTIONS OF THE ETHOXYQUIN SALT, AND USE THEREOF |
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Application Number | Priority Date | Filing Date | Title |
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DK3284/83A DK328483D0 (en) | 1983-07-15 | 1983-07-15 | ETHOXYQUINSALTE |
DK328483 | 1983-07-15 | ||
DK8400067 | 1984-07-12 | ||
PCT/DK1984/000067 WO1985000601A1 (en) | 1983-07-15 | 1984-07-12 | Ethoxyquin salts |
DK118085 | 1985-03-14 | ||
DK118085A DK159307C (en) | 1983-07-15 | 1985-03-14 | ETHOXYQUIN SALTS WITH ALKANIC ACIDS, SOLUTIONS OF THE ETHOXYQUIN SALT, AND USE THEREOF |
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DK118085D0 DK118085D0 (en) | 1985-03-14 |
DK118085A DK118085A (en) | 1985-03-14 |
DK159307B true DK159307B (en) | 1990-10-01 |
DK159307C DK159307C (en) | 1991-03-11 |
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DK118085A DK159307C (en) | 1983-07-15 | 1985-03-14 | ETHOXYQUIN SALTS WITH ALKANIC ACIDS, SOLUTIONS OF THE ETHOXYQUIN SALT, AND USE THEREOF |
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DK159307C (en) | 1991-03-11 |
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